Zeolites and Mesoporous Materials at the dawn of the 21st century, Proceedings of the 13 International Zeolite Conference, [1st ed.] 0444502386, 9780444502384, 9780080543918

Table of contents :
Content:
Preface
Pages v-vi
Anne Galarneau, Francesco Di Renzo, François Fajula, Jacques Védrine

Organizing Committee
Pages vii-x

IZA Council
Page x

Support and sponsoring
Page xi

List and schedule of sessions
Pages xii-xv

Ordered mesoporous materials — State of the art and prospects Original Research Article
Pages 1-12
F. Schüth

Clinoptilotite-heulandite: applications and basic research Original Research Article
Pages 13-27
Thomas Armbruster

Evolution of extra-large pore materials Original Research Article
Pages 29-36
Mark E. Davis

Evolution of refining and petrochemicals. What is the place of zeolites Original Research Article
Pages 37-60
Christian Marcilly

Is electron microscope an efficient magnifying glass for micro- and meso-porous materials? Original Research Article
Pages 61-71
Osamu Terasaki, Tetsu Ohsuna

Delaminated zeolites as active catalysts for processing large molecules Original Research Article
Pages 73-82
A. Corma, V. Fornés

Pentasil zeolites from Antarctica: from mineralogy to zeolite science and technology Original Research Article
Pages 83-91
A. Alberti, G. Cruciani, E. Galli, S. Merlino, R. Millini, S. Quartieri, G. Vezzalini, S. Zanardi

Use of 1H NMR imaging to study the diffusion and co-diffusion of gaseous hydrocarbons in HZSM-5 catalysts Original Research Article
Pages 93-102
P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L. Bonardet, J.-M. Dereppe, J. Fraissard

Zeolite-based nanocomposites: synthesis, characterization and catalytic applications Original Research Article
Pages 103-112
B.V. Romanovsky

Application of combinatorial tools to the discovery and commercialization of microporous solids: Facts and fiction Original Research Article
Pages 113-122
Jennifer Holmgren, David Bem, Maureen Bricker, Ralph Gillespie, Gregory Lewis, Duncan Akporiaye, Ivar Dahl, Arne Karlsson, Martin Plassen, Rune Wendelbo

The local structures of transition metal oxides incorporated in zeolites and their unique photocatalytic properties Original Research Article
Pages 123-132
Masakazu Anpo, Shinya Higashimoto

12-O-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI zeolite
Page 133
F. Thibault-Starzyk, A. Vimont, J.-P. Gilson

12-O-02 - Structure/reactivity correlation in Fe/ZSM5 for deNOx applications. In-situ XAFS characterization and catalysis
Page 133
A.A. Battiston, J.H. Bitter, D.C. Koningsberger

12-O-03 - Interaction of diazines with faujasites studied by IR spectroscopy, temperature-programmed desorption, and molecular modeling methods
Page 133
J. Döbler, E. Geidel, B. Hunger, K.H.L. Nulens, R.A. Schoonheydt

12-O-04 - DRIFT study of dinitrogen and dihydrogen adsorption on Li- and Na- forms of LSX zeolite
Page 134
V.B. Kazansky, A.I. Serykh, E. Tichomirova, V.Yu. Borovkov, M. Bulow

06-O-01 - The effect of stoichiometry and synthesis conditions on the properties of mesoporous M41S family silicates
Page 134
W.J. Roth, J.C. Vartuli

06-O-02 - What are circular crystals?
Page 134
F. Marlow

06-O-03 - Hierarchically mesostructured zeolitic materials with the MFI structure
Page 135
D. Trong On, P. Reinert, L. Bonneviot, S. Kaliaguine

06-O-04 - Pore size engineering of MCM-48: the use of different additives as expanders
Page 135
M. Mathieu, E. Van Bavel, P. Van Der Voort, E.F. Vansant

10-O-01 - Investigation of indium loaded zeolites and additionally promoted catalysts for selective catalytic reduction of NOx by methane
Page 135
F.-W. Schütze, H. Berndt, M. Richter, B. Lücke, C. Schmidt, T. Sowade, W. Grünert

10-O-02 - Ion exchange of alkali metals and control of acidic/basic properties of MCM-22 and MCM-36
Page 136
J.-O. Barth, R. Schenkel, J. Kornatowski, J.A. Lercher

10-O-03 - Insertion compounds of metal halides with porosils: “Structured Gases”
Page 136
P. Behrens, M. Hartl, G. Wirnsberger, A. Popitsch, B. Pillep

10-O-04 - Site selective adsorption and catalytic properties of iron in FER and BEA zeolites
Page 136
Z. Sobalík, J.E. àponer, Z. Tvarůžková, A. Vondrová, S. Kuriyavar, B. Wichterlová

17-O-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single cylindrical pore
Page 137
K. Morishige, Y. Ogisu

17-O-02 - Structural study of benzene, tetrachloroethene and trichloroethene sorbed phases in silicalite-1
Page 137
N. Floquet, J.P. Coulomb, G. Weber, O. Bertrand, J.P. Bellat

17-O-03 - Molecular ordering of the adsorbed phase within the microporous model aluminophosphate AlPO4-11 at cryogenic temperatures
Page 137
N. Dufau, N. Floquet, J.-P. Coulomb, P.L. Llewellyn, J. Rouquerol

17-O-04 - Adsorption properties of a supercritical fluid on mesoporous molecular sieves under high pressure
Page 138
Ya. Goto, N. Setoyama, Y. Fukushima, T. Okubo, Yu. Goto, Y. Imada, Y. Kubota, Y. Sugi

23-K-01 - Delaminated zeolites as active catalysts for processing large molecules
Page 138
A. Corma, V. Fornés

23-O-02 - Pd-zeolites as catalysts for the Heck reaction: a screening of reaction parameters affecting catalyst heterogeneity
Page 138
M. Dams, D.E. De Vos, L. Drijkoningen, P.A. Jacobs

23-O-03-Beckmann rearrangement of cyclohexanone oxime over meso-porous MCM-41-and MCM-48-type materials
Page 139
R. Gläser, H. Kath, J. Weitkamp

23-O-04 - Knoevenagel condensation between ethylcyanoacetate and benzaldehyde over base catalysts immobilized on mesoporous materials
Page 139
Youngyun Choi, Keun-Sik Kim, Jong-Ho Kim, Gon Seo

23-O-05 - One-step synthesis of MIBK from acetone over Pt/X catalysts
Page 139
L.V. Mattos, F.B. Noronha, J.L.F. Monteiro

02-O-01 - Small angle X-ray scattering on TPA-Silicalite-1 precursors in clear solutions: influence of silica source and cations
Page 140
C.J.Y. Houssin, B.L. Mojet, C.E.A. Kirschhock, V. Buschmann, P.A. Jacobs, J.A. Martens, R.A. van Santen

02-O-02 - Nucleation processes in zeolite synthesis revealed through the use of different temperature-time profiles
Page 140
C.S. Cundy, J.O. Forrest, R.J. Plaisted

02-O-03 - High yield synthesis of colloidal crystals of faujasite zeolites
Page 140
Qinghua Li, D. Creaser, J. Sterte

02-O-04 - Colloid chemical properties of silicalite-1 nanoslabs
Page 141
S. Kremer, C. Kirschhock, P. Rouxhet, P.A. Jacobs, J.A. Martens

02-O-05 - Atomic force microscopy (AFM) used to relate surface topography growth mechanisms in SSZ-42
Page 141
M.W. Anderson, N. Hanif, J.R. Agger, C.-Y. Chen, S.I. Zones

11-O-01 - Gold-based mono-and bimetallic nanoparticles on HY zeolites
Page 141
G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin, J. Fraissard

11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on zeolites and evidence for pore mouth plugging determined from model conversion over stepwise silanised samples
Page 142
H.P. Röger, H. Mantein, W. Böhringer, K.P. Möller, C.T. O'Connor

11-O-03 - Templating role of F− towards D4R units: study of the transformation of the fluorogallophosphate Mu-3 into, Mu-2
Page 142
A. Matijasic, P. Reinert, L. Josien, A. Simon, J. Patarin

11-O-04 - Modification of the Si/Ti ratio in ETS-10
Page 142
G. Koermer, A. Thangaraj, S. Kuznicki

11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by chemical vapour deposition
Page 143
P. Marturano, L. Drozdová, A. Kogelbauer, R. Prins

18-O-01 - An experimental adsorbent screening study for CO2 removal from flue gas
Page 143
P.J.E. Harlick, H. Halsall-Whitney, F. Handa Tezel

18-O-02 - Amino acids in BEA type channels
Page 143
C. Buttersack, A. Perlberg

18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2 hydrocarbons on modified LTA-type zeolites
Page 144
C.J. Guo, D. Shen, M. Bülow

18-O-04 - A novel adsorbent for the separation of propane/propene mixtures
Page 144
W. Zhu, F. Kapteijn, J.A. Moulijn

18-O-05 - Iodide removal using zeolite-based reactive adsorption
Page 144
S. Kulprathipanja, B. Spehlmann

24-O-01 - Dehydroisomerization of n-butane to isobutene over Pd modified silicoaluminophosphate molecular sieves
Page 145
Y. Wei, G. Wang, Z. Liu, C. Sun, L. Xu

24-O-02 - Conversion of methane over Ag-Y in the presence of ethene
Page 145
T. Baba, H. Sawada, Y. Abe, Y. Ono

24-O-03 - Peculiarities in the hydroconversion of n-hexadecane over bifunctional catalysts
Page 145
L. Perrotin, A. Finiels, F. Fajula, T. Cholley

24-O-04 - Hß catalyzed heterogeneous aziridination of olefins
Page 146
B. Chanda, R. Vyas, A.V. Bedekar, B.B. Kasture, V.N. Joshi

24-O-05 - MCM-41 as support for metallocene catalysts - ethylene polymerization
Page 146
C.A. Henriques, M.F.V. Marques, S. Valange, Z. Gabelica, J.L.F. Monteiro

01-K-01 - Pentasil zeolites from Antarctica: from mineralogy to zeolite science and technology
Page 146
A. Alberti, G. Cruciani, E. Galli, S. Merlino, R. Millini, S. Quartieri, G. Vezzalini, S. Zanardi

01-O-02 - Natural zeolites mineralization in the Oligocene-Miocene volcano-sedimentary succession of Central Sardinia (Italy)
Page 147
P. Cappelletti, G. Cerri, M. de Gennaro, A. Langella, S. Naitza, G. Padalino, M. Palomba, R. Rizzo

01-O-03 - Cation location and its influence on the stability of clinoptilolite
Page 147
M.N. Johnson, G. Sankar, C.R.A. Catlow, D. O'Connor, P. Barnes, D. Price

01-O-04 - The structure of Li-phillipsite
Page 147
A.F. Gualtieri

01-O-05 - Ion-exchange features of intermediate-silica sedimentary phillipsite
Page 148
C. Colella, E. Torracca, A. Colella, B. de Gennaro, D. Caputo, M. de Gennaro

15-O-01 - Proton jumps in dehydrated acidic zeolite catalysts. Rate predictions based on ab-initio calculations
Page 148
M. Sierka, J. Sauer

15-O-02 - Ab-initio simulation of dynamical processes in zeolites
Page 148
L. Benco, T. Demuth, J. Hafner, F. Hutschka, H. Toulhoat

15-O-03 - A theoretical study of the methylation of toluene by methanol over acid mordenite
Page 149
A. Vos, X. Rozanska, R. Schoonheydt, R. van Santen, F. Hutschka, J. Hafner

15-O-04 - Coverage effects on adsorption of water in faujasite: an ab-initio cluster and embedded cluster study
Page 149
J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong, T.N. Truong

15-O-05 - The beckmann rearrangement catalyzed by silicalite: a spectroscopic and computational study
Page 149
G.A. Fois, G. Ricchiardi, S. Bordiga, C. Busco, L. Dalloro, G. Spanò, A. Zecchina

07-O-01 - Ordered mesoporous carbon molecular, sieves by templated synthesis: the structural varieties
Page 150
R. Ryoo, S.H. Joo, S. Jun, T. Tsubakiyama, O. Terasaki

07-O-02 - One-pot synthesis of phenyl functionalized porous silicates with hexagonal and cubic symmetries
Page 150
V. Goletto, M. Impéror, F. Babonneau

07-O-03 - State and redox behavior of iron in MCM-41
Page 150
G. Pál-Borbély, Á. Szegedi, K. Lázár, H.K. Beyer

07-O-04 - A comparative study of Cu interaction with niobium-and aluminium-containing MCM-41 molecular sieves
Page 151
M. Ziolek, I Sobczak, I. Nowak, P. Decyk, J. Stoch

07-O-05 - A novel synthesis strategy leading to the formation of stable transition-metal-oxide mesostructures
Page 151
X.S. Zhao, J. Drennan, G.Q. Lu

25-O-01 - Shape-selective methylation of 4-methybiphenyl into 4,4'-dimethybiphenyl over modified ZSM-5 catalysts
Page 151
J.-P. Shen, L. Sun, C. Song

25-O-02 - Facile friedel-craft's alkylation of phenol with 4-hydroxybutan-2-one over β and Y zeolites to produce raspberry ketone
Page 152
K.K. Cheralathan, I.S. Kumar, B. Arabindoo, M. Palanichamy, V. Murugesan

25-O-03 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene catalyzed by MTW zeolite
Page 152
G. Pazzuconi, G. Terzoni, C. Perego, G. Bellussi

25-O-04 - Transalkylation reaction of phenol with trimethylbenzenes over Y and EMT zeolites
Page 152
V. Hulea, I. Fechete, P. Caullet, H. Kessler, T. Hulea, C. Chelaru, C. Guimon, E. Dumitriu

25-O-05-Benzene alkylation with alkanes over modified MFI catalysts
Page 153
A.V. Smirnov, E.V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko, I.I. Ivanova

19-K-01-Use of 1H NMR imaging to study the diffusion and co-diffusion of gaseous hydrocarbons in HZSM-5 catalysts
Page 153
P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L. Bonardet, J.-M. Dereppe, J. Fraissard

19-O-02-Studies of adsorption, diffusion and molecular simulation of cyclic hydrocarbons in MFI zeolites
Page 153
L. Song, Z.L. Sun, L.V.C. Rees

19-O-03-The effect of silanisation on the intracrystalline diffusivity of ZSM-5
Page 154
W.L. Duncan, K.P. Möller

19-O-04-Interference microscopy as a tool of choice for investigating the role of crystal morphology in diffusion studies
Page 154
O. Geier, S. Vasenkov, E. Lehmann, J. Kärger, R.A. Rakoczy, J. Weitkamp

19-O-05-Estimation of the interphase thickness and permeability in polymer-zeolite mixed matrix membranes
Page 154
A. Erdem-Şenatalar, M. Tather, Ş.B. Tantekin-Ersolmaz

16-O-01 Simulating shape selectivity in alkane hydroconversion by zeolites
Page 155
M. Schenk, T.L.M. Maesen, B. Smit

16-O-02-Molecular dynamics of the faujasite (111) surface
Page 155
B. Slater, C.R.A. Catlow

16-O-03-Adsorption of xylene isomers and water in faujasites. A molecular simulation study
Page 155
S. Buttefey, A. Boutin, A.H. Fuchs

16-O-04-Reaction dynamics in acidic zeolites: room temperature tunneling effects
Page 156
J.T. Fermann, S.M. Auerbach

16-O-05-Molecular modeling of multicomponent diffusion in zeolites and zeolite membranes
Page 156
M.J. Sanborn, A. Gupta, L.A. Clark, R.Q. Snurr

05-O-01-SOMS: Sandia octahedral molecular sieves. A new class of ion exchangers selective for the removal of Sr2+ from waste streams
Page 156
T.M. Nenoff, M. Nyman, A. Tripathi, J.B. Parise, W.T.A. Harrison, R.S. Maxwell

05-O-02-Hydrothermal synthesis of various titanium phosphates in the presence of organic amine templates
Page 157
Yunling Liu, Yunlong Fu, Jiesheng Chen, Yongcun Zou, Wenqin Pang

05-O-03-On the role of azamacrocycles and metal cations in the syntheses of metalloaluminophosphates STA-6, -7 and -8
Page 157
R. Garcia, E.F. Philp, A.M.Z. Slawin, P.A. Wright, P.A. Cox

05-O-04-Chiral transference and molecular recognition in novel Co(en)3Cl3-templated zinc phosphates
Page 157
Jihong Yu, Yu Wang, Zhan Shi, Ruren Xu

05-O-05-Very open microporous materials: from concept to reality
Page 158
A.K. Cheetham, H. Fjellvg, T.E. Gier, K.O. Kongshaug, K.P. Lillerud, G.D. Stucky

26-O-01-The isomerization selectivity in FCC process
Page 158
L.-J. Yan, M.-Y. He, J. Fu, J. Long

26-O-02-Design of zeolite catalyst for paraffin isomerisation
Page 158
J. Houžvička, C.J.H. Jacobsen, I. Schmidt

26-O-03-Cyclohexane ring opening on metal-zeolite catalysts
Page 159
T.V. Vasina, O.V. Masloboishchikova, E.G. Khelkovskaya-Sergeeva, L.M. Kustov, P. Zeuthen

26-O-04-Selective ring opening of naphthenic molecules
Page 159
M. Daage, G.B. Mc Vicker, M.S. Touvelle, C.W. Hudson, D.P. Klein, B.R. Cook, J.G. Chen, S. Hantzer, D.E.W. Vaughan, E.S. Ellis

26-O-05-Reforming of FCC heavy gasoline and LCO with novel borosilicate zeolite catalysts
Page 159
C.Y. Chen, S.I. Zones

21-K-01-Zeolite-based nanocomposites: synthesis, characterization and catalytic applications
Page 160
B.V. Romanovsky

21-O-02-Methods of synthesis for the encapsulation of dye molecules in molecular sieves
Page 160
M. Wark, M. Ganschow, Y. Rohlfing, G. Schulz-Ekloff, D. Wöhrle

21-O-03-MCM-41 silica monoliths and diluted magnetic semiconductors: a promising union for fabricating nanosized quantum wires
Page 160
F. Brieler, M. Brehm, L. Chen, P.J. Klar, W. Heimbrodt, M. Fröba

Citation preview

Studies in Surface Science and Catalysis 135

ZEOLITES AND MESOPOROUS MATERIALS AT THE DAWN OF THE 21 STCENTURY

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Studies in Surface Science and Catalysis Advisory Editors: B. Delmon and J.T. Yates Vol. 135

ZEOLITES AND M E S O P O R O U S M A T E R I A L S AT THE DAWN OF THE 21 sTC E N T U R Y Proceedings of the 13t" International Zeolite Conference, Montpellier, France, 8-13 July 2001

Edited by

A. Galarneau, F. Di Renzo and F. Fajula

Ecole Nationale Superieure de Chimie de Montpellier, 8 Rue de I'Ecole Normale, 34296 Montpellier Cedex 5, France

J. Vedrine

University of Liverpool, Leverhuime Centre for Innovative Catalysis, P.O. Box 147, Liverpool L69 3BX, U.K.

2001 ELSEVIER

Amsterdam - London - New York - Oxford - Paris - Shannon - Tokyo

ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands © 2001 Elsevier Science B.V. All rights reserved. This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. Special rates are available for educational institutions that wish to make photocopies for non-profit educational classroom use. Permissions may be sought directly from Elsevier Science Global Rights Department, PO Box 800, Oxford OX5 1DX, UK; phone: (+44) 1865 843830, fax: (+44) 1865 853333, e-mail: [email protected]. You may also contact Global Rights directly through Elsevier's home page (http://www.elsevier.nl), by selecting 'Obtaining Permissions'. In the USA, users may clear permissions and make payments through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA; phone: (+1) (978) 7508400, fax: (+1) (978) 7504744, and in the UK through the Copyright Licensing Agency Rapid Clearance Service (CLARCS), 90 Tot~enhamCourt Road, London WlP 0LP, UK; phone: (+44) 207 631 5555; fax: (+44) 207 631 5500. Other countries may have a local reprographic rights agency for payments. Derivative Works Tables of contents may be reproduced for intemal circulation, but permission of Elsevier Science is required for extemal resale or distribution of such material. Permission of the Publisher is required for all other derivative works, including compilations and translations. Electronic Storage or Usage Permission of the Publisher is required to store or use electronically any material contained in this work, including any chapter or part of a chapter. Except as outlined above, no part of this work may be reproduced, stored in a retdeval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the Publisher. Address permissions requests to: Elsevier Science Global Rights Department, at the mail, fax and e-mail addresses noted above. Notice No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made. First edition 2001 Library of Congress Cataloging in Publication Data A catalog record from the Library of Congress has been applied for. ISBN: 0-444-50238-6 ISSN: 0167-2991

ii i ~ The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper). Pnnted in The Nethedands.

Preface

The International Zeolite Conference is one of the pillars on which the identity of the zeolite community stands, at the same level of the definitions of zeolite structures provided by the Structure Commission of the International Zeolite Association, the dedicated journal which was Zeolites and is now Microporous and Mesoporous Materials, and the meetings of several national and regional zeolite associations. The 13th International Zeolite Conference has been held in Montpellier, France, from July 8 to 13, 2001, organized by the French Zeolite Group on behalf of the IZA. It has been preceded by a School on the Industrial Applications of Zeolites, held in Poitiers, and followed by a Field Trip in the natural zeolite localities of Massif Central. These proceedings are the expression of the oral and poster communications which have been presented during the Conference. They are subdivided into 32 thematic sessions going from the genesis of materials to their applications through their characterization. The paper volume contains the full texts of the 5 plenary and 6 keynote lectures and informative summaries of 150 oral and 540 poster presentations. It is intented to provide the participants a complete guide to the scientific programme. In order to gather all the communications in a handy document, the full texts of oral and poster presentations are available in a CD-ROM. These contributions have been selected among the 903 submissions received from a total of 57 countries! The evaluation was possible through the timely and efficient refereeing by the members of the International Advisory Board. The editors would like to namely acknowledge the dedication of the members of the Paper Selection Committee: Alberto Alberti, Giuseppe Bellussi, Colin Cundy, Jean-Pierre Gilson, Annick Goursot, Philip Llewellyn, Johann Martens, Jo~l Patarin, Cl6ment Sanchez, Alain Tuel and Herman van Bekkum. With the 13th IZC, zeolite science enters the new millennium with a vitality and an audience never reached before. Besides the fields of zeolite science always represented at IZCs (synthesis, characterization, catalysis .... ), some subjects strengthen their position (mesoporous materials, theory and modelling), new areas emerge (advanced materials, environmental and life sciences) and older ones regain interest (natural zeolites). The understanding and development of the unique properties of porous materials relies on a unique blend of multidisciplinary knowledge: material science, with the implication of organic and colloid chemistry, to prepare micro- and mesoporous materials, surface and adsorption science sustained by theory and modelling to understand the peculiar behavior of molecules in confined systems, special branches of catalysis, physics, chemical engineering and life science to design novel applications. The gathering of these elements is at the basis of a fruitful and evolutionary zeolite science, as it is hopefully reflected by these proceedings. Before concluding, the editors address a special and grateful acknowledgement to all the staff of the "Laboratoire de Mat6riaux Catalytiques et Catalyse en Chimie Organique" from Montpellier for their outstanding involvement all along the Conference organization.

vi

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The vitality of zeolite community is witnessed by the trend of the contributions to International Zeolite Conferences.

Montpellier, April 12, 2001

Anne Galarneau

Francois Fajula

Francesco Di Renzo

Jacques V6drine

vii ORGANIZING COMMITTEE General Chairman Ecole Nationale Sul~rieure de Chimie de Montpellier, France Francois Fajula Scientific Chairman Jacques Vedrine University of Liverpool, UK Secretary Francesco Di Renzo Ecole Nationale Sup6rieure de Chimie de Montpellier,~France Treasurer Pascale Massiani

Universit6 Pierre et Marie Curie, Paris, France

Pre-Conference School Michel Guisnet Universit6 de Poitiers, France Jean-Pierre Gilson Universit6 de Caen, France Field Trip Subcommittee Philippe Rocher Service Gtologique Rtgional Auvergne, Clermont-Ferrand, France Alain Tuel Institut de Recherche sur la Catalyse, Villeurbanne, France Finance Jean-Pierre Gilson

Universit~ de Caen, France

Publications Anne Galarneau

Ecole Nationale Suptrieure de Chimie de Montpellier, France

Liaison to the IZA Council

Giuseppe Bellussi

EniTecnologie, San Donato Milanese, Italy

INTERNATIONAL ADVISORY BOARD Belgium

Janos B.Nagy Peter Jacobs Johan Martens Bulgaria Christo Minchev Canada Serge Kaliaguine China Da-Dong Li Zhongmin Liu

Faeultts N. D. de la Paix, Namur Katholieke Universiteit Leuven, Hevedee Katholieke Universiteit Leuven, Hevedee Bulgarian Academy of Sciences, Sofia Universit6 Laval, Quebec, Sainte Foy SINOPEC R/PP, Beijing Dalian Institute of Chemical Physics, Dalian

viii Jilin University, Changchun Ruren Xu Croatia Ruder Boskovic Institute, Zagreb Boris Subotic Cuba Gerardo Rodriguez Universidad de la Habana, Facultad de Fisica, La Habana -Fuentes Czech Republic Blanka Wichterlova J. Heyrovsky Institute of Physical Chemistry, Praha France Institut Lavoisier, Versailles G~rard Ferey Universit6 Pierre et Marie Curie, Paris Jacques Fraissard Ecole Nationale Sup6rieure de Chimie de Montpellier Annick Goursot Philippe Llewellyn Universit6 de Provence, Marseille Institut Fran~ais du P6trole, Rueil-Malmaison Alain M6thivier Ecole Nationale Sup6rieure de Chimie de Mulhouse Joel Patarin Universit6 Pierre et Marie Curie, Paris Cl6ment Sanchez TFE, Groupement de Recherches de Laeq, Lacq Jacques Tellier Georgia George Tsitsiehvili Georgian Academy of Sciences, Tbilisi Germany Institut far Anorganische Chemie, Hannover Peter Behrens Ludwig-Maximilians Universitat, Munchen Thomas Bein Wolfgang Hoelderich RWTH-Aachen, Aachen Fritz-Haber Inst. Max Plank Gesellschaft, Berlin Hellmut Karge Leipzig Fakultat for Physik und Geowissenschaften, Leipzig Jorg Karger Technische Universitat MOnchen Johannes Lercher Max Planck Institut ft~ Kohlenforshung, Muelheim Ferdi Sch0th Johannes Gutemberg Universitat, Mainz Klaus Unger Universitat Stuttgart Jens Weitl~mp Hungary Hungarian Academy of Sciences, Budapest Herman Beyer Hungarian Academy of Sciences, Budapest Denes Kallo Jozsef Attila University, Szeged Imre Kiricsi India National Chemical Laboratory, Pune Paul Ratnasamy Italy Universit~ di Perugia Alberto Alberti Giuseppe Bellussi EniTecnologie SpA, San Donato Milanese Universith di Salerno, Fisciano Paolo Ciambelli Universith di Napoli Federico II, Napoli Carmine Colella Universith di Torino Bite Fubini Universith di Torino Adriano Zecchina Japan Osaka Prefecture University, Osaka Mazakazu Anpo Daido Hoxan, Inc., Sakai, Osaka Tomoyuki Inui Mazakazu Iwamoto Tokyo Institute of Technology, Yokohama

Yoshio Ono Tokyo Institute of Technology, Yokohama Takashi Tatsumi Yokohama National University, Yokohama Osamu Terasaki Tohoku University, Sendai Tatsuki Yashima Tokyo Institute of Technology, Yokohama Korea Hakze Chon Korea Advanced Institute of Science and Technology, Taejon Ryong Ryoo Korea Advanced Institute of Science and Technology, Taejon Norway SINTEF, Oslo Michael Stocker New Zealand Neil Milestone Industrial Research Ltd, Lower Hutt The Netherlands Koos Jansen Delft University of Technology, Delft Thomas Maschmeyer Waterman Institute, Delft Herman van Bekkum Delft Unniversity of Technology, Delft Rutger van Santen Eindhoven University of Technology, Eindhoven Poland Miroslaw Derewinski Polish Academy of Sciences, Cracow Mafia Ziolek A. Mickiewicz University, Poznan Romania Emil Radu Russu ICERP SA, Ploiesti Russia Irina Ivanova Moscow State University, Moscow Leonid Kustov Russian Academy of Sciences, Moscow South Africa University of Capetown, Rondebosch Ciryl O'Connor Spain Avelino Corma Universidad Politecnica de Valencia Joaquim PerezPariente Instituto de Catalisis y Petroleoquimica CSIC, Madrid Switzerland Thomas Armbruster Universitat Bern Lynne Mc Cusker ETH Zarich Attain Pfenninger CU Chemie Uetikon AG, Uetikon Taiwan National Tsing Hua University, Hsinchu Kuei-Jtmg Chao United Kingdom Michael Anderson UMIST Chemistry Department, Manchester Royal Institution of Great Britain, London Richard Catlow Eric Coker BP Amoco Chemicals, Sunbury on Thames UMIST Chemistry Department, Manchester Colin Cundy Eric Derouane University of Liverpool USA John Armor Air Products & Chemicals Inc., PA - Allentown Kenneth Balkus Jr. University of Texas at Dallas, TX- Richardson David Bish Los Alamos National Laboratory, NM - Los Alamos

Anthony Cheetham University of California, CA- Santa Barbara University of California, CA- Santa Barbara Brad Chmelka California Institute of Technology, CA - Pasadena Mark Davis Dow Chemical Company, MI - Midland Juan Garces Dow Chemical Company, MI - Midland Charles Kresge SUNY - College at Brockport, NY - Brockport Fred Mumpton Alexandra Navrotsky University of California at Davis, CA - Davis Arizona State University, AZ - Tempe Michael O'Keeffe Thomas Pinnavaia Michigan State University, MI - East Lansing University of California, CA- Santa Barbara Galen Stucky Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta Robert Thompson Worcester Polytechnic Institute, MA - Worcester NEC Research Institute, NJ- Princeton Michael Treaty Pennsylvania State University, PA- University Park David Vaughan UOP, Inc., IL - Des Plaines Stephen Wilson Chevron Research & Tech. Co., CA- Richmond Stacey Zones

IZA COUNCIL President Jens Weitkamp

Universitat Stuttgart, Germany

Vice-President Cyril T. O'Connor

University of Capetown, Rondebosch, South Africa

Secretary Koos Jansen

Delft University of Technology, Delft, The Netherlands

Treasurer Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta, USA Members Giuseppe Bellussi Hakze Chon Tomoyuku Inui Hellmut G. Karge Johannes Lercher Johan A. Martens Lynne Me Cusker Michael St0cker Michael Treaty Ruren Xu Tatsuaki Yashima

EniTecnologie, San Donato Milanese, Italy Korea Advanced Institute of Science and Technology, Taejon, Korea Daido Hoxan, Inc., Sakai, Osaka, Japan Fritz-Haber Inst. Max Plank Gesellschaft, Berlin, Germany Technische Universitat M0nchen, Germany Katholieke Universiteit Leuven, Heverlee, Belgium ETH Z0rich, Switzerland SINTEF, Oslo, Norway NEC Research Institute, NJ - Princeton, USA Jilin University, Changchun, China Tokyo Institute of Technology, Tokyo, Japan

Support and Sponsoring (As of April 17, 2001) The Organizing Committee wishes to thank various institutions and companies for their financial support to IZC 13. Their contribution allowed a reduced registration fee for students and a bursary programme.

Institutions Minist&e de la Recherche CNRS R6gion Languedoc-Roussillon District de Montpellier Conseil G6n~ral de l'H&ault Universit~ Montpellier II Ecole Nationale Sup6rieure de Chimie de Montpellier St Nikon Foundation

Partners ExxonMobil TotalFinaElf UOP Institut Franqais du P6trole

Sponsors and Friends Air Liquide DSM Research Dow Chemicals EniTecnologie Grace Davison Haldor Topsoe Procatalyse Rhodia

xii

,,

Sessions

,,

,

List and schedule of sessions Oral ,

,,

Poster

01- Mineralogy of natural zeolites ......................................

Tuesday am

Tuesday pm

02- Zeolite nucleation and growth .......................................

Monday pm

Monday pm

03- New methods of zeolite synthesis ................................

Thursday pm

Thursday pm

04- Isomorphous substitutions ............................................

Friday am

Thursday pm

05- Synthesis of new materials ............................................

Tuesday pm

Tuesday pm

06- Fundamentals of micelle templating ..............................

Monday am

Monday pm Tuesday pm

07- New mesoporous molecular sieves ................................

Tuesday am

08- Syntheses with non-ionic surfactants ............................

Friday pm

Wednesday pm

09- Crystal structure determination .....................................

Wednesday am

Wednesday pm

10- Host-guest chemistry ....................................................

Monday am

Monday pm

11- Post-synthesis modification .........................................

Monday pm

Monday pm

12- In-situ spectroscopy and catalysis ...............................

Monday am

Monday pm

13- Frameworks and acid sites .............................................

Friday pm

Thursday pm

14- Frameworks, cations, clusters .......................................

Friday am

Thursday pm

15- Modelling and theoretical studies A ..............................

Tuesday am

Tuesday pm

16- Modelling and theoretical studies B ..............................

Tuesday pm

Tuesday pm

17- Principles of adsorption ................................................

Monday am

Monday pm

18- Adsorption and separation processes ...........................

Monday pm

Monday pm

19- Diffusion: fundamental approach ..................................

Tuesday pm

Tuesday pm

20- Zeolite membranes and films .........................................

Wednesday am

Wednesday pm

21- Nanoeomposite fundamentals and applications ............

Wednesday am

Wednesday pm

22- Advanced materials ........................................................

Thursday pm

Thursday pm

chemistry .............................................................................

Monday pm

Monday pm

24- New routes to hydrocarbon activation ..........................

Tuesday am

Tuesday pm

25- Conversion of aromatics ................................................

Tuesday pm

Tuesday pm

26- Catalysis for oil refining ................................................

Wednesday am

Wednesday pm

23- Micro- and mesoporous materials in fine

27- Selective oxidation and sulfur resistance .......................

Thursday pm

Thursday pm

28- Confinement and physical chemistry for catalysis .......

Friday am

Wednesday pm

29- New approaches to catalyst preparation ......................

Friday pm

Wednesday pm

30- Environmental catalysis .................................................

Friday am

Wednesday pm

31- Environment-friendly applications of zeolites...: .......... Friday pm

Thursday pm

32- Zeolite minerals and health sciences ..............................

Thursday pm

Thursday pm

xiii

Frequently a s k e d questions:

When do I have to present my oral communication? Look in the authors index section the code S-O-x corresponding to your communication(s) where S is the session number, 0 meaning oral and x the position of the communication, then refer to the previous page. Oral communications start in the morning at l Oh (except on Monday (l 0h30)) and in the afternoon at 16h30 and last 30 min each including 10 min discussion. -

When do I have to present my poster communication? Look in the authors index section the code S-P-x corresponding to your communication(s) where S is the session number, P meaning poster, then refer to the previous page. Poster communications are from 14h to 16h each day except on friday. Posters of the day session should be hanged during the morning coffee break (lOh-lOh30). -

Further details on the programme are provided in the following pages.

CONFERENCE PROGRAMME - -

13:OO

Lunch

Lunch

Lunch

Lunch

Lunch

13:30 A

14:OO

Poster1

14:30

Sessions

Poster III

Poster I1

29-0- 08-0- 31-0- 13-0-

Poster N

01

Exhibition

Sessions

Exhibition

Sessions

Exhibition

Sessions

Exhibition

02 15:OO 1930 16:OO

02 12 06 17 10 18 11 23 Coffee Break/Exhibition

16:30 23-K- 02-001 01 17:OO 23-0- 02-002 02 17:30 23-0- 02-003 03 18:OO 23-0- 02-00 4 0 4 18:30 23-0- 02-005 05

01 16 05 19 07 24 15 25 Coffee BreakExhibition

11-0- 18-0 25-0- 19-K- 16-0- 05-001

01

01

01

01

01

08 09 20 21

03 22 04 27 13 31 14 32 Coffee BreakExhibition

26 28 29 30

02

02

02

02

02-

11-0- 18-0 25-0- 19-0 16-0- 05-003

03

03

03

03

evening outing at

01 02

02

02

02

03

05 05 05. 2 1:00 CONCERT

03

03

0 4 0 4 0 4 0 4

27-0- 03-0- 22-0- 32-0,

05 05 05 05 20:OO CONFERENCE

DINER

NB: Keynotes (S-K-01) (grey) will begin 10 min before the start of oral sessions

03

01

02

02

02

29-0- 084- 31-0- 13-003

03

03

03

29-0- 08-0 31-0- 1343 0 4 0 4 0 4 0 4

Conciudiig Remarks

01

27-0- 03-0- 22-0- 32-0-

0 4 0 4 0 4 0 4 0 4 0 4 05

01

"MANADE Saint Gabriel" 27-0- 03-0- 22-0- 32-0-

03

ll-0- 18-0- 25-0- 19-0- 16-0 05-005

01

27-0- 03-0- 22-0- 32-0-

ll-0- 18-0- 25-0- 19-0 16-0 05-005

01

27-0- 03-K- 22-0- 32-0

16.30 Departure forthe

ll-0- 18-0- 25-0- 19-0- 16-0- 05-002

01

29-0- 084- 31-0- 13-0-

17:OO Departure to FIELD TRIP

This Page Intentionally Left Blank

xvii

SCIENTIFIC PROGRAMME AND CONTENT OF PROCEEDINGS

Plenaries PL-1- Monday 9h - Ordered mesoporous materials - State of art and prospects F. Schiith PL-2- Tuesday 8h30 - Clinoptilolite-heulandite: applications and basic research T. Armbruster

13

PL-3- Wednesday 8h30 - Evolution of extra-large pore materials M.E. Davis

29

PL-4- Thursday 8h30 - Evolution of refining and petrochemicals. What is the place of zeolites? C. Marcilly

37

PL-5- Friday 8h30 - Is electron microscope an efficient magnifying glass for microand meso- porous materials? O. Terasaki and T. Oshuna

61

Note: The conference has been divided into 32 sessions. Each communication has a code S-M-x with S being the number of the Session, M = K (keynote), O (oral), P (poster) and x the number of the communication.

Keynotes 23-K-01- Monday 16h20- Delaminated zeolites as active catalysts for processing large molecules A. Corma and V. Forn~s

73

01-K-01- Tuesday 9h50 - Pentasil zeolites from Antartica: from mineralogy to zeolite science and technology A. Alberti, G. Cruciani, E. Galli, S. Merlino, 1~ Millmi, S. Quartieri, G. Vezzalini and S. Zanardi

83

19-K-01- Tuesday 16h20 - Use of 1H NMR imaging to study the diffusion and codiffusion of gaseous hydrocarbons in HZSM-5 catalysts P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L. Bonardet, J.-M. Dereppe and J. Fraissard

93

21-K-01- Wednesday 9h50 - Zeolite-based characterization and catalytic applications B. K Romanovsky

nanocomposites:

synthesis,

03-K-0 I- Thursday 16h20 - Application of combinatorial tools to the discovery and commercialization of microporous solids: facts and fiction J. Holmgren, D. Bem, M. Bricker, 1L Gillepsie, G. Lewis, D. Akporiaye, I. Dahl, A. Karlsson, A#..Plassen and R. Wendelbo

103

113

xviii

30-K-01- Friday 9h50 - The local structures o f transition metal oxides incorporated in zeolites and their unique photocatalytic properties

M. Anpo and S. Higashimoto

123

Note: In the b o o k are only the summaries o f the communications. The text o f the full papers o f oral and poster c o m m u n i c a t i o n s are in the C D - R O M . , Programme

o f o r a l s e s s i o n s (a~. lOh30-12h30 and pm 16h30-19h)

S u m m a r y pages

Monday am 12061017-

In-situ spectroscopy and catalysis .......................................................... F u n d a m e n t a l s o f micelle templating ........................................................ H o s t - g u e s t chemistry ............................................................................... PrinciPles o f a d s o r p t i 0 n ................. ... ....... .. ........................ .... . ..... ..,,.,: .....

133 134 135 137

Monday p m 23- Micro- and m e s o p o r o u s materials in fine chemistry ............................... 02- Zeolite nucleation and growth ................................................................. 11- Post-synthesis modification .................................................................... 18- Adsorptio n and separation processes .................................... ..:... .... ... .... ..

138 140 141 143

Tuesday am 24- N e w routes to hydrocarbon activation .................................................... 01- M i n e r a l o g y o f natural zeolites ................................................................ 15- M o d e l l i n g and theoretical studies A ........................................................ 07- N e w m e s o p o r 0 u s molecular sieves ..........................................................

145 146 148 150

Tuesday pm 25- Conversion o f aromatics .......................................................................... 19- Diffusion: fundamental approach ............................................................. 16- M o d e l l i n g and theoretical studies B ......................................................... 05- Synthesis .of n e w materials ............. ..:...:... ....... ......................................

151 153 155 156

Wednesday am 26212009-

Catalysis for oil refining .......................................................................... N a n o c o m p o s i t e fundamentals and applications ...................................... Zeolite m e m b r a n e s and films ................................................................... Crystal structure determination ...............................................................

158 160

161 163

Thursday pm 27032232-

Selective oxidation and sulfur resistance .................................................. N e w m e t h o d s o f zeolite synthesis ........................................................... A d v a n c e d materials .................................................................................. Zeolite minerals and health sciences ........................................................

165 166 168 170

Friday am 30280414-

E n v i r o n m e n t a l catalysis ........................................................................... C o n f i n e m e n t and physical chemistry for catalysis ................................. I s o m o r p h o u s substitutions ...................................................................... F r a m e w o r k s , cations , clusters ....... ::. ...... :..::...,.,,:. .................. :. ........ :.:;::..

171 173 175 176

Friday pm 29083113-

N e w a p p r o a c h e s to catalyst preparation ................................................ Syntheses with non-ionic surfactants ...................................................... Environment-friendly applications o f zeolites ........................................ F r a m e w o r k s and acid sites .......................................................................

178 179 181 182

xix

Posters should be hanged during the morning coffee break (1 Oh- 10h30).

Programme o f poster sessions (14h00-16h30)

,

Summary pages

Monday 0206101112171823-

Zeolite nucleation and growth ................................................................. Fundamentals o f micelle templating ........................................................ Host-guest chemistry ............................................................................... Post-synthesis modification .................................................................... In-situ spectroscopy and catalysis .......................................................... Principles o f adsorption ........................................................................... Adsorption and separation processes ...................................................... Micro- and mesoporous materials in fine chemistry ...............................

185 198 206 208 217 222 226 230

Tuesday 01- Mineralogy o f natural zeolites ................................................................ 05- Synthesis o f new materials ...................................................................... 07- N e w mesoporous molecular sieves .......................................................... 15- Modelling and theoretical studies A ........................................................ 16- Modelling and theoretical studies B ......................................................... 19- Diffusion: fundamental approach ............................................................ 24- N e w routes to hydrocarbon activation .................................................... 25- Conversion o f aromatics ..........................................................................

240 244 249 256 264 269 271 280

Wednesday 0809202126282930-

Syntheses with non-ionic surfactants ...................................................... Crystal structure determination ............................................................... Zeolite membranes and films ................................................................... Nanocomposite fundamentals and applications ...................................... Catalysis for oil refining .......................................................................... Confinement and physical chemistry for catalysis ................................. New approaches to catalyst preparation ................................................ Environmental catalysis ...........................................................................

284 288 291 296 301 307 311 320

Thursday 0304131422273132-

N e w methods o f zeolite synthesis ........................................................... Isomorphous substitutions ...................................................................... Frameworks and acid sites ....................................................................... Frameworks, cations, clusters .................................................................. Advanced materials .................................................................................. Selective oxidation and sulfur resistance .................................................. Environment-friendly applications o f zeolites ........................................ Zeolite minerals and health sciences ........................................................

330 335 340 347 359 365 369 373

AUTHOR INDEX

377

SUBJECT I N D E X

399

This Page Intentionally Left Blank

xxi

F u l l p a p e r s (Texts included in the CD-ROM) O1 - M i n e r a l o g y

of Natural

Zeolite

0 1 - O - 0 2 - Natural zeolites mineralization in the Oligocene-Miocene volcanosedimentary succession of Central Sardinia (Italy) P. CappellettL G. Cerri, M. de Gennaro, A. Langella, S. Naitza, G. Padalino, M. Palomba and R. Rizzo

147

01-O-03 - C a t i o n location and its influence on the stability of clinoptilolite M.N. Johnson, G. Sankar, C.R.A. Catlow,. D. O'Connor, P. Barnes and D.Price

147

0 1 - O - 0 4 - The structure of Li-phillipsite A.F. Gualtieri

147

01-O-05 - Ion-exchange features of intermediate-silica sedimentary phillipsite C. Colella, E. Torracca, A. Colella, B. de Gennaro and D. Caputo and M. de Gennaro

148

0 l - P - 0 6 - Zeolites in impact craters M. V. Naumov

240

0 l - P - 0 7 - AI ordering in a dachiardite framework M. Kato and K. Itabashi

240

0 l-P-08 - Chemical composition and ion-exchange properties of a natrolite from Zahedan Region, Iran A.R. Sardashti, H. Kazemian and M. Akramzadeh Ardakani

240

0 l-P-09 - Physical, chemical and structural characterization of the volcanic tuff from the Maramures area, Romania R. Pode, G. Burtica, S. Herman, A. Iovi and 1. Calb

241

0 l-P-10 - Heulandite group zeolites from the Paleogene fresh water lake Blateshnitza Graben, Southwest Bulgaria Z. Milakovska, E. Djourova and R. Tzankarska

241

0 l-P-11 - Isodimorphism of templates in zeolites. New crystal chemistry of analcime and its analogues V. V. Bakakin

241

0 l-P-12 - Evaluation of clinoptilolite tuffs from Russia as ion exchangers using NH4 ions 1. V. Komarova, N.K. Galkina, V.A. Nikashina, B.G. Anfilov and K.I. Sheptovetzkaya

242

xxii 0 l-P-13 - Mineralogy, chemistry and ion-exchange properties of the zeolitized tufts from the Sheinovets caldera, E Rhodopes (South Bulgaria)

R. Ivanova, Y. Yanev, Tz. lliev, E. Koleva, T. Popova and N. Popov

242

0 l-P- 14 - Synthesis of titanium, niobium, and tantalum silicalite- 1 by microwave heating of the mixed oxide xerogel precursors

W.S. Ahn, K.Y. Kim, M.H. Kim and Y.S. Uh

242

0 l-P-15 - Different silver states stabilized in natural clinoptilolites

N. Bogdanchikova, B. Concepcion Rosabal, V. Petranovskii, M. Avalos-Borja and G. Rodriguez-Fuentes

243

0 l-P-16 - Physical-chemical and adsorptive properties of Armenia natural zeolites

F. Grigoryan, A. Hambartsumyan, tl. Haroyan and A. Karapetyan

243

0 l-P-17 - The sorption equilibria in natural zeolite-aqueous solutions systems

J. Perik, M. Trgo and S. Cerjan-Stefanovik

243

02 - Z e o l i t e N u c l e a t i o n a n d G r o w t h

02-0-01 - Small angle X-ray scattering on TPA-Silicalite-1 precursors in clear solutions: influence of silica source and cations

C.J.Y. Houssin, B.L. Mojet, C.E.A. Kirschhock, V. Buschmann, P.A. Jacobs, J.A. Martens and R.A. van Santen

140

02-0-02 - Nucleation processes in zeolite synthesis revealed through the use of different temperature-time profiles

C.S. Cundy, J.O. Forrest and R.J. Plaisted

140

02-0-03 - High yield synthesis of colloidal crystals of faujasite zeolites

Qinghua Li, D. Creaser and J. Sterte

140

02-0-04 - Colloid chemical properties of silicalite-1 nanoslabs

S. Kremer, C. Kirschhock, P. Rouxhet, PA. Jacobs and J.A. Martens

141

02-0-05 - Atomic force microscopy (AFM) used to relate surface topography growth mechanisms in SSZ-42

M. W. Anderson, N. Hanif J.R. Agger, C.-Y. Chen and S.I. Zones

141

02-P-06 - Epitaxial overgrowth of MAZ onto EMT type zeolite crystals

A.M. Goossens, V. Buschmann and J.A. Martens

185

02-P-07 - The transformation of zeolite A and X into nitrate cancrinite under low temperature hydrothermal reaction conditions

J. C. Buhl and C. Taake

185

xxiii 02-P-08 - Comparison of crystal linear growth rates for silicalite-1 in thermal and microwave syntheses C.S. Cundy and J. O. Forrest

185

02-P-09 - Effect of initial hydrogel milling on Na-ZSM-5 synthesis C. Falamaki, M. Edrissi and M. Sohrabi

186

0 2 - P - 1 0 - Synthesis and characterization of zeolite Z S M - 2 5 S.B. Hong, W.C. Paik, W.M. Lee, S.P. Kwon, C.-H. Shin, I.-S. Nam and B.-H. Ha

186

02-P-11 - A study on the crystallization of a lamellar aluminophosphate APO-M to a three-dimensional aluminophosphate APO-CJ3 K. Wang, J. Yu, Y. Song, Y. Zou and R. Xu

186

0 2 - P - 1 2 - S y n t h e s i s o f nanosized offretite crystals J. Hedlund and E. Kurpan

187

02-P-13 - Silicon oxide plays a driving role in the synthesis of microporous SAPO- 11 Z-Q. Liu and R. Xu

187

0 2 - P - 1 4 - S y n t h e s i s o f nanocrystal zeolite Y and its host effect H. Yang, R. L i, B. Fan and K. Xie

187

02-P-15 - Tailoring crystal size and morphology of zeolite ZSM-5 Ming Liu and S. Xiang

188

02-P-16 - Modeling of silicalite crystallization from clear solution K.A. Car&son, J. Warzywoda and A. Sacco, Jr.

188

02-P- 17 - Interaction/synergistic effect of Mg 2+ and Ba 2+ on the size and morphology of the zeolite L crystals S. Ferchiche, J. Warzywoda and A. Sacco, Jr.

188

0 2 - P - 1 8 - In-situ NMR study of mechanisms of zeolite A formation M. SmaihL S. Kallus and J.D.F. Ramsay

189

- E f f e c t s o f synthesis parameters on zeolite L crystallization Y.S. Ko, S.H. Chang and W.S. Ahn

189

0 2 - P - 2 0 - Some aspects of NU-86 zeolite crystallization S. V. Dudarev, A. V. Toktarev, G. V. Echevsky, C.L. Kibby and D.J. O'Rear

189

0 2 - P - 2 1 - S y n t h e s i s o f zeolite Sr, K-ZK-5 P.C. Russell S.L. Stuhler. A.L. Kouli, J. Warzywoda and A. Sacco, Jr.

190

02-P-19

xxiv 02-P-22 - Evidence for in-situ directing agent modification in zeolite syntheses J.C. Vartuli, G.J. Kennedy, B.A. Yoon and A. Malek

190

02-P-23 - The influence of different silica sources on the crystallization kinetics of zeolite Beta

W. Schmidt, A. E Toktarev, E Schath, K.G. lone and K. Unger

190

02-P-24 - Population balance: a powerful tool for the study of critical processes of zeolite crystallization

B. Subotic, T. Antonid and J. Bronik

191

02-P-25 - Synthesis of TMA-SOD from a novel type layered silicate by solid state transformation

Y. KiyozumL F. MizukamL Y. Akiyama, T. lkeda and T. Nishide

191

02-P-26 - Direct conversion of bulk-materials into MFI zeolites by a bulkmaterial dissolution technique

S. Shimizu and H. Hamada

191

02-P-27 - Synthesis of a new microporous silicate using DABCO-based structuredirecting agent

Y. Kubota, J. Pldvert, T. Honda, P. Wagner, M.E. Davis, T. Okubo, Ya. Goto, Y. Fukushima and Y. Sugi

192

02-P-28 - Heteroepitaxial connection of zeolites with different pore structures

T. Wakihara, J. Pldvert, S. Nair, M. Tsapatsis, S. Yamakita, Y. Ogawa, H. Komiyama, M. Yoshimura, M.E. Davis and T. Okubo

192

02-P-29 - Study of zeolite A crystallization from clear solution by hydrothermal synthesis and population balance simulation

J. Bronic, P. Frontera, E Testa, B. Subotic, R. Aiello and J. B.Nagy

192

02-P-30 - Synthesis of zeolite SSZ-35 using N-methyl hexahydrojulolidinium salt as a new family of structure-directing agents (SDAs)

Y Kurata, T.-A. Hanaoka and H Hamada

193

02-P-31 - The Fitting equation for zeolite crystallization with seeds

V. Toktarev and S. V. Dudarev

193

02-P-32 - Influence of the thermal treatment of the aluminosilicate gel precursor on the zeolite nucleation

C. Kosanovi~, B. SubotiO and D. Kralj"

193

02-P-33 - Efficient co-templating roles of amines and amides admixed with alkylammonium salts for the stabilisation of new A1PO4-n topologies

C. Borges, M.F. Ribeiro, C. Henriques, M.T. Duarte, J.P. Lourenqo and Z. Gabelica

194

XXV

02-P-34 - Static synthesis of zeolite M C M - 2 2 Y.-M. Wang, X.- T. Shu and M.- Y. He

194

02-P-35 - Synthesis of pure silica Beta by the conventional hydrothermal method W Guo, J. Yao, Y. Luo and Qi. Li

194

02-P-36 - Hydrothermal transformation of a layered silicate, Na-magadiite, into mordenite zeolite T. Selvam and W Schwieger

195

02-P-37 - In-situ diagnostic of zeolite crystal growth by real time ultrasound monitoring R. Herrmann, W Grill T.J. Kim, O. Scharf R. Schertlen, M. Schmachtl, W Schwieger, C. Stenzel, H. Toufar and Y. Venot

195

02-P-38 - Effect of ageing on the decomposition of tetra-alkylammonium ions as studied by microwave heating A. Arafat, H. van Bekkum, Th. Maschmeyer and J. C. Jansen

195

02-P-39 - Synthesis of siliceous mordenite from system free of amine X. Qi, X. Liu and Z Wang

196

02-P-40 - High-resolution solid state MAS NMR studies on the role of promoter (phosphate) in the nucleation and crystallization of Silicalite -1 (Si-MFI) P.R. Rajamohanan, P. Mukherjee, S. Ganapathy and R. Kumar

196

02-P-41 - The influence of concentration on the structure-directing effects of diethylenetriamine in the synthesis of porosils P. Behrens, V.J. Hufnagel and A.M. Schneider

196

0 2 - P - 4 2 - Synthesis of high-silica MWW zeolite L.M. Vtjurina, S.S. Khvoshchev and I. V. Karetina

197

03- New

Methods

of Zeolite

Synthesis

03-0-02- Mesoporous zeolites CJ.H. Jacobsen, J. Hou~,vicka, A. Carlsson and I. Schmidt

167

03-0-03 - Synthesis of novel zeolites SSZ-53 and SSZ-55 using organic templating agents derived from nitriles S.A. Elomari and S.I. Zones

167

03-0-04 - Synthesis of IFR-type zeolites optimized for spectroscopic study B.S. Duersch and L. W. Beck

167

xxvi 03-0-05 - Competitive role of sodium and potassium cations during hydrothermal zeolite crystallization from Na20-K20-A1203-SiO2-H20 gels A.F. Ojo, F.R. Fitch, M. Balow and M.-L. Lau

168

03-P-06 - Zeolitization of a spanish bentonite in seawater medium. Effect of alkaline concentration and time R. Ruiz, C. Blanco, C. Pesquera and E Gonz61ez

330

03-P-07 - Silicalite-1 spheres prepared from preformed resin-silicate composites L. Tosheva and J. Sterte

330.

03-P-08 - The synthesis of offretite single crystals using pyrocatechol as complex agent E Gao, G. Zhu, Xiaotian Li, S. Qiu, B. Wei, C. Shao and O. Terasaki

330

03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran G.-Q Guo, Y-J. Sun and Y.-C. Long

331

03-P- 10 - Utilization of dry-gel conversion method for the synthesis of gallosilicate zeolites Beta, ZSM-5 and ZSM- 12 R. Bandyopadhyay, Y. Kubota, S. i Nakata and Y. Sugi

331

03-P-11 - A novel method for the synthesis of cancrinite type zeolites C.F. Linares, S. Madriz, M.R. Goldwasser and C. Urbina de Navarro

331

03-P-12 - High-throughput strategies for the hydrothermal synthesis of zeolites and related materials N. Stock, N. Hilbrandt, K. Choi and T. Bein

332

03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr.

332

03-P-14 - Influence of nano-particle agglomeration on the catalytic properties of MFI zeolite S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata

332

03-P-15 - Rapid and mass production of porous materials using a continuous microwave equipment D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park

333

03-P- 16 - Hydrothermal synthesis of vanadium-containing microporous aluminophosphates via the design of experiments approach L. Frunza, P. Van Der Voort, E.F. Vansant, R.A. Schoonheyd and B.M. Weckhuysen

333

xxvii 03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for use in a membrane reactor

E.E. McLeary, A. W. Hoogesteger, R.D. Sanderson and J.C. Jansen

333

03-P-18 - Mixed alkali templating in the Si/A1 = 3 and 10 systems: a combinatorial study

G.J Lewis, D.E. Akporiaye, D.S. Bem, C. Bratu,.I.M. Dahl, A. Karlsson, R.C. Murray, R.L. Patton, M. Plassen and R. Wendelbo

334

03-P-19 -Factors affecting composition and morphology of mordenite

F. Hamidi, M. Pamba, A. Bengueddach, F. Di Renzo and F. Fajula

334

04- Isomorphous Substitutions 04-0-01 - Direct synthesis of Cu(I)-MFI zeolite in the presence of Cu(II) methylamino complexes as mineralizing and reducing agents

S. Valange, F. Di Renzo, E. Garrone, F. Geobaldo, B. Onida and Z. Gabelica

175

04-0-02 - Preparation and catalytic properties of a novel type of zeolites with basic properties

S. Ernst, M. Hartmann and S. Sauerbeck

175

04-0-03 - Preparation and characterization of iron-substituted zeolites

G. Giordano, A. Katovic, A. Fonseca and J. B.Nagy

175

04-0-04 - Influence of the nature of T atoms on the morphology and crystal size of KZ-2 and ZSM-22 zeolites isomorphously substituted with AI or Fe

M. DerewihskL M. Kasture, J. Krydciak and M. Stachurska

176

04-0-05 - Synthesis and characterisation of novel large-pore vanadosilicates AM13 and AM-14

P. Brand6o, A. Philippou, N. Hanif, J. Rocha and M. Anderson

176

04-P-06 - Uniform distribution of nickel during the synthesis of Si-ZSM-5 through solid-state transformation

M. Salou, Y. Kiyozumi, E Mizukami, S. Niwa, M. lmamura and M. Haneda

335

04-P-07-Synthesis, characterization and catalytic activity of FeBEA and FeMFI zeolite obtained by xerogel wetness impregnation

O.A. Anunziata, L.B. Pierella, E.J. Lede and F.G. Requejo

335

04-P-08 - A novel method for the synthesis of chromium aluminosilicate with BEA structure

X.-H. Tang, L.-R. Pan, J.-Z. Wang and H. -X. Li

335

xxviii 04-P-09 - Pure SAPO, CoAPSO and ZnAPSO ATO-like molecular sieves through optimized synthesis procedures

A. Azzouz, N. Bflba, M. Attou, A. Zvolinschi and S. Asaftei

336

04-P-10 - Relation between amount of the niobium ammonium complex in the reaction mixture and the crystal size of an Nb- MFI zeolite

H. Munhoz Jr., S. Rodrigues," P.K. Kiyohara and W. Sano

336

04-P-11 - Spectroscopy of the formation of microporous transition-metal ion containing aluminophosphates under hydrothermal conditions

B.M. Weckhuysen, D. Baetens and R.A. Schoonheydt

336

04-P-12 - Co-templated synthesis of CrAPO-5 with various organic acids

J. Kornatowski, G. Zadrozna, J.A. Lercher and M. Rozwadowski

337

04-P-13 - How to increase the amount of framework Co 2+ in microporous crystalline aluminophosphates?

W. Fan, R.A. Schoonheydt and B.M. Weckhuysen

337

0 4 - P - 1 4 - Preparation of zinc containing zeolite catalysts

A. Katovic, E. Szymkowiak, G. Giordano, S. Kowalak, A. Fonseca and J. B.Nagy

337

04-P-15 - Synthesis of Zn and Fe substituted mordenite using citric acid as complexing agent

M. Dong, J.-G. Wang and Y.-H. Sun

338

04-P-16 - ET(Zr)S-4 molecular sieve' kinetic and morphological characterization

D. Vuono, P. De Luca, A. Fonseca, J. B.Nagy and A. Nastro

338

0 4 - P - 1 7 - Influence of alcali cations on the incorporation of iron into MFI structure in fluoride media

F. Testa, F. Crea, R. Aiello, K. L6zdr, P. Fejes, P. Lentz and J. B.Nagy

338

04-P-18 - Synthesis and characterization of Co-containing zeolites of MFI structure

E. Nigro, F. Testa, R. Aiello, P. Lentz, A. Fonseca, A. Oszko, P. Fejes, A. Kukovecz, I. Kiricsi and J. B.Nagy

339

05 - Synthesis of New Materials

05-0-01 - SOMS: Sandia Octahedral Molecular Sieves. A new class of ion exchangers selective for the removal of Sr 2÷ from waste streams

T.M. Nenoff M. Nyman, A. Tripathi, J.B. Parise, W.T.A. •Harrison and RS. Maxwell

156

xxix 05-0-02 - Hydrothermal synthesis of various titanium phosphates in the presence of organic amine templates Yunling Liu, Y. Fu, J. Chen, Y. Zou and W. Pang

157

05-0-03 - On the role of azamacrocycles and metal cations in the syntheses of metalloaluminophosphates STA-6,-7 a n d - 8 R. Garcia, E.F. Philp, A.M.Z Slawin, P.A. Wright and P.A. Cox

157

05-0-04 - Chiral transference and molecular recognition in novel Co(en)3Clatemplated zinc phosphates J. Yu, Yu Wang, Z Shi and R. Xu

157

05-0-05 - Very open microporous materials: from concept to reality A.K. Cheetham, H. Fjellvgtg, T.E. Gier, K.O. Kongshaug, K.P. Lillerud and G.D. Stucky

158

05-P-06 - Synthesis and structures of GIS, ABW and GME beryllophosphate molecular sieves from amine solutions H. Zhang, M. Chen, Z. Shi, Y. Zhou, Xin Xu and D. Zhao

244

05-P-07 - Microporous gallosilicate TNU materials and their implications for the synthesis of low-silica molecular sieves W.C. P a i l M.A. Camblor and S.B. Hong

244

05-P-08 - Synthesis and characterization of novel nickel phosphates from nonaqueous systems Yunling Liu, L. Zhang, P. Zhang, Y. Zou and W. Pang

244

05-P-09- Synthesis, characterization and properties of an anionic aluminophosphate molecular sieve with Br6nsted acidity W. Yan, J. Yu, R. Xu, Y. Han, K. Sugiyama and O. Terasaki

245

05-P-10 - Synthesis and characterization of an open-framework aluminophosphate [AIP206(OH)2][H30] containing propeller-like chiral motifs W Fan, J. gu, Z Shi and R. Xu

245

05-P-11 - Synthesis and characterization of an aluminum-substituted manganese phosphate with GIS topology H.-M. Yuan, Y.-S. Jiang, W. Chen, J.-S. Chen and R. Xu

245

05-P-12 - Synthesis and characterisation of novel microporous framework cerium and europium silicates D. Ananias, P. Ferreira, A. Ferreira, J. Rocha, J.P. Rainho, C.M. Morals and L.D. Carlos

246

xxx

05-P-13 - Novel microporous framework stannosilicates Z. Lin and J. Rocha

246

05-P- 14 - Magadiite intercalated M C M - 2 2 M. MunsignattL A.J.S. Mascarenhas, A.L.S. Marques and H. O. Pastore

246

05-P-15 - Synthesis of aluminum phosphite microporous materials N. Li and S. Xiang

247

0 5 - P - 1 6 - Synthesis, characterization and structural aspects of novel microporous indium L.M. King, J. Gisselquist, S.C. Koster, D.S. Bem, R.W. Broach, S.G. Song and R.L. Bedard

247

05-P-17 - Synthesis and characterization of the silicoaluminophosphate SAPO-47 L. Xu, Z. Liu, P. Tian, Y. Wei, C. Sun and ShL Li

247

05-P-18 - Synthesis, characterization and catalysis of SAPO-56 and MAPSO-56 molecular sieves P Tian, Z. Liu, L. Xu and C. Sun

248

05-P-19 - Synthesis and structural characterization of a novel microporous zeolitic type aluminium phosphate C. Sassoye, S. Girard, C. Mellot-Draznieks, T. Loiseau, C. Hugeunard, F. Taulelle and G. Fdrey

248

05-P-20 - Hydrothermal synthesis and crystal structures of two novel open frameworks: (enH2)3[Co3W4P4028] and (dapH2)3[Co3WnP4028] B. Yah, Y. Xu, N.K. Goh and L.S. Chia

248

06- Fundamentals

of Micelle Templating

06-0-01 - The effect of stoichiometry and synthesis conditions on the properties of mesoporous M41S family silicates W.J. Roth and J. C. Vartuli

134

06-0,02 - What are circular crystals? F. Marlow

134

06-0-03 - Hierarchically mesostructured zeolitic materials with the MFI structure D. Trong On, P. Reinert, L. Bonneviot and S. Kaliaguine

135

06-0-04 - Pore size engineering of MCM-48: The use of different additives as expanders M. Mathieu, E. Van Bavel, P Van Der Voort and E.E Vansant

135

xxxi 06-P-05 - X-ray diffraction analysis of ordered mesoporous silica M. Ookawa, Y. Yogoro, T. Yamaguchi and K. Kawamura

198

06-P-06 - Active MCM-48 supported catalysts: different strategies to increase the structural and chemical stability P. Van Der Voort, M. Mathieu and E.F. Vansant

198

06-P-07 - Strong acidic and high temperature hydrothermally stable mesoporous aluminosilicates with well-ordered hexagonal structure Zo. Zhang, Y. Han, R. Wang, S. Qiu, D. Zhao and F.-S. Xiao

198

06-P-08 - Studies on the synthesis of A I - l V I C M - 4 1 G.A. Eimer, L.B. Pierella and O.A. Anunziata

199

mesoporous materials

06-P-09 - Controlled synthesis of microporous and mesoporous silica-based molecular sieves in the presence of dodecyldimethylbenzylammonium chloride Z Y. Yuan, W. Zhou, L.M. Peng, J.-Z Wang and H.X. Li

199

06-P-10 - Formation of double-mesopore silica and its transformation into MCM-41 X.-Z. Wang, T. Dou, Y.-Z. Xiao and BI Zhong

199

06-P-11 - The synthesis and hydrothermal stability of directly usable hexagonal mesoporous silica by efficient primary amine template extraction in acidified water K. Cassiers, P. Van Der Voort and E.F. Vansant

200

06-P-12 - Synthesis and characterization of highly ordered chromium-substituted MCM-48 materials with tailored pore sizes C. Pak and G.L. Haller

200

06-P-13 - Preparation and characterisation of mesoporous silica spheres R. Van Grieken, D.P. Serrano, C. Martos and A.M. Melgares

200

06-P-14 - Rapid synthesis of high quality MCM-41 silica via ultrasound irradiation X.-H. Tang, Yanquing Wang, W Huang, S. Liu, O. Palchik, E. Sominski, Y. Koltypin and A. Gedanken

201

06-P-15 - Synthesis of mesoporous aluminosilicate FSM-materials derived from synthetic and natural Saponite T. Linssen, M. Barroudi, P. Cool and E.F. Vansant

201

06-P-16 - 129Xe NMR and adsorption studies of Si-MCM-48 and A1-MCM-48 G. Oye, M.-A. Springuel-Huet, J. Fraissard, M. StOcker and J. Sjoblom

201

xxxii 06-P-17 - 27A1.NMR studies on A1-MCM-41 molecular sieves synthesized with different Si/AI ratios and different aluminum sources

W. BOhlmann and D. Michel

202

06-P-18 - Control of formation of mesoporous SBA-3 and SBA-1 through organic additives

S. Che and T. Tatsumi

202

06-P-19 - The influence of A1, La or Ce in the thermal and hydrothermal properties of MCM-41 mesoporous solids

R.A.A. Melo and E.A. Urquieta-Gonzdlez

202

06-P-20- Controlling the assembly of silica mesoporous materials by varying the decrease in pH

J. Rathous~, J. Cejka, P.J. Kooyman, M. Slabovd and A. Zukal 06-P-21

-

203

Characterisation of MCM-41 aged for different periods

H. Al-Megren, T.-C Xiao, A.P.E. York, J. Sloan, S. Al-Khowaiter, S.-E Ji and ML.H. Green

203

06-P-22 - Synthesis and characterization of silica and aluminosilica-surfactant nanocomposites

E. Popovici, A. Visan, D. Filip, G. Burtica and R. Pode

203

06-P-23 - Improved thermal stability of mesoporous alumina support of catalysts for the isomerization of light paraffins

V. Gonzdlez-Peha, C. Mdrquez-Alvarez, E. Sastre and J. Pdrez-Pariente

204

06-P-24 - Synthesis of mesoporous molecular sieves MCM-48 under several reaction conditions

S. Rodrigues da Rocha and L. Domiciano Fernandes

204

06-P-25 - Parallel synthesis of mesostructured materials

P. Behrens and C. Tintemann

204

06-P-26 - Mesostructural transformation in the presence of fluoride anions

Q-H. Xia, K. Hidajat and S. Kawi

205

06-P-27 - Swelled Micelle-Templated Silicas (MTS): structure control and hydrophobic properties

D. Desplantier-Giscard, A. Galarneau, F. Di Renzo and F. Fajula

205

06-P-28 - Synthesis of pure and iron-containing mesoporous silica. Effect of washing and removal of template on the porous structure

L. Pasqua, E Testa, R. Aiello, E Di Renzo and E Fajula

205

xxxiii

07 - N e w M e s o p o r o u s M o l e c u l a r Sieves

07-0-01 - Ordered mesoporous carbon molecular sieves by templated synthesis: the structural varieties

R. Ryoo, S.H. Joo, S. Jun, T. Tsubakiyama and O. Terasaki

150

07-0-02 - One-pot synthesis of phenyl functionalized porous silicates with hexagonal and cubic symmetries

V. Goletto, M. Impdror and F. Babonneau

150

07-0-03 - State and redox behavior of iron in MCM-41

G. Pdl-Borb~ly, A. Szegedi, K. L6zdr and H.K. Beyer

150

07-0-04 - A comparative study of Cu interaction with niobium- and aluminumcontaining MCM-41 molecular sieves

M. Ziolek, I. Sobczak, I. Nowak, P. Decyk and J. Stoch

151

07-0-05 - A novel synthesis strategy leading to the formation of stable transitionmetal-oxide mesostructures

X.S. Zhao, J. Drennan and G.Q. Lu

151

07-P-06 - Vanadosilicate: Cubic mesoporous molecular sieve

M. Chatterjee, T. lwasaki, Y. Onodera, H. Hayashi, T. Ebina and T. Nagase

249

07-P-07 - Synthesis and characterization of mesoporous Cu-silica spheres via a novel co-assemble route

P. Zhang, N. Bai, X. Meng and W. Pang

249

07-P-08 - Synthesis and characterization of mesostructured alumina prepared in the presence of dodecylphosphate

L. Sicard, B. Lebeau, C. Marichal, J. Patarin and F. Kolenda

249

07-P-09 - Synthesis and characterizations of mesoporous zirconia-based oxide composites

J. Zha, D. Wu, Y.-H. Sun," Zh. Zhang, H. Zhang and D. Zhao

250

07-P-10 - Preparation and catalytic property of FeL/Y composite by a new method

B. Fan, W. Fan and R. L i

250

07-P-11 - Mesoporous zirconia: an anionic surfactant inorganic composite, precursor of a tridimensional porous material.

G. Pacheco and J.J. Fripiat

250

07-P-12 - Synthesis of micelle templated TiO2 mesophases by a sol-gel approach: effect of the surfactant removal

D.P. Serrano, G. Calleja, R. Sanz and P. Pizarro

251

xxxiv 07-P-13 - Preparation and characterization of iron oxide nanoparticles in the channels of MCM-41

C.M. Yang and K.J. Chao

251

07-P-14 - The evaluation of iron chromophore concentrations from iron containing MCM-41

C. Nenu, R. Ganea, R Bfrjega, Gr. Pop and M. Pitu

251

07-P-15 - Synthesis and characterization of the mesoporous material of single crystal particles

B. Lee, J. N. Kondo, D. Lu and K. i Domen

252

07-P-16 - Stabilization of uniformly sized and dispersed copper particles in new Cu-Zn-A1 mesoporous catalysts

S. Valange, J. Barrault, A. Derouault and Z. Gabelica

252

07-P-17 - A direct synthesis route to the mesoporous silicate SBA-2 bearing thiol groups

I. Diaz, F. Mohino, J. Pdrez-Pariente, E. Sastre, P.A. Wright and W. Zhou

252

07-P-18 - Template synthesis and characterisation of nanoporous alumina with narrow pore size distribution from inorganic salts

H. Y. Zhu, P. Cool G. Q. (Max) Lu and E. F Vansant

253

07-P-19 - Preparation and characterization of copper oxide modified MCM-41 molecular sieves

C. Minchev, R. KOhn, T. Tsoncheva, M. Dimitrov and M. Fr6ba

253

07-P-20 - Crystalline, mesoporous NiO-ZrO2-based solid oxide fuel cell catalysts

P. Ratnasamy, D. Srinivas, H.S. SonL A.J. Chandwadkar, H.S. Potdar, C.S. Gopinath and B.S. Rao

253

07-P-21 - Application of the AASBU method to the prediction of inorganic structures built exclusively of sodalite cages

S. Girard, P. PullumbL C. Mellot-Draznieks and G. F~rey

254

07-P-22 - Novel synthesis of nanoporous carbons using colloidal templates

S.B. Yoon, 1.S. Shin and J.-S. Yu

254

07-P-23 - Synthesis and characterization of mesoporous cerium silicate analogues of MCM-41 type molecular sieves

S. Laha, P. Mukherjee and R. Kumar

254

XXXV

07-P-24 - Synthesis of mesoporous materials using filtrate of alkali treatment of MFI zeolite M. Ogura, E. Kikuchi and M. Matsukata

255

08- Syntheses with Non-Ionic surfactants 08-0-01 - Mesoporous MSU-X silica tuned for filtration and chromatography applications C. Boissibre, A. Larbot and E. Prouzet

179

08-0-02 - Highly ordered mesoporous silicas synthesis using deca(oxyethylene) oleylether as surfactant: variation of the weight percentage of surfactant and incorporation of transition metal cations G. Herrier and B.-L. Su

180

08-0-03 - Silica walls of calcined mesostructured SBA-15 materials templated by triblock copolymers M. Imp&or and A. Davidson

180

08-0-04 - Template / AISBA-15 interaction: double resonance N M R study and consequences on structural properties J.-B. d'Espinose de la Caillerie, Y. Yue and A. Gdd~on

180

08-P-05 - The double-step synthesis of MSU-X silica: decoupling the assembly mechanism E. Prouzet, C. BoissiOre, N. Hovnanian and A. Larbot

284

08-P-06 - Steam - stable aluminosilicate MSU-S mesostructures assembled from zeolite seeds Yu Liu, W. Zhang and T.J. Pinnavaia

284

08-P-07 - A study on the mesoporous silica structures templated by triblock copolymers C.-P. Kao, H.-P. Lin, M.-C. Chao, H.-S. Sheu and C.-Y. Mou

284

08-P-08 - Study of methyl modified MSU-X silicas Y. Gong, Z Li, S. Wan, D. Wu, Y.-H. Sun, F. Deng, Q. Luo and }1. Yue

285

08-P-09 - Study of mesoporous materials with ultra high surface area prepared from alternate surfactants and silicate sources J. F. P~rez-Ardvalo, J.M. Dominguez, E. Terrds, A. Rojas-Herndndez and M. Miki

285

08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials from gels containing non-ionic surfactants 1. Diaz, F. Mohino, E. Sastre and J. Pdrez-Pariente

285

xxxvi 08-P-11 - Secondary hydrolysis process to synthesize highly ordered mesoporous silica from nonionic surfactant with long hydrophilic chain J. Fan, C. Yu and D. Zhao

286

08-P-12 - Mesostructure design using mixture of nonionic amphiphilicblock copolymers J.M. Kim, S.-E. Park and G.D. Stucky

286

08-P-13 - Stability of mesoporous material SBA-15 and its benefit in catalytic performance C. Nie, L. Huang, D. Zhao and Q. Li

286

08-P-14 - Comparative study of the wall properties in highly-ordered silicate and aluminosilicate mesostructured materials of the MCM-41 and SBA-15 types L.A. Solovyov, V.B. Fenelonov, A. Yu. Derevyankin, A.N. Shmakov, E. Haddad, A. Gedeon, S.D. Kirik and V.N. Romannikov

287

09-Crystal Structure Determination 09-O-01 - Localisation of K + ions in (Na,K)-LSX and K-LSX zeolites by Rietveld analysis and 39KNMR spectroscopy. A new cationic site in the orthorhombic dehydrated K-LSX at room temperature J.L. Paillaud, P. Caullet, L. Delmotte, J.C. Mougenel, S. Kayiran and B. Lledos

163

09-0-02 - NMR crystallography of A1PO4-CJ2 F. Taulelle and C. Huguenard

163

09-0-03 - FOS-5, a novel zeotype with 3D interconnected 12- ring channels T. Conradsson, X. Zou and M.S. Dadachov

164

09-0-04 - Neutron diffraction study of protons in four lanthanum exchanged X and LSX zeolites D.H. Olson, B.H. Toby and B.A. Reisner

164

09-0-05 - Optimized synthesis and structural properties of lithosilicate RUB-29 So-Hyun Park, J.B. Parise and H. Gies

164

09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated fully Cd(II)-exchanged zeolite X E. E Choi, S.H. Lee, Y.W. Han, E Kim and K. Serf

288

09-P-07 -The structure of a copper molybdate and its relation to other natural and synthetic porous materials based on transition metal polyhedra L. A. Palacio, A. Echavarria, A. Simon and C. Saldarriaga

288

xxxvii 09-P-08 - A 3-D open-framework nickel aluminophosphate [NiA1P2Os][C2N2H9]: assembly of 1-D AIP2083 chains through [NiOsN] octahedra B. Wei, Jihong Yu, Guangshan Zhu, F. Gao, Y. Li, R. Wang, Bo Gao, Xian. Xu, S. Qiu and O. Terasaki

288

09-P-09 - Structural modifications induced by high pressure in scolecite and heulandite: in-situ synchrotron X-ray powder diffraction study G. Vezzalini, S. Quartieri, A. Sani and D. Levy

289

09-P- 10 - Preparation, characterization, and crystal structures of fully indiumexchanged zeolite X N.H. Heo, S. W. Jung, S.W. Park J.S. Noh, W.T. Lim, M. Park and K. Serf

289

09-P-11 - Structural investigation by powder X-ray diffraction and solid state nuclear magnetic resonance of A1PO4-SOD M. Roux, C. Marichal, d.L. Paillaud, L. Vidal, C. Fernandez, C. Baerlocher and J.M. Chezeau

289

09-P-12 - Layered germanates with 9-membered rings X. Zou, T. Conradsson and M.S. Dadachov

290

09-P-13 - Dehydration dynamics of mordenite by in-situ time resolved synchrotron powder diffraction study: a comparison with electrostatic site energy calculations. A. Martucci, M. Sacerdoti and G. Cruciani

290

09-P-14 - Study of water vapor adsorption in the organically-lined channels of A1MepO-13 using X-ray powder diffraction K. Maeda, L.B. McCusker and C. Baerlocher

290

10- Host-Guest Chemistry 10-O-01 - Investigation of indium loaded zeolites and additionally promoted catalysts for selective catalytic reduction of NO× by methane F.-W. Schatze, H. Berndt, M. Richter, B. L~icke, C. Schmidt, T. Sowade and W. Granert

135

10-0-02 - Ion exchange of alkali metals and control of acidic/basic properties of MCM-22 and MCM-36 J.-O. Barth, R. Schenkel, J. Kornatowski and J.A. Lercher

136

10-0-03 - Insertion compounds of metal halides with porosils: "Structured Gases" P. Behrens, M. Hard, G. Wirnsberger, A. Popitsch and B. Pillep

136

xxxviii 10-0-04 - Site selective adsorption and catalytic properties of iron in FER and BEA zeolites Z Sobalik, J.E. Sponer, Z. Tvarfi~,kovd, A. Vondrovd, S. Kuriyavar and B. Wichterlovd

136

10-P-05 - Non-acidic zinc zeolite systems: preparation methods, formation processes and catalytic properties in dehydrogenation of methanol N. Ya. Usachev, E.P. Belanova, A. V. Kazakov, V.P. Kalinin, A.S. Fomin, 1.M. Krukovsky, G. V. Antoshin and O.K. Atal 'yah

206

10-P-06 - Incorporation of Ga ions into Y zeolites by reductive solid-state ion exchange R.M. MihdlyL H.K. Beyer and M. Keindl

206

10-P-07 - Heavy metal exchanged zeolites as precursors for high temperature stable phases W. Schmidt and C. Weidenthaler

206

10-P-08 - Preparation and characterization of H-ZSM-5 exchanged with cobalt by solid state ion exchange M. Mhamdi, S. Khaddar-Zine, A. Ghorbel, Y. Ben Taarit and C. Naccache

207

10-P-09 - Cyclic chemical vapour deposition of TEOS on ZSM-5: effect of deposition temperature on shape selective performance H. Manstein, K.P. Moller and C.T. O'Connor

207

11 - Post-synthesis Modification 11-O-01 - Gold-based mono- and bimetallic nanoparticles on HY zeolites G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin and J. Fraissard

141

11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on zeolites and evidence for pore mouth plugging determined from model conversion over stepwise silanised samples H.P. ROger, H. Mantein, W. BOhringer, K.P. MOller and C.T. O'Connor

142

11-O-03-Templating role of F towards D4R units : study of the transformation of the fluorogallophosphate Mu-3 into Mu-2 A. Matijasic, P. Reinert, L. Josien, A. Simon and J. Patarin

142

11-O-04 - Modification of the Si/Ti ratio in ETS-10 G. Koermer, A. Thangaraj and S. Kuznicki

142

11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by chemical vapour deposition P Marturano, L. Drozdovd, A. Kogelbauer and R. Prins

143

xxxix

1 l-P-06 - Dealumination of zeolite KL

E.E. Knyazeva, V.V. Yuschenko, F. Fajula and I.I. Ivanova

208

1 l-P-07 - Formation of acidic hydroxyl groups during preparation of Pt/KL catalysts as studied by ~H MAS NMR

T. Sato, S.-I. 1to, K. Kunimori and S. Hayashi

208

1 l-P-08 - Synthesis and characterization of mesopore Y Zeolite

B. Ma, W.F. Sun, Z.L. Sun and L.R. Chen

208

1 l-P-09 - Controlling the pore size of Hi3 zeolite by improved chemical vapor deposition of (CH3)3Si-O-Si(CH3)3

Y. Chun, X. Ye, Q.H. Xu and A.-Z. Yan

209

1 l-P- 10 - Influence of pH of the solution on realumination of BEA zeolite

Y. OumL R. Mizuno, K. Azuma, S. Sumiya, S. Nawata, T. Fukushima, T. Uozumi and T. Sano

209

1 l-P-11 - Formation of carbon-intercalated molybdenum sulfides

J.-S. Chen, Y. Wang, Y. Guo, Y. Zou and W. Xu

209

1 l-P- 12 - Characterization of partly-detemplated GaPO4-LTA

S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen

210

1 l-P-13 - Another study on the microwave heating of zeolite - without special loading materials

J. Dong, L. Xie, X. Jing, H. Xu, F. Wu and J. Hao

210

1 I-P-14 - Microwave plasma treatment as an effective technique for activation of zeolite catalysts

I.I. Lishchiner, O. V. Malova and E.G. Krasheninnikov

210

1 l-P-15 - Synthesis and characterization of microporous titanium-silicate materials

S. Mintova, B. Stein, J.M. Reder and T. Bein

211

1 l-P-16 - From borosilicate to gallo- and aluminosilicate zeolites: new methods for lattice substitution via post-synthetic treatment

C.Y. Chen and S. 1. Zones

211

1 l-P-17 - Studies on the structure of zeolite Y modified by radio-frequency fluorocarbon plasma treatment

S. Yamazaki, T. Nishimura, K. Furukawa, H. Ijiri and K. Tsutsumi

211

11-P-18 - Dual-temperature reagent-less ion-exchange separations on zeolites

V.D. Timofeevskaja, O.T. Gavlina, V.A. Ivanov and El. Gorshkov

212

1 l-P-19 - Rare earth exchange in small pore zeolites and its effect on their hydrothermal stability

G. Cao, M.J. Shah and W.A. Wachter

212

1 l-P-20 - Modification of mordenite and natural clinoptilolite by copper: role of drying temperature

I. Rodriguez-lznaga, V. Petranovskii, G. Rodriguez-Fuentes, N. Bogdanchikova and 3/1. Avalos

212

1 l-P-21 - Study on the acidity of modified HY zeolites prepared by combination of chemical dealumination and hydrothermal treatment

M. Han, L.-P Zhou, X.-W. Li and L.-Q. She

213

11-P-22 - Modification of Beta-zeolite by dealumination and realumination

J. Y. Zhang, L-P. Zhou and X. W. Li

213

11-P-23 - Ultrastable zeolites Y (USY) modified with phosphorus and boron

A. V. Abramova, Ye. V. Slivinsky, L. Ye. Kitaev, A.A. Kubasov, H. Lechert, W.D. Basler, V. V. Yushchenk and Z M. Matieva

213

11-P-24 - Structural properties and sieving effects of surface modified ZSM-5

S. Zheng, tl. Heydenrych, H.P. ROger, A. Jentys and J.A. Lercher

214

11-P-25 - The use of binary adsorption studies to investigate the effect of hydrothermal treatment on zeolites Rho and Mordenite

L.H. Callanan, C.T. O'Connor and E. van Steen

214

11-P-26 - Acid sites in thermal transformations of Ca-rich clinoptilolite

G.P. Valueva, I.S. Afanassiev, E.A. Paukshtis, Y.V. Seryotkin, N.K. Moroz and A.A. Budneva

214

11-P-27 - The effect of calcination on the isomorphously substituted microporous materials using ozone

D. Mehn, A. Kukovecz, I. Kiricsi, F. Testa, E. Nigro, R. Aiello, G. Daelen, P. Lentz, A. Fonseca and J. B.Nagy

215

11-P-28 - Alumination of siliceous zeolites

A. Omegna, M. Haouas, G. Pirngruber and R. Prins

215

11-P-29 - New hydrophobic Ti-Beta catalyst obtained by silylation and its catalytic performance for olefin epoxidation.

A. Corma, M.E. D6mine, J.A. Gaona, M.T. Navarro, F. Rey and S. Valencia.

215

1 l-P-30 - MFI zeolite with uniform mesopores created by alkali treatment

M. Ogura, E. Kikuchi and M. Matsukata

216

xli 12 - In-situ Spectroscopy and Catalysis 12-0-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI zeolite

F. Thibault-Starzyk, A. Vimont and J.-P. Gilson

133

12-O-02 - Structure/reactivity correlation in Fe/ZSM5 for deNOx applications. In-

situ XAFS characterization and catalysis A.A. Battiston, J.H. Bitter and D.C. Koningsberger

133

12-0-03 - Interaction of diazines with faujasites studied by IR spectroscopy, temperature-programmed desorption, and molecular modeling methods

J. DObler, E. Geidel, B. Hunger, K.H.L. Nulens and R.A. Schoonheydt

133

12-0-04 - DRIFT study of dinitrogen and dihydrogen adsorption on Li- and Naforms of LSX zeolite

V.B. Kazansky, A.I. Serykh, E. Tichomirova, V. Yu Borovkov and M. Bulow

134

12-P-05 - Study of relationship between mordenite acidity and structure with calcination temperature

Z. Zhu, Q. Chen and We. Chen

217

12-P-06 - Infrared observation of the stable carbenium ions formed by adsorption of olefins on zeolite Y at low temperatures

S. Yang, J.N. Kondo and K. Domen

217

12-P-07 - Characterization of aluminosilicate zeolites by UV-Raman spectroscopy

Y. Yu, G. Xiong, C. Li and F.-S. Xiao

217

12-P-08 - Adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodiumion exchanged faujasites with different Si/A1 ratios

1.A. Beta, H. BOhlig, J. DObler, H. Jobic, E. Geidel and B. Hunger

218

12-P-09 - DRIFT and FTIR spectra of N2 and C2H4adsorbed on CuNaY

G. Habner and E. Roduner

218

12-P-10 - Raman study of the building units in the zeolite structure

P.P.H.J.M. Knops-Gerrits, X.-Y. Li, N.-T. Yu and P.A. Jacobs

218

12-P-11 - Positron annihilation study in MCM-41

1t. Y. Zhang, Y.J. He, Y.B. Chen, H.Y. Wang and T. Horiuchi

219

12-P-12 - N M R studies on the pyrrole adsorption over Na +, Li + exchanged zeolites of type FAU

M. Sdlnchez-S6nchez and T. Blasco

219

xlii 12-P-13 - Variable-temperature FTIR study of the equilibrium between C-bonded and O-bonded carbon monoxide in H-ZSM-5 G. Turnes Palomino, M. Peharroya Mentruit, A.A. Tsyganenko, E. Escalona Platero and C. Otero Aredn

219

12-P-14 - Role of the various acid sites in MOR on o-xylene conversion: An insitu I.R. approach O. Marie, F. Thibault-Starzyk, P. Massiani and J.C. Lavalley

220

12-P-15 - FTIR- Studies on adsorption and decomposition of NO on in-situ synthesized ZSM-5/cordierite catalysts N. Guan, X. Shan, X. Zeng, S. Xiang, A. Trunschke and M. Baerns

220

12-P-16 - Acid sites in dealuminated mordenite V.L. Zholobenko and G.P. Mitchell

220

12-P-17 - Infrared study of iron-exchanged Y zeolite and its HDS activity M Nagai, O. Uchino and S. Omi

221

13 - F r a m e w o r k s and Acid Sites 13-0-01 - Where are the acid sites in zeolites? A novel NMR approach to measure B/A1 ordering around structure directing agents H. Koller, M. Kalwei, C. Fild, R.F. Lobo, MA. Camblor, L.A. Villaescusa and L. van W~illen

182

1 3 - 0 - 0 2 - The effect of the nature of heteroatoms (A1, Fe, B) on their distribution in the ZSM-5 structure J. D~degek, M. Tudor and J. (~ejka

182

13-0-03 - Toward the quantification of aluminum in zeolites using highresolution solid-state NMR C. Fernandez, A.-A. Quoineaud, V. Montouillout, S. Gautier and S. Lacombe

183

13-0-04 - Acidity of ITQ-2 zeolite as studied by FT-IR spectroscopy of adsorbed molecules in comparison with that of MCM-22 B. Onida, F. Geobaldo, L. Borello and E. Garrone

183

13-P-05 - In-situ FTIR studies of the acidity of H3PWl2040 and its porous salts. Interaction with H20, NH3 and pyridine N. Essayem, A. Holmqvist, G. Sapaly, J.C. V~drine and Y. Ben Tdarit

340

13-P-06 - Dynamics of p-nitroaniline in the micropore of zeolite ZSM-5 studied by solid-state N M R S. Hayashi and Y. Komori

340

xliii 13-P-07 - The use of microcalorimetry to study the effects of post-synthesis treatments on the modification of the acidity of several HY-type zeolites A. Auroux and M.L. Occelli

340

13-P-08 - ESR investigations of the catalytic properties of Lewis acid sites in Hmordenite T.M. Leu and E. Roduner

341

13-P-09 - External surface acidity of modified zeolites: ESR via adsorption of stable nitroxyl radicals and IR spectroscopy A.B. Ayupov, G.V. Echevsky, E.A. Paukshtis, D.J. O'Rear and C.L. Kibby

341

13-P-10 - Very strong acid site in HZSM-5 formed during the template removal step; its control, structure and catalytic activity A. Kohara, N. Katada and M. Niwa

341

13-P-11- Correlation between liB NMR isotropic chemical shifts and structural parameters in borates and boro-silicates J. Pl~vert, F. Di Renzo and F. Fajula

342

13-P-12 - Investigation of the paramagnetic effect of oxygen in the Z3Na MAS NMR and 23Na MQMAS NMR spectra of LiNaX R.J. Accardi, M. Kalwei and R.F. Lobo

342

13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laserinduced fluorescence of adsorbed quinoline A. Lassoued, J. Thoret, P. Batamack, A. Gdddon and J. Fraissard

342

13-P- 14 - Dynamic behaviour of acetonitrile molecules adsorbed in ALPO4-5 and SAPO-5 studied by solid NMR method S. lshimaru, M. lchikawa, K. Gotoh and R. lkeda

343

13-P-15 - Determination of the Si/A1 ratio of faujasite-type zeolites C.H. Rascher, J.-C. Buhl and W. Lutz

343

13-P-16 - Theoretical investigation of the chemical shift anisotropy of toluene adsorbed on zeolite X A. Simperler, A. Philippou, D.-P. Luigi, R.G. Bell and M. W. Anderson

343

13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR spectroscopy J. Datka, B. Gil and K. G6ra-Marek

344

13-P-18 - Aluminium species in activated zeolites: solid-state NMR spectroscopy of the active sites B.H. Wouters, T.-H. Chen and P.J. Grobet

344

xliv

13-P-19 - Aluminium distribution in high silica pentasil ring zeolites B. Wichterlovd, J. Dgdedek, Z Sobalik and J. Cejka

344

13-P-20 - Effects of hydration on A1PO4-14 and AIPO4-18 structures: 31p MAS and 27A1 3Q-MAS NMR study

C. V. Satyanarayana, R. Gupta, K. Damodaran, S. Sivasanker and S. Ganapathy

345

13-P-21 - Comparative study of the acidity of the structurally related faujasite type zeolites: FAU, EMT and ZSM-20

H. Kosslick, R. Fricke, H. Miessner, D.L. Hoang and W. Storeck

345

13-P-22 - The effect of flexible lattice aluminum in zeolites during the nitration of aromatics

M. Haouas, A. Kogelbauer and R. Prins

345

13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double resonance solid state NMR

S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux and S. Ganapathy

346

13-P-24 - Measurement of MQMAS heteronuclear correlation spectra in microporous aluminophosphates

C. Fernandez and M. Pruski

346

13-P-25 - FTIR studies of the interaction of aromatic and branched aliphatic compounds with internal, external and extraframework sites of MFI-type zeolite materials

7". Armaroli, A. Guti~rrez Alejandre, M. Bevilacqua, M. Trombetta, F. Milella, J. Ramirez and G. Busca

346

14- Frameworks, Cations, Clusters 14-0-01 - Imaging the mesopores in zeolite Y using three-dimensional transmission electron microscopy

A.H. Janssen, A.J. Koster and K.P. de Jong

176

14-O-02 - 170 NMR studies of the structure and basic properties of zeolites

D. Freude, T. Loeser and U. Pingel

177

14-0-03 - Theoretical interpretation of UV-VIS spectra of Cu- and Ag-species in zeolites: structure vs. transition energies.

P. Nachtigall, M. Davidov6, M. Silhan and D. Nachtigallovd

177

14-0-04 - Silver ions and quantum-sized silver sulfide clusters in zeolite A D. Brtihwiler, C. Leiggener and G. Calzaferri

177

xlv 14-O-05 - Elucidating the nature and reactivity of cobalt ions in CoAPOs. A combined FTIR and EPR study of NO and NO2 adsorbed at 77 K and 298 K

E. Gianotti, M.C. PaganinL G. Martra, E. Giamello, S. Coluccia and L. Marchese

178

14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite

T. Ohgushi and K. Ishimaru

347

14-P-07 - Adsorption of DTBN at monovalent cations in zeolite y as studied by electron spin resonance spectroscopy

M. Gutjahr, W. BOhlmann, R. BOttcher and A. POppl

347

14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES studies at Mo K and LIH-edges

F.G. Requejo, E.J. Lede, L.B. Pierella and O.A. Anunziata

347

14-P-09 - EPR studies on nitrogen monoxide in zeolites

H. Yahiro, N.P. Benetis, A. Lund and M. Shiotani

348

14-P-10 - Evidence of partially broken bridging hydroxyls in molecular sieves from IH MAS spin echo NMR spectroscopy

T.-H. Chen, B.H. Wouters and P.J. Grobet

348

14-P-11 - Structure change of molecular sieve SAPO-37 at high temperature studied by 27A1 MQ MAS NMR

T.-H. Chen, B. Wouters and P. Grobet

348

14-P-12 - Effects of molecular confinement on structure and catalytic behaviour of metal phthalocyanine complexes encapsulated in zeolite-Y

S. Seelan, D. Srinivas, M.S. Agashe, N.E. Jacob and S. Sivasanker

349

14-P-13 - Investigations on isomorphous substitution and catalytically active centres in MeAPO-31 (Me = Mn, Co, Zn, Ti)

N. Novak Tusar, A. Ristic, A. Ghanbari-Siahkali, J. Dwyer, G. Mali, I. Arcon and V. Kaucic

349

14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-1) synthetized by different methods

N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. CagnolL S.G. Marchetti and A.A. Yeramian

349

14-P-15 - Behaviour of Fe(III) ions in Y zeolites in the presence of Cu(II) and Ag(I) ions: an ESR study

A.L. Kustov, E.E. Knyazeva, E.A. Zhilinskaya, A. Aboukais and B. V. Romanovsky

350

14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in zeolites

Y. Huang, J.H. Leech and R.R. Poissant

350

xlvi 14-P-17 - High-temperature MAS NMR investigation of the mobility of cations and guest compounds in zeolites X and Y M. Hunger, A. Buchholz and U Schenk

350

14-P-18 - Generation of long-lived electron-hole pairs through sorption of biphenyl into acidic ZSM-5 zeolites I. Gener, A. Moissette, H. Vezin, J. Patarin and C. Br~mard

351

14-P-19 - Defects study in microporous materials by HRSEM, HRTEM and diffraction techniques G. Gonzalez, Z Lopez and R. Reichelt

351

14-P-20 - The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites and their photocatalytic reactivity S. Higashimoto, M. Matsuoka, M. Che and M. Anpo

351

14-P-21 -Characterization of aluminium and iron sites in MCM-22 J. (;ejka, J. D~dedek, J. Kotrla, M. Tudor, N. Zilkovct and S. Ernst

352

14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ M6ssbauer study K. L6z6r, N. Zilkov6 and J. Cejka

352

14-P-23 - C o m p a r a t i v e properties of modified HEMT and HY zeolites from the FTIR study of CO adsorption: effect of the dealumination and amorphous debris on the Br6nsted acidity O. Cairon and T. Chevreau

352

14-P-24 - Raman spectroscopic study of 2,2'-bip;cridine sorbed into ZSM5 A. Moissette, C. Br~mard, 1. Gener and N. Louchart

353

14-P-25 - Fractals of silica aggregates Z. Li, D. Wu, Y.-H. Sun, J. Wang, Yi Liu and B. Dong

353

14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3 studied by XAFS and UV-VIS spectroscopies H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi

353

14-P-27 - Quantification of electric-field gradients in the supercage of Y zeolites by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I = 1/2) Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard

354

14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion exchange in aqueous medium or in the solid state M.S. Batista, M.A.M. Torres, E. Baggio-Saitovich and E.A. Urquieta-Gonz6lez

354

xlvii

14-P-29 - Laser ablation mass spectrometry : a technique for observing zeolite occluded molecules

S. Jeong, K.J. Fisher, G.D. Willett and R.F. Howe

354

14-P-30 - Characterisation of TS-1 active sites by adsorption of organic probes C. Flego, A. Carati and M.G. Clerici

355

14-P-31 - NIR FT-Raman spectroscopy on molecular sieves E. LOftier and M. Bergmann

355

14-P-32 - Characterization of Zn and Fe substituted mordenite by XAFS M. Dong, J.-G. Wang and Y.-H. Sun

355

14-P-33 - Identification of vanadium species in VAPO and VAPSO aluminophosphate by UV resonance raman spectroscopy

Jia. Yu, Z. Liu, Q. )(in and C. Li

356

14-P-34 - On the interaction of H20 with TS-1: a spectroscopic and ab-initio study

A. Damin, G. Ricchiardi, S. Bordiga, F. Bonino, A. Zecchina, F. Ricci, G. Span6, F. Villain, and C. Lamberti

356

14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of the support (SiO z and All3 and SiB zeolites).

S. Dzwigaj, M. Matsuoka, M. Anpo and M. Che

356

14-P-36 - Characterization ofNi, Pt zeolite catalysts by TEM and EDX M.H. Jord6o and D. Cardoso

357

14-P-37 - NMR and ESR investigations of alkali metal particles in NaY zeolite F. Rachdi and L.C. de M~norvat

357

14-P-38 - Topochemical changes in large MFI-type crystals upon thermal treatment in oxidizing and non-oxidizing atmosphere

O. Pachtov6, B. Bernaue, J.-A. Dalmon, S. Miachon, I. Jirka, A. Zik6nov6 and M. Kodi(ik

357

14-P-39 - Structure of Fe(III) sites in iron substituted aluminophosphates: a computational and X-ray spectroscopic investigation

C. Zenonos, A. Beale, G. Sankar, D.W. Lewis, J.M. Thomas and C.R.A. Catlow

358

14-P-40 - Possible formation of Cu+2(CO)2(H20)n complexes in a ZSM-5 zeolit.e prepared by direct synthesis: evidence for the occurrence of Cu+-Cu + pairs?

F. Geobaldo, B. Onida, M. Rocchia, S. Valange, Z Gabelica and E. Garrone

358

xlviii 15 - Modelling and Theoretical Studies A 15-0-01 - Proton jumps in dehydrated acidic zeolite catalysts. Rate predictions based on ab-initio calculations

M. Sierka and J. Sauer

148

15-0-02 - Ab-initio simulation of dynamical processes in zeolites L. Benco, T. Demuth, J.Hafner, F. Hutschka and 14. Toulhoat

148

15-0-03 - A theoretical study of the methylation of toluene by methanol over acid mordenite

A. Vos, X. Rozanska, R. Schoonheydt, R. van Santen, F. Hutschka and J. Hafner

149

15-0-04 - Coverage effects on adsorption of water in faujasite: An ab-initio cluster and embedded cluster study

J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong and T.N. Truong

149

15-0-05 - The Beckmann rearrangement catalyzed by silicalite: a spectroscopic and computational study

G.A. Fois, G. Ricchiardi, S. Bordiga, C. Busco, L. Dalloro, G. Span6 and A. Zecchina

149

15-P-06 - A reactivity index study to choose the best template for zeolite synthesis

A. Chatterjee and T. lwasaki

256

15-P-07 - Effects of ion-exchanged alkali metal cations on the photolysis of alkyl ketones included within ZSM-5 zeolite cavities: A study of ab-initio molecular orbital calculations

H. Yamashita, S. Takada, M. Nishimura, H. Bessho and M. Anpo

256

15-P-08 - Encapsulated guest atoms within the basic beta cage of sodalitic zeolite. A theoretical ab-initio study

N. U. Zhanpeisov and M. Anpo

256

15-P-09 - n-Hexane aromatization over Pt-alkaline zeolites: ab-initio calculations on the influence of the exchanged cations and zeolite type (L, 13 and Y) on electronic properties of Pt

S.B. Waghmode, P. Bharathi, R. Vetrivel and S. Sivasanker

257

15-P-10 - A theoretical study of adsorption of carbon monoxide on Ag-ZSM-5 zeolite

S. Jungsuttiwong, P. Khongpracha, T.N. Truong and J. Limtrakul

257

15-P-11 - A theoretical/spectroscopic study of the coordination of transition metal ions in zeolites

A. Delabie, M.H. Groothaert, R.A. Schoonheydt and K. Pierloot

257

xlix 15-P-12 - Ab-initio study of the adsorption and reactions of hydrocarbons in mordenite T. Demuth, L. Benco, J. Hafner, H. Toulhoat and F. Hutschka

258

15-P- 13 - Properties of C u 2+ and Cu + cations in MFI framework: DFT and IR studies E. Broclawik, J. Datka, B. Gil and P. Kozyra

258

15-P-14 - Nonempirical (ab-initio) and semiempirical calculations of the elementary fragments of zeolites. Permeability of rings zeolite fragments A.V. Gabdrakipov, L.D. Volkova, N.A. Zakarina and V.Z Gabdrakipov

258

15-P-15 - Modelling light alkane transformation over HZSM-5 zeolite X. Wang, F. Lemos and F.R. Ribeiro

259

15-P-16 - Activity-acidity relationship in Y zeolite: an experimental and quantumchemical study X. Wang, M.A.N.D.A. Lemos, F. Lemos, C. Costa and F.R. Ribeiro

259

15-P-17 - DFT study of structure changes in hydrated A1PO4-n: The case of A1PO4-34 G. Poulet, A. Tuel and P. Sautet

259

15-P-18 - A mechanistic exploration of alkene epoxidation mediated by H202 within porous titanosilicate catalysts C.M. Barker, N. Kaltsoyannis and C.R.A. Catlow

260

15-P-19 - Transition-state shape-selectivity insights from a Fukui function overlap method L.A. Clark and R. Q. Snurr

260

15-P-20 - A DFT study of the isomerization reactions of aromatics catalyzed by acidic zeolites X. Rozanska, R.A. van Santen, F. Hutschka and J. Hafner

260

15-P-21 - Ab-initio investigation of non-framework aluminum species in zeolites D. Lopes Bhering, C.J.A. Mota and A. Ramirez-Solis

261

15-P-22 - A DFT study of the cracking reaction of thiophene activated by zeotype catalysts: role of the basic Lewis site X. Rozanska, R.A. van Santen and F. Hutschka

261

15-P-23 - Modelling transition metal cations in zeolites: how do they interact with the framework? D. Berthomieu, A. Goursot, J-M. Ducdr~, G. Delahay, B. Coq and A. Martinez

261

15-P-24 - Theoretical prediction of IR spectra of guest molecules in zeolites: the stretching frequency of CO adsorbed at various cationic sites in ZSM-5 T.A. Wesolowski, A. Goursot and J. Weber

262

15-P-25 - Development of a tight-binding treatment for zeolites M. Elstner, A. Goursot, Z. Hajnal, T. Heine and J. Weber

262

15-P- 26 - 1-D growth of selenium wires in silicalite-1 zeolite C. Bichara and R.J.-M. Pellenq

262

15-P-27 - Cumulative coordinates for approximations of atomic multipole moments in cationic forms of aluminosilicates A. V. Larin and D.P. Vercauteren

263

15-P-28 - Computer simulations of water in zeolites C. Bussaia, R. Haberlandt, S. Hannongbuai and S. Jost

263

16 - Modelling and Theoretical Studies B 16-0-01 Simulating shape selectivity in alkane hydroconversion by zeolites M. Schenk, T.L.M. Maesen and B. Smit

155

16-O-02 - Molecular dynamics of the faujasite (111) surface B. Slater and C.R.A. Catlow

155

16-0-03 - Adsorption of xylene isomers and water in faujasites. A molecular simulation study S. Buttefey, A. Boutin and A.H. Fuchs

155

16-0-04 - Reaction dynamics in acidic zeolites: room temperature tunneling effects J. T. Fermann and S.M. Auerbach

156

16-0-05 - Molecular modeling of multicomponent diffusion in zeolites and zeolite membranes M.J. Sanborn, A. Gupta, L.A. Clark and R.Q. Snurr

156

16-P-06 - Location of triethylmethylammonium ions in MFI by combining molecular modeling and X-ray diffraction R. Millini

264

16-P-07 - A hypothetical zeolite structure MCR16: topological design and template choice B. Li, P. Sun, Q. Jin and D. Ding

264

16-P-08 - Computational analysis of the shape-selective isopropylation of biphenyl over large pore zeolites

J. Joffre, D. Mravee and P. Moreau

264

16-P-09 - De novo simulation and spectroscopic study of iron speciation in ZSM-5 and CIT-5

P.-PH.J.M. Knops-Gerrits and W.A. Goddard III

265

16-P-10 - Exact statistical mechanical treatment of a lattice model of hydrocarbon adsorption on zeolites

G. Manos, L.J. Dunne, Z Du and M.F. Chaplin

265

16-P-11 - Computational studies of the structure of Na- and H-Mordenite

A.E. Gray, A. 0 'Brien and D. W. Lewis

265

16-P-12 - Monte Carlo simulation of isobutane in silicalite

D. Paschek and R. Krishna

266

16-P- 13 - Characterisation of hypothetical zeolite frameworks

M.D. Foster, R.G. Bell and J. Klinowski

266

16-P-14 - Cation mobility and the sorption of chloroform in zeolite NaY: a molecular dynamics study

N.A. Ramsahye and R.G. Bell

266

16-P- 15 - Computational studies of the calcination of fluorinated gallophosphates: exploration of their template-free calcined forms

S. Girard, J.D. Gale, C. Mellot-Draznieks and G. Fdrey

267

16-P-16 - Molecular simulation studies on the effectiveness of template type on TS- 1 crystal morphology

tl. Zhou, H. He and Z Jing

267

16-P-17 - A molecular dynamic approach on the selective conformational change of ethylene glycol in sodalite cage

M. Sato

267

16-P-18 - The mutual influence of dynamic processes acting in different time scales

S. Fritzsche, R. Haberlandt, A. Schfiring and M. Wolfsberg

268

16-P-19 - Lattice-dynamical calculations for zeolites of natrolite group

S. V. Goryainov and M.B. Smirnov

268

16-P-20 - Kinetic modelling of the dynamic interaction between NO and N20 over Cu-ZSM5

R. Pirone, P. Ciambelli, A. Di Benedetto, B. Palella and G. Russo

268

lii

17- Principles of Adsorption 17-0-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single cylindrical pore

K. Morishige and Y. Ogisu

137

17-0-02 - Structural study of benzene, tetrachloroethene and trichloroethene sorbed phases in silicalite-1

N. Floquet, J.P Coulomb, G. Weber, O. Bertrand and J.P Bellat

137

17-0-03 - Molecular ordering of the adsorbed phase within the microporous model aluminophosphate A1PO4-11 at cryogenic temperatures

N. Dufau, N. Floquet, J-P. Coulomb, P.L. Llewellyn and J. Rouquerol

137

17-0-04 - - Adsorption properties of a supercritical fluid on mesoporous molecular sieves under high pressure

Ya. Goto, N. Setoyama, Y. Fukushima, T. Okubo, Yu. Goto, Y. lmada, Y. Kubota and Y. Sugi

138

17-P-05 - Confinement in model host materials: experimental study of quasi-(1 d) systems.

J.P. Coulomb, N. Floquet, C. Martin, Y. Grillet and J. Patarin

222

17-P-06 - Studies on desorption behavior of organics on siliceous ferrierite B. Qian, Y. Zeng and Y.-C. Long

222

17-P-07 - Investigation of hydrocarbon adsorption on large and extra-large pore zeolites

C. Y. Chen and S.I. Zones

222

17-P-08 - Different chemisorption methods applied to zeolite supported Pt-catalysts

J.C. Groen, J. P~rez-Ramirez and L.A.A. Peffer

223

17-P-09 - Structure vs. adsorption properties of 5A zeolites H. Paoli, T. Bataille, B. Rebours, A. M~thivier and H. Jobic

223

17-P-10 - Hydrogen adsorption in lithium exchanged Na A zeolites S. Kayiran, F. Darkrim and A. Gicquel

223

17-P- 11 - Macroscopic and microscopic investigations of the interaction of a chloroalkene on a MFI zeolite

V. Francois, S. Maure, F. Bouvier, G. Weber, O. Bertrand, J.P. Bellat and C. Paulin

224

17-P-12 - Sorption and pore condensation behavior of pure fluids in mesoporous MCM-48 silica, MCM-41 silica and controlled pore glass

M. Thommes, R. KOhn and M. FrOba

224

liii

17-P-13 - Pore size analysis with H20 adsorption measurement of organically modified MCM-41 type materials

N. Igarashi, K. Nakai, K. Hashimoto and T. Tatsumi

224

17-P-14 - Adsorption of carbon dioxide by X zeolites exchanged with Z n 2+ and Cu2+: isosteric heat and adsorption isotherms

A. Khelifa, Z. Derriche and A. Bengueddach

225

17-P-15 - A combination of high resolution manometry, gravimetry and microcalorimetry to study the co-adsorption of Ar/N2 mixtures on 5A and 13X zeolites

S. Moret, F. Rouquerol, J. Rouquerol and P.L. Llewellyn

225

17-P-16 - Gas adsorption microcalorimetry on zeolites under supercritical conditions up to 15 bars

T. Poyet, F. Rouquerol, J. Rouquerol and P.L. Llewellyn

225

18- Adsorption and Separation Process 18-0-01 - An experimental adsorbent screening study for CO2 removal from flue gas

P.J.E. Harlick, H. Halsall-Whitney and F. Handan Tezel

143

18-0-02 - Amino acids in BEA type channels

C. Buttersack and A. Perlberg

143

18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2 hydrocarbons on modified LTA-type zeolites

C.J. Guo, D. Shen and M. Btilow

144

18-0-04 - A novel adsorbent for the separation of propane/propene mixtures

W. Zhu, F. Kapteijn and J. A. Moulijn

144

18-0-05 - Iodide removal using zeolite-based reactive adsorption

S. Kulprathipanja and B. Spehlmann

144

18-P-06 - Evaluation of mesoporous silicas as stationary phases for high performance liquid chromatography (HPLC)

L. Sierra, B. Lopez, A. Ramirez and J.-L. Guth

226

18-P-07 - Adsorption of N-nitrosamines by zeolites in solutions

Ying Wang, J.H. Zhu, D. Yan, W. Y. Huang and L.L. Ma

226

18-P-08 -An adsorption-desorption process for separation of C8 aromatics

G.-Q. Guo and Y.-C. Long

226

liv 18-P-09 - Preparation of Na-A zeolite capillary columns by in-situ synthesis

D. Kou, Z. Li, J. Wu, Ming Liu and S. Xiang

227

18-P-10 - Adsorption of C02, S02 and NH3 on zeolitic materials synthesized from fly ash

S. Herndndez, R. Juan, X. Querol, N. Moreno, P. Ferrer and J.M. Andrds

227

18-P-11 - Dibenzothiophene adsorption over zeolites with faujasite structure

J.L. Sotelo, M.A. Uguina, M.D. Romero, J.M. G6mez, V.I. Agueda and M.A. Ortiz

227

18-P-12 - Pressure swing adsorption of ethyl acetate on silica MCM-41

S. Namba, D. Yomoda, J. Aoyagi, K. Minagawa, T. Kugita and J. Izumi

228

18-P-13 - P occlusion in LTA: an approach for enhancing N2 adsorption properties

L. Johnson and M. Miller

228

18-P-14 - Sulfur guard bed material from local bentonite deposits

S. Mikhail and T. Zaki

228

18-P- 15 - Simulation for removal of binary solvent vapor by adsorption onto high silica zeolite.

K. Chihara, T. Saito, H. Suzuki, H. Yamaguchi and Y. Takeuchi

229

1 9 - Diffusion: Fundamental Approach 19-0-02 - Studies of adsorption, diffusion and molecular simulation of cyclic hydrocarbons in MFI zeolites

L. Song, Z L. Sun and L. V. C Rees

153

19-0-03 - The effect of silanisation on the intracrystalline diffusivity of ZSM-5

W.L. Duncan and K. P. MOller

154

19-0-04 - Interference microscopy as a tool of choice for investigating the role of crystal morphology in diffusion studies

O. Geier, S. Vasenkov, E. Lehmann, J. Kgirger, R.A. Rakoczy and J. Weitkamp

154

19-0-05 - Estimation of the interphase thickness and permeability in polymerzeolite mixed matrix membranes

A. Erdem-~enatalar, M. Tather and ~.B. Tantekin-Ersolmaz

154

19-P-06 - Modeling of sulfur dioxide breakthrough curves from ternary wet mixtures on MOR type zeolite

M. Mello, M. EiO, S. Ho&var and U. Lavrendid-Stangar

269

lv 19-P-07 - The diffusion and sorption dynamics of acetylene in zeolites Gy. Onyesty6k, J. Valyonand and L. K C. Rees

269

19-P-08 -Transient uptake measurements using an oscillating microbalance: effect of acid leaching on the diffusivity of n-hexane in Pt/H-Mordenite S. van Donk, A. Broersma, O.L.J. Gijzeman, J.H. Bitter and K.P. de Jong

269

19-P-09 - Use of 129XeNMR spectroscopy to study gaseous hydrocarbon diffusion in a fixed bed of HZSM-5 zeolite M.-A. Springuel-Huet, P N'Gokoli-Kekele, C. Mignot, J.-L. Bonardet and J. Fraissard

270

19-P-10 - Adsorption and diffusion of alkanes and their mixtures in silicalite studied with positron emission profiling technique A. O. Koriabkina, D. Schuring, A.M. de Jong and R.A. van Santen

270

2 0 - Zeolite Membranes and Films 20-0-01 - Polyamines as strong covalent linkers for the assembly of mono and double layers of zeolite crystals on glass K. Ha, Y.S. Chun, A. Kulak, Y.S. Park, Y. -J. Lee and K.B. Yoon

161

20-0-02 - The use of seeds in the synthesis of mono-and bi-layered zeolite membranes L. Gora, G. Clet, J.C. Jansen and Th. Maschmeyer

162

20-0-03 - Growth of oriented mordenite membranes on porous (x-AI203 supports G. Li, X. Lin, E. Kikuchi and M. Matsukata

162

20-0-04 - Depth-sensitive structural study of silicalite-1 films with grazing incidence X-ray diffraction S. Mintova, T.H. Metzger and T. Bein

162

20-0-05 - Regeneration of supercritical carbon dioxide by alumina supported MFI zeolite and mesoporous silica membranes K.J. Chao, C.H. Kao, Y.W. Chiu, X.R. Lin and C.S. Tan

163

20-P-06 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type zeolite membranes as reactors X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu

291

20-P-07 - Preparation of high-permeance ZSM-5 tubular membranes by varyingtemperature synthesis Y.-S. Li, Xio. Zhang, J.-G. Wang and S. Guo

291

lvi

20-P-08 - Synthesis of FAU type films on steel supports using a seeding method

Z Wang, J. Hedlund and J. Sterte

291

20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials

O. Ohrman, U Nordgren, J. Hedlund, D. Creaser and J. Sterte

292

20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in zeolite A membranes

M. Lassinantti, J. Hedlund and J. Sterte

292

20-P-11 Pure-silica zeolite low-k dielectric thin films by spin-on process

Zhen. Wang, H. Wang, A. Mitra, L. Huang and Yu. Yan

292

20-P-12 - Preparation of silicalite-1 and beta zeolite/ceramic composite membranes and removal of trace phenol and benzene from water through them 293

Xiansen Li and S. Xiang 20-P-13 - Factors affecting film thickness in the preparation of supported ZSM-5 zeolite

E.I. Basaldella, A. Kikot, J.E Bengoa andJ. C. Tara

293

20-P-14 - Growing zeolite films onto gold surfaces

E I. Basaldella, A. Kikot, J.O. Zerbino and J.C. Tara

293

20-P- 15 - Diffusivities of zeolite coatings

M. Tather, ~.B. Tantekin-Ersolmaz andA. Erdem-~enatalar

294

20-P-16 - Crystal growth mechanism of LTA and FAU and densification process of zeolite film by seed growth

I. Kumakiri, Y. Sasaki, W. Shimidzu, T. Yamagushi. and S.-I. Nakao

294

20-P-17 - In-situ synthesis of ZSM-5 on aluminum surfaces F. Scheffler and W. Schwieger

294

20-P- 18 - Conceptual process design of an all zeolite membrane reactor for the hydroisomerization of CflC6

E.E. McLeary, R.D. Sanderson, C. Luteijn, E.J.W. Buijsse, L. Gora, Th. Maschmeyer and J. C. Jansen

21 - N a n o c o m p o s i t e

Fundamentals

295

and Applications

21-O-02 - Methods of synthesis for the encapsulation of dye molecules in molecular sieves

M. Wark, M. Ganschow, Y. Rohlfing, G. Schulz-Ekloff and D. Wohrle

160

lvii 21-O-03 -MCM-41 silica monoliths and diluted magnetic semiconductors: a promising union for fabricating nanosized quantum wires

F. Brieler, M. Brehm, L. Chen, P.J. Klar, W. Heimbrodt and M. FrOba

160

21-O-04 - Potential microlasers based on AIPO4-5/DCM composites

O. Weifl, F. Schuth, L. Benmohammadi and F. Laeri

161

21-O-05 - Light-emitting BN, Si, and SiC nanoparticles encapsulated in molecular sieves

Xiaotian Li, C. Shao, F. Gao, S. Qiu, F.-S. Xiao and O. Terasaki

161

2 l-P-06 - Fabrication of hollow fibers and spheres composed of zeolites by layerby-layer adsorption method

E Tang, Y.-J. Wang, X.-D. Wang, W.-L. Yang and Z. Gao

296

2 l-P-07 - The zeolitisation of diatoms to create hierarchical pore structures

S.M. Holmes, R.J. Plaisted, P. Crow, P. Foran, C.S. Cundy and M. W Anderson

296

2 l-P-08 - Generating the narrowest single-walled carbon nanotubes in the channels of A1PO4-5 single crystals

G.D. Li, Z.K. Tang, N. Wang, K.H. Wong and J.S. Chen 21-P-09

-

296

Zeolite- an effective nucleating agent of NazHPO4" 12H20

J. Dong, X. Jing and Yu. Zhang

297

2 l-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite hosts

Yi. Zhang, Xu. Wang and Xi. Wang.

297

2 l-P-11 - Encapsulation of Mn(bipy)2 into the zeolite Y prepared via different routes

B. Fan, W Cheng and R. Li

297

2 l-P-12 - Preparation of zeolite Beta/polystyrene beads and the corresponding hollow spheres

V. Valtchev and S. Sferdjella

298

2 l-P-13 - Synthesis, characterization and catalysis of manganese(II) complexes encapsulated in NaX and NaY zeolites

J.M. Silva, R. Ferreira, C. Freire, B. de Castro and J. L. Figueiredo

298

2 l-P-14 - Guest-host interactions in systems containing liquid crystals confined to molecular sieves

S. Frunza, L. Frunza, A. SchOnhals, H.-L. Zubowa, H. Kosslick and R. Fricke

298

2 l-P-15 - Zeolite Beta ordered macroporous structures with improved mechanical strength and controlled mesoporosity

V. Valtchev, S. Sferdjella and H. Kessler

299

lviii 2 l-P- 16 - Synthesis of zeolites with organic lattice

K. Yamamoto, Y. Takahashi and T. Tatsumi

299

2 l-P-17 - Crystallization mechanism of A1MePO-I3

Y. Qi, G. Wang and Z. Liu

299

2 l-P-18 - Crystal structure and magnetic properties of rubidium clusters in zeolite LTA

T. Ikeda and T. Kodaira

22 - Advanced

300

Materials

22-0-01 - The effect of the location of framework negative charge on the ordering of templates in zeolite IFR

R.E. Morris and L.A. Villaescusa

168

22-0-02 - A new family of microporous vanadium phosphates and related compounds with organic coordination

S. Feng, Z. ShL L. Zhang, H. Zhao, D. Zhang and Z Dai

168

22-0-03 - Catalytic properties of novel nickel(II) phosphate with nanoporous structure

J.-S. Chang, D.S. Kim, S.-E. Park, P.M. Forster, A.K. Cheetham and G. Ferey

169

22-0-04 - Characterization of corrosion-resistant zeolite coatings on A1 alloys

H. Wang, Zhen. Wang, X. Cheng, A. Mitra, L. Huang and Y. Yan

169

22-0-05 - Template synthesis and catalysis of bimetallic platinum-rhodium and palladium nanowires in mesoporous materials

A. Fukuoka, Y. Sakamoto, S. Inagaki, iV. Sugimoto, Y. Fukushima and M. Ichikawa

169

22-P-06 - Tailored generation of titanium oxide species within porous Si-MCM-41

P. Prochnow, G. Schulz-Ekloff M. Wark, J.K. Thomas, A. Zukal and J. Rathousky

359

22-P-07 - Optical switching with photochromic dye molecules encapsulated in the pores of molecular sieves by in-situ synthesis

C. Schomburg, D. WOhrle, G. Schulz-Ekloff and M. Wark

359

22-P-08 - Formation of carbon nanotubes on various molecular sieves supported metal oxides

A. M Zhang, Q H. Xu, J.J. Zhao and J.M. Cao

359

lix 22-P-09- Encapsulation of Tb[(C1BOEP)4P](acac) in Si-MCM-41 by the method of ship-in-bottle and its luminescent properties at 77 K

Q Xu, Z. Zhao, L. LL G. Liu, 11. Ding, J. Yu and R. Xu

360

22-P-10 - A new adsorbent with magnetic properties based on natural clinoptilolite

V. Pode, V. Georgescu, V. Dalea, R. Pode and E. Popovici

360

22-P-11 - Preparation of microcalorimetric gas sensors with CoAPO-5

S. Mintova, J. Visser and T. Bein

360

22-P-12 - Study of cation-exchange properties of an organozeolite

V.A. Nikashina, E.M. Kats, 1. V. Komarova, N.K. Galkina and K.1. Sheptovetskaja

361

22-P-13 - Advanced electrode materials based on mesoporous aluminumstabilized anatase

A. Attia, S.H. Elder, R. Jir6sek, L. Kavan, P. Krtil, J. Rathousk~ and A. Zukal

361

22-P-14 - Dye-zeolite assemblies for optical sensing applications

J.L. Meinershagen and T. Bein

361

22-P-15 - A new sorbent based on clinoptilolite-containing tuff modified by polyethylene

1.N. Meshkova, V.A. Nikashina, T.M. Ushakova, V.G. Grinev, N. Yu. Kovaleva, A.A. Zaborskii, T.A. Ladygina and L.A. Novokshonova

362

22-P-16 - Molecular sieves from pillaring of some romanian bentonite

E. Popovici, 1. Bedelean, D. Pop, G. Singurel, D. Macocinschi and H. Bedelean

362

22-P-17 - Electronic states and arrangements of AgI and CuI clusters incorporated into zeolite LTA

T. Kodaira and T. Ikeda

362

22-P-18 - PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical properties

G. Telbiz, O. Shvets, V. Vozny and M. Brodyn

363

22-P-19 - Application of the molecular sieves as matrices for the pigments

S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk

363

22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction and fluorescence properties

363

G. Telbiz, O. Shvets, S. Boron, V. Vozny, M. Brodyn and G. Stucky 22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the structural type MCM-41

B. Onida, B. Bonelli, M. Lucco-Borlera, L. Flora, C. Otero Aredn and E. Garrone

364

lx 23 - M i c r o - a n d M e s o p o r o u s

M a t e r i a l s in F i n e C h e m i s t r y

23-0-02 - Pd-zeolites as catalysts for the Heck reaction: a screening of reaction parameters affecting catalyst heterogeneity M. Dams, D.E. De Vos, L. Drij'koningen and P.A. Jacobs

138

23-0-03 - Beckmann rearrangement of cyclohexanone oxime over mesoporous MCM-41 and MCM-48 type materials R. Glaser, 11. Kath and J. Weitkamp

139

23-0-04 - Knoevenagel condensation between ethylcyanoacetate and benzaldehyde over base catalysts immobilized on mesoporous materials Y. Choi, K.-S. Kim, J.-H. Kim and G. Seo

139

23-0-05 - One-step synthesis of MIBK from acetone over Pt/X catalysts L. V. Mattos, F.B. Noronha andJ.L.F. Monteiro

139

2 3 - P - 0 6 - Selective hydroxyethylation of furfuryl alcohol with aqueous acetaldehyde in the presence of H-form zeolites A. Finiels, W. Balmer and C. Moreau

230

23-P-07 - Selective synthesis of monooctylamines by ammonia alkylation with octanol using NaY, ZSM-5, SAPO-5, SAPO-1 l, SAPO-31, SAPO-34 S. Amokrane, R. Rebai, S. Lebaili, D. Nibou and G. Marcon

230

23-P-08 - Conversion of monoethanolamine in other organic nitrogen compounds on H-mordenite and H-clinoptilolite G. Torosyan, S. Sargsyan and A. Grigoryan

230

23-P-09 - The influence of ammonia adsorption on Y Zeolite and natural clinoptilolite activity in ethanol transformation L. Akhalbedashvili, A. Mskhiladze and Sh. Sidamonidze

231

23-P-10 - Enantioselective synthesis and separation of terminal epoxides and diols using a catalytic membrane system containing chiral Co(III) salen S.-D. Choi and G.-J. Kim

231

23-P-11 - Asymmetric trimethylsilylcyanation of benzaldehyde catalyzed by chiral Yi(IV) salen complexes immobilized on MCM-41 J.-H. Kim and G.-J. Kim

231

23-P-12 - Mechanistic study of aniline methylation over acidic and basic zeolites Y 1.1. lvanova, E.B. Pomakhina, A.1. Rebrov, Yu.G. Kolyagin, M. Hunger and J. Weitkamp

232

23-P-13 - Heterogeneous base catalysis" characterization of zeolites and mixed oxides using nitromethane as a NMR probe molecule and activity in the Michael condensation of nitromethane and cyclohex-2-en-l-one E. Lima, L.-C. de Mdnorval, M. Laspdras, J.-F. Eckhard, D. Tichit, P. Graffin and F. Fajula

232

lxi 23-P-14 - Synthesis of ot-pinene derivatives using redox-mesoporous molecular sieves

Y.-W. Suh, T.-M. Son, N.-K. Kim, W.-S. Ahn and H.-K. Rhee

232

23-P-15 - Ring opening reactions of methyloxirane over DZSM-5 and DA1MCM-41 molecular sieves - A mechanistic study

A. Fdsi, I. Pdlink6, ,4. GOmOry and I. Kiricsi

233

23-P-16 - Hydrodechlorination of 1,2,4-trichlorobenzene on Ni/A1-MCM-41 catalysts

Y. Cesteros, P. Salagre, F. Medina, J.E. Sueiras and G.L. Haller 23-P-17

-

233

Adsorption of cytochrome c onto ordered mesoporous silicates

J. Deere, E. Magner, J.G. Wall and B.K. Hodnett

233

23-P-18 - Vapor phase Beckmann rearrangement of cyclohexanone oxime over tantalum pillared magadiite

S.J. Kim, M.H. Kim, Y. Ko, G. Seo and Y.S. Uh

234

23-P-19 - Hydration of a-pinene over heteropolyacids encaged.in USY zeolites

J. Vital, A.M. Ramos, I.F. Silva, J.E. Castanheiro, M.N. Blanco, C. Caceres, P. Vasquez, L. Pizzio and H. Thomas

234

23-P-20 - Selective adsorption of trans unsaturated fatty acid compounds in MFI type zeolites

S. Paulussen, M. Goddeeris and P.A. Jacobs

234

23-P-21 - Novel delaminated zeolites are more active acid catalysts than conventional zeolites and mesoporous AI/MCM-41 for the synthesis of fine chemicals

M.J. Climent, A. Corma, V. Fornds, H. Garcia, S. Iborra, J. Miralles and I. Rodriguez

235

23-P-22 - The design of zeolites catalysts for the synthesis of orange blossom and apple fragrances

M.J. Climent, A. Corma and A. Velty

235

23-P-23 - Catalytic in-situ infrared spectroscopic study of n-butyraldehyde aldol condensation

U. Rymsa, M. Hunger and J. Weitkamp

235

23-P-24- Oxyhalogenation of aromatic compounds in presence of KC1 or KBr and H202 over zeolites.

N. Narender, P. Srinivasu, S.J. Kulkarni and K. V. Raghava~

236

lxii 23-P-25 - Synthesis and characterization of mesoporous Pt-MCM-41 and its application in enantioselective hydrogenation of 1-phenyl-1,2-propanedione

E. Toukoniitty, B. Sevcikovdt, N. Kumar, P. Mdiki-Arvela, T. Salmi, J. Vdiyrynen, T. Ollonqvist, E. Laine, P.J. Kooyman and D. Yu. Murzin

236

23-P-26 - Isomerization of p-eugenol on palladium-containing zeolites

Ts.M. Ramishvili, M.K. Charkviani and L.D. Kashia

236

23-P-27 - The use of MCM-22 as catalyst for the Beckmann-rearrangement of cyclohexanone oxime to e-caprolactam

G. Dahlhoff U. Barsnick, W. Eickelberg and W.F. HOlderich

237

23-P-28 - Nickel supported on zirconium doped mesoporous silica as catalysts for the gas phase hydrogenation of acetonitrile

P. Braos-Garcia, L. Diaz, P. Maireles-Torres, E. Rodriguez-Castell6n and A. Jim6nez-L6pez

237

23-P-29 - Synthesis of fine chemicals intermediates over basic zeolites

C.O. Veloso, A.C. Pinto, E.N. Santos and J.L.F. Monteiro

237

23-P-30 - Selective chlorination of diphenylmethane over zeolite K-L 238

A.P. Singh and S.M. Kale 23-P-31 - Butylation of phenol on medium pore A1PO4 -11, -31 and -41 structures: effect of silicon incorporation

C. V. Satyanarayana, U. Sridevi and B.S. Rao

238

23-P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate in presence of zeolite A 238

J. W. Yoo and Z. Mouloungui 23-P-33 - Transfer hydrogenation of unsaturated ketones catalyzed by Al-isopropoxide dispersed on MCM-41

J. Wahlen, D.E. De Vos, M. De bruyn, PJ. Grobet and PA. Jacobs

2 4 - N e w R o u t e s to H y d r o c a r b o n

239

Activation

24-0-01 - Dehydroisomerization of n-butane to isobutene over Pd modified silicoaluminophosphate molecular sieves

Y. Wei, G. Wang, Z. Liu, C. Sun and L. Xu

145

24-0-02 - Conversion of methane over Ag-Y in the presence of ethene

T. Baba, H. Sawada, Y. Abe and Y. Ono

145

24-0-03 - Peculiarities in the hydroconversion of n-hexadecane over bifunctional catalysts

L. Perrotin, A. Finiels, F. Fajula and T. Cholley

145

lxiii 24-0-04 - HI3 catalyzed heterogeneous aziridination of olefins

B. Chanda, R. Vyas, A. V. Bedekar, B.B. Kasture and V.N. Joshi

146

24-0-05 - MCM-41 as support for metallocene catalysts - ethylene polymerization

C.A. Henriques, M.F.V. Marques, S. Valange, Z Gabelica and J.L.F. Monteiro

146

24-P-06 - Study of coke and deactivation over H-Beta zeolite

Z Zhu, T. Ruan, Q. Chen, W. Chen and D. Kong

271

24-P-07- Photoionization of N-alkylphenothiazines in transition-metal-ion modified mesoporous silica SBA-15 molecular sieves

Z. Luan and L. Kevan

271

24-P-08 - Potential use of AIMCM-41 for activation of metallocene catalyst

T. Sano, T. Niimi, T. Miyazaki, S. Tsubaki, Y. Oumi and T. Uozumi

271

24-P-09 - Activation of butanes with olefins carbenium cations over zeolite catalysts

S.E. Dolinsky and V.A. Plakhotnik

272

24-P-10 - Immobilization and mobilization of surface species during transformation of ethylene over HZSM-5 catalysts

Ziktinovgt, M. Ko~iHk, M. Derewihski, P. Sarv, J. Dubsk~, P. Hudec and A. SmieJkovd

272

24-P-11 - Zeolite-L as support of Fe microcystals for the Fischer-Tropsch synthesis

M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, A.A. Yeramian and S. G. Marchetti

272

24-P-12 - Nb- and Ti-containing silica-based mesoporous molecular sieves as catalysts for photocatalytic oxidation of methane

J. Xin, X. Chen, J. Suo, Xia. Zhang, L. Yan and Shuben Li

273

24-P-13 - Catalytic properties of micelle templated microporous and mesoporous materials for the conversion of low-density polyethylene

J. Aguado, D.P. Serrano, R. Van Grieken, J.M. Escola and E. Garagorri

273

24-P-14 - Epoxidation of propylene in fixed bed reactor using supported titanium silicalite catalyst

X.S. Wang, Gang Li, H.S. Yan and X. W. Guo

273

24-P-15 - Acetylene and alkene oligomerization on ETS-10 having induced Bronsted acidity

A. Zecchina, C. Paz& C. Otero Aredn, G. Turnes Palomino, F.X. Llabr& i Xamena and S. Bordiga

274

lxiv 24-P-16 - Isomerization of n-butane over small crystals of H-Beta and Pt-H-Beta zeolite catalysts N. Kumar, M. Vaini, V. Nieminen, R. Byggningsbacka, L.-E. Lindfors, T. Salmi, D. Yu. Murzin and E. Laine

274

24-P-17 - Ethylene oligomerization with nickel-containing NaX zeolite M.O. de Souza, F.M.T. Mendes, R.F. de Souza, J.H. Z. dos Santos, L. Caumo, V. Conz, F. Majolo and L. V. Barbosa

274

24-P-18 - Studies of the methanol to hydrocarbons reaction using isotopic labeling: mounting evidence for a hydrocarbon pool mechanism S. Kolboe

275

24-P-19 - Formation and reactivity of alkoxy species through the reaction of alkylhalides with metal-exchanged zeolites R.J. CorrOa and C.J.A. Mota

275

24-P-20 The use of ITQ-7 as catalyst for alkylation of isobutane with 2-butene A. Corma, M.J. Diaz-Cabaftas, C. Martinez and S. Valencia

275

24-P-21 Butene isomerization over ferrierite and SUZ-4 zeolite V.L. Zholobenko and C.L.T. Stevens

276

24-P-22 - Volatile products of the conversion of cyclohexene over AI-MCM-41 M. Rozwadowski, M. Lezanska, J. Wloch, K. Erdmann, G. Zadrozna and J. Kornatowski

276

24-P-23 M. Laniecki

276

-

-

-

C u - Y

zeolite catalysts for methanol and ethanol steam reforming

24-P-24 - Hexenes obtaining on the nickel - ion exchanged zeolites M.K. Munshieva

277

24-P-25 - Catalytic sites of mesoporous silica in degradation of polyethylene A. Satsuma, T. Ebigase, Y. Inaki, H. Yoshida, S. Kobayashi, Md.A. Uddin, E Sakata, and T. Hattori

277

24-P-26 - The nature of medium acidity in [CuO/ZnO/ZrO2]SAPO-34 hybrid catalyst for CO2 hydrogenation: the study of the interactions between metal oxides and acid sites in zeolite S.-K. Ihm, S.-W. Back, Y.-K. Park and K.-C. Park

277

24-P-27 - Reaction pathways for the aromatization of cyclohexane and cyclohexene on Zn/H-ZSM-5 zeolites A. Urdgt, G. Telbiz and I. Sgmdulescu

278

lxv 24-P-28 - Coke species and coking mechanism of SAPO-34 in MTO process

Y. Qi, G. Wang, Z. Liu, L. Xu, X. Gao and W. Cui

278

24-P-29 - Pt-2,2'bipyridine complex encapsulated in Y zeolite - catalysts for ethylene selective dimerization

R. Zavoianu and E. Angelescu

278

24-P-30 - Aromatics formation from C4-C4- technical fraction over zinc- and zinc/copper-containing ZSM-5 zeolites

N. Bilba, Gh. Iofcea, 1. Asafiei, D.M. Padurariu and C.C. Pavel

279

24-P-31 - Aromatization of mixed-C4 hydrocarbons over the HZSM-5 catalysts modified by Zn and Ni cations

L. Wei, J.Z. Gui, H.S. Ding, X.T. Zhang, H.Y. Li, L. Song, Z.L. Sun and L. V.C. Rees

279

25 - C o n v e r s i o n of A r o m a t i c s

25-0-01 - Shape-selective methylation of 4-methybiphenyl into 4,4'dimethybiphenyl over modified ZSM-5 catalysts

J.-P. Shen, L. Sun and C. Song

151

25-0-02 - Facile Friedel-Craft's alkylation of phenol with 4-hydroxybutan-2-one over 13 and Y zeolites to produce raspberry ketone

K.K. Cheralathan, 1.S. Kumar, B. Arabindoo, M. Palanichamy and V. Murugesan

152

25-0-03 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene catalyzed by MTW zeolite

G. Pazzuconi, G. Terzoni, C.Perego and G. Bellussi

152

25-0-04 - Transalkylation reaction of phenol with trimethylbenzenes over Y and EMT zeolites

V. Hulea, 1. Fechete, P. Caullet, H. Kessler, T. Hulea, C. Chelaru, C. Guimon and E. Dumitriu

152

25-0-05 - Benzene alkylation with alkanes over modified MFI catalysts

A. V. Smirnov, E. V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko and 1.1. Ivanova

153

25-P-06 - Isopropylation of napthalene over large pore zeolites

R.K. Ahedi, S. Tawada, Y. Kubota and Y. Sugi

280

25-P-07 - Shape-selective tert-butylation of biphenyl over HM, HY and HI3 zeolites in the liquid phase

D. Mravec, J. Horniakovd, M. Krdlik, M. Hronec, J. Joffre and P. Moreau

280

lxvi 25-P-08 - 1-Acetyl-2-methoxynaphthalene isomerization over zeolites. Effect of pore structure. V. Moreau, E. Fromentin, P. Magnoux and M. Guisnet

280

25-P-09 - Alkylation of phenol with propylene over solid acid catalysts B. Wang, C. W. Lee, T.-X. Cai and S.-E. Park

281

25-P-10 - Transalkylation of trimethylbenzene with toluene over large pore zeolites J. Cejka, A. Krejdi and J Hanika

281

25-P-11 - Physicochemical characterization and catalytic activity of A1-HMS for N-methylation of aniline JM. Campelo, A. Garcia, D. Luna, J.M Marinas, A.A. Romero and J.J. Toledano

281

25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular sieve A1MCM-41 in the Friedel-Crafis reaction of bulky aromatic compounds H. Hamdan, A.B. Kim and M.N. Mohd Muhid

282

25-P-13 - Naphthalene alkylation with methanol employing solid catalysts J. Aguilar-P, A. Corma, J.A. de los Reyes, L. Noreha, G. Muhoz, J.M. Sanchez, A. Torales and I. Herndndez

282

25-P-14 - Alkylation of biphenyl and naphthalene with propene. Is zeolite Beta a shape-selective catalyst? D.M. Roberge and W.F. Holderich

282

25-P-15 - Alkylation of benzene by propane with participation of space divided centres S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov

283

25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts supported on mesoporous materials M-W. Kim, W.-G. Kim, J.-H. Kim, Y. Sugi and G. Seo

283

25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta C.R. Patra, S. Kartikeyan and R. Kumar

283

26 - Catalysis for Oil Refining

26-0-01 - The isomerization selectivity in FCC process L.-J. Yan, M-Y. He, J. Fu and J. Long

158

26-0-02 - Design of zeolite catalyst for paraffin isomerisation J. Hou~vidka, C.J.H. Jacobsen and I. Schmidt

158

26-0-03 - Cyclohexane ring opening on metal-zeolite catalysts T.V. Vasina, O.V. Masloboishchikova, E.G. Khelkovskaya-Sergeeva, L.M. Kustov and P. Zeuthen

159

lxvii 26-0-04 Selective ring opening of naphthenic molecules M. Daage, G.B. Mc Vicker, M.S. Touvelle, C. W. Hudson, D.P. Klein, B.R. Cook, J.G. Chen, S. Hantzer, D.E.W. Vaughan and E.S. Ellis

159

26-0-05 - Reforming of FCC heavy gasoline and LCO with novel borosilicate zeolite catalysts C. Y. Chen and S.I. Zones

159

26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of metal-acid balance and metal location L.B. Galperin, S.A. Bradley and T.M. Mezza

301

26-P-07 - Hydrodesulfurization of benzothiophene over noble metals supported on mesoporous silica MCM-41 M. Sugioka, A. Seino, T. Aizawa, J.K.A. Dapaah, Y. Uemichi and S. Namba

301

26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating catalysts K.S. Rawat, M.S. Rana and G. Murali Dhar

301

26-P-09 - Highly active, selective and stable ferrierite-based catalysts for the skeletal isomerization of n-C5-C7 C.P. Nicolaides, J. Makkonen and M. Tiitta

302

26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or aromatics) on various zeolite catalysts A. Raichle, H. Scharl, Y. Traa and J. Weitkamp

302

26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as model reactions to investigate the pore topology of Nu-88 zeolite. S. Lacombe, A. Patrigeon and E. Benazzi

302

26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on AIMCM-41. Effect of the support Si/A1 molar ratio T. Klimova, M. Calder6n and J. Ramirez

303

26-P-13 - Hydrogenation and ring opening of mono- and diaromatics for Diesel upgrading on Pt/Beta catalysts M.A. Arribas, J.J. Mahiques and A. Martinez

303

26-P-14 - Hydro denitrogenation activity of N i O - MoO3 catalysts supported on various mesoporous alumino silicates K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar

303

26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and large-pore zeolite: effect of the zeolite nature on the location of NiMo sulfide in relation with catalytic properties J. Leglise, D. Cornet, M. Badlala, C Potvin and J.-M. Manoli

304

-

Ixviii 26-P-16 - Effect of zeolite acidity characteristics on the deactivation behavior of bifunctional large-pore zeolite catalysts during cyclopentane hydroconversion S. Gopal and P G. Smirniotis

304

26-P-17 - Characterization and catalytic activities of MCM-41 supported WS2 hydrotreating catalysts T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao

304

26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over bifunctional mesoporous molecular sieves C. Bischof and M. Hartmann

305

26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on zeolite catalyst A. Holl6, J. Hancs6k and D. Kall6

305

26-P-20 - Application of adsorption Dubinin-Radushkevich equation for study of n-pentane and m-xylene conversion catalysts microporous structure S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev

305

26-P-21 - Hydroisomerization of n-hexadecane over Pt/A1-MCM-41 catalysts: two different A1 incorporation methods K.-C. Park and S.-K. Ihm

306

26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for hydrotreating catalysts N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova and K. Jiratova

306

26-P-23 - New catalysts for isomerization of long-chain n-paraffins M.I. Levinbuk, L.M. Kustov, T.V. Vasina, O.V. Masloboishchikova, M.L. Pavlov, I.E. Gorbatkina and V.A. Khavkin

306

27 - Selective

Oxidation

and Sulfur Resistance

27-0-01 - Singular catalytic properties of Ti-MWW in the selective oxidation of alkenes P. Wu, T. Komatsu, T. Yashima and T. Tatsumi

165

27-0-02 - Epoxidation of propylene over T S - 1 containing trace aluminum X. Guo, Xi. Wang, Min Liu, Gang Li, Yo. Chen and J. Xiu

165

27-0-03 - One step benzene oxidation to phenol using N20 over acid zeolites G. Juttu and R.F. Lobo

165

27-0-04 - Dual pathways for benzene hydrogenation on Pt/mordenites: implication for sulfur tolerance L. Simon, J.G. van Ommen, A. Jentys and J.A. Lercher

166

lxix 27-0-05 - Sulfur resistance of PtPd catalysts: preparation, characterization and catalytic testing K. Thomas, C. Binet, T. Chevreau, D. Cornet and J.-P. Gilson

166

27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons: preparation, characterization and catalytic activity U. Arnold, R.S. da Cruz, D. Mandelli and U. Schuchardt

365

27-P-07 - High catalytic activity of Fe(III)-substituted aluminophosphate molecular sieves (FeAPO) in oxidation of aromatic compounds X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D. Jiang, S. Qiu, and F.-S. Xiao

365

27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with cations of the transition metals A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev, T.N. Shakhtakhtinsky, G.A. Ali-zade and K.1. Matiyev

365

27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation of thioethers with hydrogen peroxide M. Ziolek, A. Lewandowska, M. Renn, 1. Nowak, P. Decyk and J. Kujawa

366

27-P-10 - Biomimetic oxygen transfer by Co and Cu complexes immobilized in porous matrices K. Hernadi, I. P6link6, E. BOngyik and I. Kiricsi

366

27-P-11 Titanium molecular sieves convert hydrogen peroxide into 102 F.M. van Laar, D.E. De Vos, P. Grobet, J.-M. Aubry, L. Fiermans and P.A. Jacobs

366

27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: the effect of copper and aluminum content in the reducibility and in the activity of Cu active species M.S. Batista and E.A. Urquieta-Gonz6lez

367

27-P- 13 - Oxidizing conversion of isobutanol on zeolites S. Zulfugarova

367

27-P-14 - Photocatalytic production of H202 over heterogenized quinone in zeolite J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park

367

27-P-15 - Liquid-phase oxidation of cyclohexane in the presence of chromium and iron ETS-10 materials A. Valente, P. Brand, o, Z. Lin, F. Gonqa!ves, 1. Portugal M. W. Anderson and J. Rocha

368

27-P- 16 - Effect of oxygen concentration on catalyst deactivation rate in vapor phase Beckmann rearrangement over acid catalysts T. Takahashi and T. Kai

368

-

lxx 27-P-17 - On the role of the titanium active site in the phenol/anisole hydroxylation over titanium substituted crystalline silicates

U WilkenhOner, D.W. Gammon and E. van Steen

368

2 8 - Confinement and Physical Chemistry for Catalysis 28-O-01 - Reactivity enhancement by molecular traffic control - a consequence of released single-file constraints

P. Brgiuer and J. Kcirger

173

28-0-02 - Aromatization of n-hexane over ZnNi/HZSM-5 catalyst induced by microwave irradiation

J.Z Gui, H.S. Ding, N.N. Liu, Y.R. Gao, Z.L. Cheng, X.T. Zhang, B. Ma, L. Song, Z.L. Sun and L. V.C. Rees

173

28-0-03 - Artificial photosynthesis using zeolites

N. Castagnola and P.K. Dutta

174

28-0-04 - Synthesis of macrocycles using molecular sieve catalysts

3/1. Radha Kishan, N. Srinivas, S.J. Kulkarni, M. Ramakrishna Prasad, G. Kamalakar and K. V. Raghavan.

174

28-0-05 - Effect of single-file diffusion on the hydroisomerization of 2,2dimethylbutane on platinum loaded H-mordenite

F.J.M.M. de Gauw, J. van Grondelle and R.A. van Santen

174

28-P-06 - Use of coke-selectivated H-ZSM-5 in xylene isomerization

E Bauer and A. Freyer

307

28-P-07 - Photocatalytic reactions on chromium containing mesoporous molecular sieves under visible light irradiation: decomposition of NO and partial oxidation of propane

H. Yamashita, K. Yoshizawa, M. Ariyuki, S. Higashimoto and M. Anpo

307

28-P-08 - Enhancing the shape selectivity ofnanocrystalline HZSM-5 zeolite v/a comprehensive modifications

H.C. Guo, X S. Wang and G.R. Wang

307

28-P-09 - Nature of shape-selective catalysis in the ethylation and the isopropylation of biphenyl over H-mordenites

Y. SugL S. Tawada, T. Sugimura, Y. lmada, Y. Kubota, T. Hanaoka and T. Matsuzaki

308

28-P-10 - Adsorption of selected amino acids from aqueous solutions on mesoporous molecular sieves

S. Ernst, M. Hartmann and S. Munsch

308

lxxi 28-P-11 - Influence of OH groups of Beta zeolites on the synthesis of MTBE

F. Collignon and G. Poncelet

308

28-P-12 - About a possibilities of effectiveness increasing of porous catalyst granules with controlled activity profile

V. V. Andreev

309

28-P-13 - Effects of channel structures of wide pore zeolites on m-cresol transformation

F. L6pez, L. Gonzdtlez, J.C. Herndmdez, A. Uzc6tegui, F.E. Imbert and G. Giannetto

309

28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid and gas phase esterification reactions. The influence of the hydrophobicity of the catalyst

M.J. Verhoef R.M Koster, E. Poels, A. Bliek, J.A. Peters and H. van Bekkum

309

28-P-15 - The influence of pore geometry on the alkylation of phenol with methanol over zeolites

G. Moon, K.P. MOller, W. BOhringer and C.T. O'Connor

310

28-P-16 - Diffusion analysis of cumene cracking over ZSM5 using a jetloop reactor

P. Schwan and K.P. MOller

310

2 9 - New Approaches to Catalyst Preparation 29-0-01 - The catalytic performance of zeolite ERS-10

C. Perego, M. Margot& L. Carluccio, L. Zanibelli and G. Bellussi

178

29-0-02 - Towards total hydrophobisation of MCM-41 type silica surface

T. Martin, A. Galarneau, D. Brunel, V. lzard, V. Hulea, A.C. Blanc, S. Abramson, F. Di Renzo and F. Fajula

178

29-0-03 - Novel Lewis-acid catalysts (NLACs): their properties, characterisation and use in catalysis

M.H. Valkenberg, C. deCastro and W.F. Hoelderich

179

29-0-04 - A controlled dispersion of A13+ onto a silica mesoporous material. A comparative study with A13+ mcorporation. •

O. Collart, A. Galarneau, F. Di Renzo, F. Fajula, P. Van Der Voort and E. F. Vansant

179

29-P-05 - Catalytic properties of MFI zincosilicates

S. Kowalac, E. Szymkowiak, 1. Lehmann and G. Giordano

311

lxxii 29-P-06 - Acidity characterization of dealuminated H-ZSM-5 zeolites by isopropanol dehydration C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis

311

29-P-07 - Acidic ZrO2/SO4 2" in mesoporous materials Y. Sun, L. Zhu, H. Lu, D. Jiang and F.-S. Xiao

311

29-P-08- HMS catalysts containing transition metals or transition metal complexes Z. Fu, Du. Yin , W. Zhao, Y. Chen, Do. Yin, J. Guo, C. Xiong and Luxi Zhang

312

29-P-09 -Synthesis of hydrophobic mesoporous molecular sieves by surface modification K.-K. Kang and H.-K. Rhee

312

29-P-10 - Guanidine catalysts supported on silica and micelle templated silicas: new basic catalysts for organic chemistry D.J. Macquarrie, D. Brunel, G. Renardand A. C. Blanc

312

29-P-11 - Texture of dealuminated mordenite catalysts modified with cerium and catalytic properties in the isopropylation of biphenyl M. Krdlik, J. Horniakova, D. Mravec, V. Jorik, M. Michvocik and P. Moreau

313

29-P-12 - Partially crystalline zeolitic material as novel solid acid catalysts Ming Liu, Z. Li, S. Lou, Q Wang and S. Xiang

313

29-P-13 - Novel mesoporous carbon as a catalyst support for Pt and Pd for liquid phase hydrogenation reactions W.S. Ahn, K.1. Min, Y.M. Chung, H.-K. Rhee, S.H. Joo and R. Ryoo

313

29-P-14 - Investigation of catalytic activity of framework and extraframework cobalt and manganese in MeAPO-34 prepared from fluoride medium A. Ristik, G. Avgouropoulos, T. Ioannides and V. Kaudid

314

29-P-15 - Preparation and characterization of bimetallic Pt-Zn catalysts supported on zeolite NaX J. Silvestre-Albero, F. Coloma, A. Sepfilveda-Escribano and F. RodriguezReinoso

314

29-P-16 - Surface modification of the uncalcined acid'made mesoporous silica materials in a one-step procedure H.-P. Lin, Y.-H. Liu, C.-P. Kao, S.-B. Liu and C.-Y. Mou

314

29-P-17 - Zirconia nanoparticles in ordered mesoporous material SBA-15 J. Sauer, S. Kaskel, M. Janicke and F. Schath

315

lxxiii 29-P-18 - Preparation using ozone treatment, characterization and application of isomorphously substituted Ti-, V- and Zr-MCM-41 catalysts D. Mdhn, J. Haldsz, E. Meretei, Z. K6nya, A. Fonseca, J. B.Nagy and 1. Kiricsi

315

29-P-19 - Preparation and catalytic evaluation of [Ga]MCM-58 and of MCM-58type catalysts with different aluminum contents S. Ernst, M. Hartmann, T. Hecht and A. Weber

315

29-P-20- IR study on the reaction path of methanol decomposition over basic zeolites M. Rep, J.G. van Ommen, L. Lefferts and J.A. Lercher

316

29-P-21 - Synthesis and characterization of highly ordered mono- and bimetallic substituted MCM-41 molecular sieves and their catalytic properties in selective oxidation of hydrocarbons V. Pdrvulescu, C. D~tscalescu and B.L. Su

316

29-P-22 - On the direct synthesis of noble metal cluster containing MCM-41 using surfactant stabilised metal nanoparticles A.B.J. Arnold, J.P.M. Niederer, W.F. Hoelderich, B. Spliethof B. Tesche, M. Reetz and H. Boenneman

316

29-P-23 - Microporous zincophosphates as solid base catalysts L.A. Garcia-Serrano, T. Blasco, J. Pdrez-Pariente and E. Sastre

317

29-P-24 - Zirconium containing AI-MCM-41- synthesis, characterisation and catalytic performance in 1-hexene isomerisation I. Eswaramoorthi, V. Sundaramurthy and N. Lingappan

317

29-P-25 - Iron containing zeolites and mesoporous silica as sulfuric acid catalyst A. Wingen, W. Schmidt, F. Schiith, A.C. Wie, C.N. Liao and K.J. Chao

317

29-P-26 - Deep-bed dealumination of ZSM-5 zeolites: changes in structure and catalytic activity P. Hudec, A. Smiegkovdl, Z Zidek, L. Sabo and B. Liptdkovd

318

29-P-27 - Fabrication of honeycomb structures with powder MCM-48 silica Y.-S. Ahn, M.-H. Han, S. Jun and R. Ryoo

318

29-P-28 - Acidic hybrid catalysts prepared by grafting large-pore silica M41S materials B. Lindlar, M. Lachinger, M. Haouas, A. Kogelbauer and R. Prins

318

29-P-29 - Preparation of tungsten carbide supported on (A1-)FSM-16 and its catalytic activity M. Nagai, K. Kunieda, S. Izuhal and S. Omi

319

lxxiv 29-P-30 - Ti-MCM-48 with different titanium loading: synthesis, spectroscopic characterization and catalytic activity

V. Dellarocca, M.L. Pe~a, F. Rey, A. Corma, S. Coluccia and L. Marchese

319

29-P-31 - Comparison of 3-aminopropylsilane linked to MCM-41 and HMS type silicas synthesised under biphasic and monophasic conditions

D.J. Macquarrie, M. Rocchia, B. Onida, E. Garrone, P. Lentz, J. B.Nagy, D. Brunel, A.C. Blanc and F. Fajula

30- Environmental

319

Catalysis

30-0-02 - Characterization and performance of ex-framework FeZSM-5 in catalytic N20 decomposition

J. Pdrez-Ramirez, G. Mul, F. Kapteijn, 1. W.C.E. Arends, A. Ribera and J.A. Moulo'n

172

30-O-03 - Effect of carbon number in hydrocarbon reductant on the selective catalytic reduction of NO over cation-exchanged MFI zeolites

A. ShichL Y. Kawamura, A. Satsuma and T. Hattori

172

30-0-04 - The temperature-dependent storage of NOx on metal-containing zeolites under dry and wet conditions

R. Fricke, M. Richter, E. Schreier, R. Eckelt and H. Kosslick

172

30-0-05 - Catalytic destruction of chlorinated VOCs.- Influence of characteristics of Pt/HFAU catalysts on the destruction of dichloromethane

L. Pinard, J. Tsou, P. Magnoux and M. Guisnet

173

30-P-06 - Effect of the reductant nature on the catalytic removal of N20 on a Fezeolite-Beta catalyst

G. Delahay, M. Mauvezin, B. Coq and S. Kieger

320

30-P-07 - Degradation of N-nitrosamines on zeolites

J.H. Zhu, B. Shen, Y. Xu, J. Xue, L.L. Ma and Q.H. Xu

320

30-P-08 - ZrO2/NaY: a new material for removal of N-nitrosamines pollution

J.H. Zhu, J.R. Xia, Ying Wang, G. Xie, J. Xue and Y. Chun

320

30-P-09 -Total oxidation of n-pentane, cyclohexane and their mixtures on the Cu-containing ZSM-5 zeolites

M.A. Botavina, IV. V. Nekrasov and S.L. Kiperman

321

30-P-10 - Modified natural zeolite in catalytic clearing of exhaust and ejected gases from nitric and carbon oxides

L. Akhalbedashvili and Sh. Sidamonidze

321

lxxv 30-P-11 - Selective catalytic reduction of N20 with light alkanes over different Fe-zeolite catalysts S. Kameoka, S. Tanaka, K. Kita, T. Nobukawa, S. Ito, T. Miyadera and K. Kunimori

321

30-P-12 - Selective catalytic reduction of NOx by NH3 over Mn supported MCM-41 mesoporous materials E.E. Iojoiu, P. Onu, S. Schmitzer and W. Weisweiler

322

30-P-13 - Transition metal exchanged-MCM-22 catalysts for N20 decomposition A.J.S. Mascarenhas, H.M.C. Andrade and H.O. Pastore

322

30-P-14 - The NO and N20 selective catalytic reduction on copper and iron containing ZSM-5 catalysts: a comparative study G. Fierro, G. Ferraris, M. Inversi, M. Lo Jacono and G. Moretti

322

30-P-15 - A comparison of different preparation methods of indium-modified zeolites as catalysts for the selective reduction of NO C. Schmidt, T. Sowade, F.-W. Schutze, 14. Berndt and W. Granert

323

30-P- 16 - Local structures of Ag+/ZSM-5 catalysts and their photocatalytic reactivity for the decomposition of N20 into N2 and 02 M. Matsuoka, W.-S. Ju and M. Anpo

323

30-P-17 - One stage catalytic cracking of plastic waste on zeolitic catalysts K. Gobin, D. Koumantaropoulos and G. Manos

323

30-P-18 - Analysis of the deep catalytic oxidation of binary CVOCs mixtures over H-ZSM-5 zeolite R. L6pez-Fonseca, J.I. Guti&rez-Ortiz, A. Aranzabal and J.R. Gonz6lez-Velasco

324

30-P-19 - Solid state MAS NMR studies of zeolites and alumina reacted with chlorofluorocarbons (CC12F2, CHC1F2) I. Hannus, Z K6nya, P. Lentz, J. B.Nagy and I. Kiricsi

324

30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water from petroleum refineries A.K. Aboul-Gheit and S.M. Ahmed

324

30-P-21 . Autoreduction of C u 2+ species in Cu-ZSM-5 catalysts studied by diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry and elemental analysis G. Moretti, G. Ferrarbx and P. Galli

325

30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the lean SCR of NOx by methane F. Bustamante, P. A vil and C. Montes de Correa

325

lxxvi 30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation of toluene over CuY zeolites

A.P. Antunes, J.M. Silva, M.F. Ribeiro, F.R. Ribeiro, P. Magnoux and M. Guisnet

325

30-P-24 - Study on relationship between the local structures of Ti-HMS mesoporous molecular sieves and their photocatalytic reactivity for the decomposition of NO into N2 and 02

J. Zhang, B. He, M. Matsuoka, H. Yamashita and M. Anpo

326

30-P-25 - Influence of synergistic effects on the selective catalytic reduction of NO× with CnHm over zeolites

S.N. Orlik and V. L. Struzhko

326

30-P-26 - Catalytic properties of Fe-Co double layered hydroxides synthesised with Beta zeolite for toluene oxidation

J. Carpentier, S. Siffert, J.F. Lamonier and A. Aboukags

326

30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and in-

s i t u - DRIFTS studies F. Heinrich, E. LOftier and W. Grunert

327

30-P-28 - Selective catalytic reduction of NO by methane over AgNaZSM-5 catalysts in the excess of oxygen

C. Shi, M. Cheng, Z Qu, X. Yang and X. Bao

327

30-P-29 - ZSM-5/Raney Fe composite used as DeNO× catalyst

B. Zong, W. Wang, L. Lu and X. T. Shu

327

30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged zeolites

B.I. Mosqueda-Jim~nez, M. Brandmair, A. Jentys, K. Seshan and J.A. Lercher

328

30-P-31 -NOx Reactivity on microporous MeAPOs. Spectroscopic and catalytic studies

A. Frache, M. Cadoni, S. Coluccia, L. Marchese, B. Palella, R. Pirone and P. Ciambelli

328

30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon removal under cold-start engine condition

H.K. Seo, J. W. Oh and S.J. Choung

328

30-P-33 - In-situ synthesized ZSM-5 on cordierite substrate and NO decomposition on the monolithic catalysts

N. Guan, X. Shan, X. Zeng, S. Liu, S. Xiang, U. Illgen and M. Baerns 30-P-34

-

329

Selective reduction of NO to N2 in the presence of oxygen

T. Furusawa, K. Seshan, S.E. Maisuls, J.A. Lercher, L. Lefferts and K. Aika

329

lxxvii 30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean NOx-SCR with methane

D. Sannino, M. Concetta Gaudino and P. Ciambelli

329

31 - E n v i r o n m e n t - F r i e n d l y Applications of Zeolites

31-O-01 - Influence of Jordanian chabazite-phillipsite tuff on nutrient concentration and yield of strawberry

K.M. Ibrahim, A.M. Ghrir and 14.N. Khoury

181

31-O-02 - Improvements in yield and quality of crops with NASA zeoponic fertilizer delivery systems: turf, flowers, vegetables and grain

R.D. Andrews and S.B. Kimi

181

31-O-03 - Fe/MFI as a new heterogeneous Fenton-type catalyst in the treatment of wastewater from agroindustrial processes

G. Centi, S. Perathoner and G. Romeo

181

31-O-04 - Investigation of the storage properties of zeolites and impregnated silica for thermochemical storage of heat

J. Jcinchen, ,4. Grimm and H. Stach

182

3 l-P-05 - Application of sorbing composites on natural zeolite basis for heavy metals contaminated territories rehabilitation

W. Sobolev, V. llyin, F. Bobonich and S. Bdrdny

369

3 l-P-06 - Investigation of lead removal from wastewater by Iranian natural zeolites using 2~2pb as a radiotracer

H. Kazemian, P. Rajec, F. Macasek and J. O. Kufacakova

369

3 l-P-07 - Purification of the waste liquid hydrocarbons using cation-exchanged forms of clinoptilolite

M.Kh. Annagiyev, S.G. Aliyeva and T. M.Kuliyev

369

3 l-P-08 - The use of transcarpathian zeolites for concentrating trace contaminants in water

V. O. Vasylechko, L. O. Lebedynets, G. V. Gryshchouk, Yu.B. Kuz 'ma, L.O. Vasylechko and V.P. Zakordonskiy

370

3 l-P-09 - Ammonia removal from drinking water using clinoptilolite and Lewatit S 100

H.M. Abd El-Hady, A. Grtinwald, K. Vlckova and J. Zeithammerova

370

3 l-P-10 - Pilot plant of ammonium removal from nitrogen industry waste waters by an Ukrainian clinoptilolite

Yu.I. Tarasevich and V.E. Polyakov

370

lxxviii 3 l-P-11- Croatian clinoptilolite and montmorillonite-rich tufts for ammonium removal

M. Rozic and S. Cerjan-Stefanovic

371

3 l-P-12 - Ammonia removal from water by ion exchange using South African and Zambian zeolite samples, and its application in aquaculture

M. Mwale and H. Kaiser

371

3 l-P- 13 - Permanent storage of chromium in hardened FAU-type zeolite/cement pastes

C. Colella, D. Caputo and B. de Gennaro

371

3 l-P-14 - Phosphorus removal from wastewater in upgraded activated sludge system with natural zeolite addition

J. Hrenovic, Y. Orhan, H. BiiyfikgfingOr and D. Tibljad

372

3 l - P - 1 5 - Application of natural zeolites to purify polluted river water

M. Okamoto and E. Sakamoto

372

3 l-P-16 - Elimination of ammonium in seawater by zeolitic products

J.M. Lopez-Alcalgl andJ.L. Lopez-Ruiz

32 - Zeolite Minerals

372

and Health Sciences

32-0-01 - Biomedical applications of zeolites

K. Pavelic, B. Subotic and M. Colic

170

32-0-02 - Zeolites and other porous materials in the toxicity of inhaled mineral dusts

I. Fenoglio, L. Prandi, M. Tomatis and B. Fubini

170

32-0-03 - Study of the reaction of a Ca-clinoptilolite and human bile

R. Sim6n Carballo, G. Rodriguez-Fuentes, C. Urbina and A. Fleitas

170

32-0-04 - In vitro adsorption of zearalenone by octadecyldimethylbenzyl ammonium-exchanged clinoptilolite-heulandite tuff and bentonite

A. Dakovic, M. Tomasevic-Canovic, V. Dondur, D. Stojsic and G. Rottinghaus

171

32-0-05 - Zeolites in sexual confusion: slow release of pheromones

J. Muftoz-Pallares, E. Primo, J: Primo and A. Corma

171

32-P-06 - Effects of dietary inclusion of natural zeolite on broiler performance and carcass characteristics

E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos and P. Fortomaris

373

lxxix 32-P-07 - Interaction studies between aspirin and purified natural clinoptilolite A. Rivera, L.M. Rodriguez-Albelo, G. Rodriguez-Fuentes and E. Altshuler

373

32-P-08 - Channel model for the theoretical study of aspirin adsorption on clinoptilolite: water influence A. Lam and A. Rivera

373

32-P-09 - In vitro and in vivo effect of natural clinoptilolite on malignant tumors M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak, V. Sverko, T. Balog and K. Pavelic

374

32-P-10 - Effects of natural clinoptilolite-rich tuff and sodium bicarbonate on milk yield, milk composition and blood profile in Holstein cows A. Nikkhah, A.R. Safamehr and M. Moradi - Shahrbabak

374

32-P-11 - Effect of natural clinoptillolite-rich tuff on the performance of Varamini male lambs A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak

374

32-P-12 - Clinoptilolite and the possibilities for its application in medicine N. Izmirova, B. Aleksiev, E. Djourova, P. Blagoeva, Z Gendjev, Tz. Mircheva, D. Pressiyanov, L. Minev, T. Bozhkova, P. Uzunov, 1. Tomova, M. Baeva, A. Boyanova, T. Todorov and R. Petrova

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Studies in Surface Sbience and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

Ordered Mesoporous Materials - State of the Art and Prospects F. Schtith MPI ftir Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mtilheim, Germany

Research in ordered mesoporous oxides has increased dramatically in intensity over the last years. Developments not foreseen at the time when MCM-41 and FSM-16 were discovered have taken place, and in some cases applications of these materials are on the horizon. This paper will cover the discoveries which have expanded the scope of research in this field and try to give an outlook where new developments could take place. 1. I N T R O D U C T I O N When one searches for the key words (MCM-41 or FSM-16 or SBA-15 or ordered mesoporous oxides or ordered mesoporous materials) in the Web of Science, almost 1500 hits were reported in F e b r u a r y 2001, 450 and this set of key words w 400 c i i does not even give hits for .o 350 (g II all relevant publications, o 300 ,Q II since in the early = 250 12. i l l publications these materials ~ 2oo I I I I '- 150 were called "mesoporous I I I I molecular sieves". Research E 100 = l i l l E = 50 increased dramatically in __111111 the recent years: About half of the 1500 publications result from 1999 or 2000. year One might have expected t h a t after an initial phase Fig. 1: Development of publications on ordered on the synthesis and mesoporous oxides since 1990. characterization of such materials, by now the applications would have moved into the center of attention. However, this proved to be the case to a limited extent only. The synthesis and characterization had to offer so m a n y new aspects, that this still seems to be the most active area of research.

In the following the major achievements - seen from a personal perspective - of the last years in the field shall be highlighted, but it is not intended to give a comprehensive review. It will then be attempted to give a projection where the research on ordered mesoporous materials might move in the future. 2. S T R U C T U R E S

After initially FSM-16 [1] and MCM-41 [2] as the hexagonal members and MCM48 [3] as the cubic Ia3d member of the ordered mesoporous materials had been synthesized, a wide range of other structures became available quite rapidly, most of which had pure surfactant liquid crystal counterparts. Some, however, were unique structures only known for silica-surfactant composites. For the hexagonally ordered mesoporous silicas the route leading to the formation of SBA-15 [4] is the most exciting novel development after the discovery of the initial pathways. Before this discovery pore sizes of ordered mesoporous silica were limited to approximately 10 nm, as reported already in the initial papers, wall thickness was always found to be around 1 nm. The use of the triblockcopolymers of the Pluronics type expanded the accessible range dramatically. Substantially higher pore sizes and a wall thickness up to 6 nm could be achieved. The blockpolymer template can easily be removed by extraction or calcination, and the resulting material has a very good stability against water. After this initial publication, many other researchers used SBA-15 instead of MCM-41 type materials for further investigations. A serious problem in analyzing the structures of ordered mesoporous materials is, however, the fact that typically X-ray diffraction patterns are obtained which have only few reflections. Thus, often only space groups can be assigned, but no full structure solution is possible. So far, most structural models are just that, i.e. models, and they still have to be confirmed by either X-ray or electron crystallography. The 2-dimensionally ordered MCM-41 and the cubic MCM-48 have until recently probably been the two examples which were structurally well characterized by XRD and TEM [5,6]. One of the most notable developments, from the structure characterization point of view as well as with respect to the structure of the materials itself, was the structure solution of SBA-1, SBA-6, and SBA-16 with a novel electron crystallographic technique [7]. This technique uses the fact that the TEM image contains information both on the phase and the amplitude of the structure factors. To obtain the 3-D image of the structure, different 2-D projections of the structure are recorded with TEM. Fourier analysis of the images taken along different directions collectively provide information on the 3-D structure in reciprocal space. This data set can be backtransformed which eventually gives the 3-D real space structure. The technique allowed to gain surprisingly detailed insight into the structure of three different ordered mesoporous silicas. Both SBA-1 and SBA-6 have interesting bimodal pore size distributions. Both structures consist of a packing of differently sized A- and B-cages, the difference between the two being the dimensions of pores and walls. The pores ]n SBA-6 have sizes of 2 nm and 3.3 x 4.1 nm, resp., in

SBA-1 pore sizes are determined to be 0.2 nm and 1.5 x 2.2 nm, resp. The smaller pore size of the SBA-1 is not fully ascertained as yet, since sorption analysis suggests a somewhat bigger size for this type of pores. For SBA-16 a bcc packing of cavities with a diameter of 9.5 nm is determined, in which the cavities are connected by pores of 2.3 nm along the [111] directions. These bimodal size distributions of structural pores observed for SBA-1 and SBA-6 are unique for ordered mesoporous materials. The pore size distribution of SBA-15 is probably also bimodal, in which the bigger, hexagonally ordered structural pores determined by the surfactant are connected by micropores through the silica walls [8]. However, these micropores do not seem to be well ordered and are rather the result Fig. 2: a) Typical TEM of calcined of the fact, that part of the KSW-2 (pH 4.0) and the corresponding triblockcopolymer surfactant ED pattern indexed as hk0 projection. penetrates the silica. b) Typical TEM and the corresponding Another very remarkable structure ED pattern of as-synthesized KSW-2 was recently reported by the group of (pH 6.0). c) Another TEM of the as- Kuroda [9]. So far all structures with synthesized KSW-2 (pH 6.0). Arrows one dimensional pore systems were imply the observed place of the bending either hexagonally packed or of silicate sheets derived from disordered. Kuroda succeeded in kanemite, from ref. [9]. synthesizing a square packing of pores (Fig. 2) in an orthorhombic structure which are most probably formed following the folded sheet mechanism originally proposed for FSM-16. Formation of the material - called KSW-2 - is possible by strict pH control during the transformation of the kanemite-surfactant composite. 3. C O M P O S I T I O N S

The first ordered mesoporous materials reported were silicas or aluminumsilicates. The majority of all published investigations is still based on such compositions. In addition, many different elements, recently listed in a comprehensive review [10], have been introduced into the framework of ordered mesoporous oxides, just as in zeolitic frameworks. Such compositions could

become important in catalytic applications, similar to the progress made in zeolite chemistry, where, for instance, TS-1 was a major advance in oxidation chemistry over zeolites. Conceptually, however, the synthesis of fully nonsiliceous frameworks was the bigger step. The possibility to extend the approach had been predicted very early [5], and the first partial success was achieved in 1994, when several different non-siliceous materials were introduced [11]. However, all those materials were not stable upon template removal. The first stable compositions were synthesized in 1995 and 1996 as TiO2 [12] and ZrPxOy [13]. From then on many other materials were obtained, not only in a mesostructured, but also in a mesoporous form. Most of these, however, where rather disordered, and the highest degree of order is still observed in the titania and zirconia based materials. Non-siliceous mesoporous materials are reviewed in a recent review [14]. The majority of the hitherto reported non-siliceous mesoporous materials are hexagonally ordered or totally disordered. We recently reported a zirconium-based cubic mesostructure [15], which at that time could not be stabilized to result in a mesoporous material. Using the phosphate route developed previously for the stabilization of the hexagonal phase [13] we now also succeeded in obtaining a mesoporous cubic zirconium oxo phosphate (Fig. 3) [16]. Other non-hexagonal structures were prepared by the route to non-siliceous materials analogous to the synthesis of SBA-15 described by the Stucky group [17]. Other than for SBA-15, the synthesis is carried out in alcohol instead of aqueous solution. The pathway is remarkable, because it allows the synthesis of various different framework compositions and probably has the highest flexibility with respect to structure, pore sizes and composition of all preparations known so far. Amongst others, it is suitable for the preparation of a well ordered mesoporous cubic titania, as Fig.4: TEM of an SBA-15 sample demonstrated by XRD, sorption and loaded with 28wt.% of Y203. The TEM. coating of the walls is visible as the high contrast.

An alternative pathway to obtain essentially non-siliceous compositions was reported recently. This route relies on the fact, that some oxides spread under suitable conditions on silica. If a mesoporous silica is thus coated with a different oxide, a material with essentially the surface area of silica, but the surface functionality of the spreaded oxide results. This has been demonstrated for rare earth oxides [ 18], a TEM image of which is shown in fig. 4. More surprising than these non-silica oxides, however, was the discovery of nonoxidic compositions: Already relatively early it was shown that noble metals could be mesostructured and even obtained in mesoporous form using the true liquid crystal templating mechanism [19]. Later on, similar structures were obtained via a "nanocasting" route with SBA-15 as a mold and a volatile Pd-precursor [20]. After dissolution of the SBA-15 mesostructured Pd-particles were left. Another highly innovative development with respect to framework composition were the materials containing carbon or even consisting of pure carbon. Silicas with partly carbonaceous walls were pioneered by the groups of Inagaki [21], Stein [22] and Ozin [23]. The synthetic feature which allows introduction of the alkyl group as an integral part of the wall structure is the use of silicon precursors of the general type RO3Si-R-SiOR3 in which the alkoxy units are hydrolized and provide the linkage to other units, but the bridging alkyl is not attacked during mesostructure formation and remains in the material. Even more fascinating is the synthesis of purely carbonaceous ordered mesoporous materials. However, here the pathway is totally different. The "nanocasting" mentioned already above has in fact been pioneered for this class of Fig. 5: TEM image of an ordered materials, called CMK-1 [24]. A silica mesoporous carbon CMK-1 obtained with a 3-dimensional pores system (the from ,,nanocasting" in a MCM-48 micropores connecting the linear pores mold (top). SEM image of particles of in SBA-15 also provide for CMK-1 (bottom), from ref. [24]

threedimensionality in this respect) is impregnated with a suitable carbon precursor, for instance sucrose/H2SO4. The carbon precursor is pyrolized in the pore system and then the silica framework is removed by leaching with NaOH or HF. The remaining mesoporous carbon structure has remarkable textural features due to the low density of carbon, such as a surface area exceeding 1500 m2/g and specific pore volumes far above 1 ml/g. In addition, the mesopore structure as well as the morphology of the particles on a micrometer scale are surprisingly perfect (Fig. 5). 4. M A C R O S T R U C T U R E S

The products resulting from the early syntheses of mesoporous silica were typically finely divided powders with no well defined morphology. Soon, however, monoliths became available from the true liquid crystal templating route [25] and from 1996 on a wide variety of different shapes, including spheres, fibers, thin films, and many other more complex morphologies were reported, some of which were designed by the process conditions, such as emulsion templating or spin casting, some of which formed spontaneously by a self-organization process. These various morphologies are covered in a recent review [26] and shall not be discussed extensively here. However, one type of morphologies has very remarkable structural properties. These are the fibers and small particles formed spontaneously in the acidic quiescent system introduced by Huo et al. [27]. At the time of the discovery of these fibers the internal architecture was not clear, although there were indications that the channels would run parallel to the fiber axis [27]. However, recently in an elegant series of observations, the group of Marlow clarified the internal structure of the fibers [28,29]: The fibers have a circular internal structure, with the channels of the hexagonal mesostructure whirling around the fiber Fig. 6: TEM image of the fiber center axis (Fig. 6). The smaller particles with of an ordered mesoporous fiber circular or distorted circular symmetry taken perpendicular to the fiber axis reported in several publications probably on a microtomed sample, from ref. have a very similiar internal structure, [28]. which is, however, formed presumably from a slightly different kind of seed. This kind of internal organization raises several highly interesting questions, for instance concerning the mechanism of formation of such structures. Even more fascinating seems to be the fact that these ordered mesostructured fibers are a novel type for the organization of solid

matter. The objects are neither crystals (no translation periodicity) nor quasicrystals, but objects with a rotational type of symmetry, called circulites [30]. This leads to an altered reciprocal space, where the fibers are not represented as points, as a crystal would, but rather as complex ring structures. The altered reciprocal space structure is not just a mathematical construct, but has, for instance, consequences for the diffraction behavior of the fibers.

5. A P P L I C A T I O N S First obvious applications of ordered mesoporous materials were seen in catalysis, where a need for zeolite-like materials with bigger pore sizes was identified to process heavier residues more efficiently. However, since the acidity of ordered mesoporous materials does so far not substantially exceed that of amorphous aluminumsilicates, the high expectations could not be met. If one asks critically, where the advantages of ordered mesoporous materials over more conventional supports lie, enthusiams will most probably be dampened. For catalysis, one of the major points is the high surface area of MCM-41, FSM-16, SBA-15 and all related materials, which can be exploited for depositing metals, incorporating metals in the walls, or grafting species to the walls. However, this high surface area is achieved on the expense of a relatively high susceptibility to hydrothermal degradation and a rather expensive synthesis. Silicas with approximately half the surface area of ordered mesoporous silica are accessible by much cheaper and simpler routes. This is not quite the same for non-siliceous compositions, but here no major efforts seem to have been directed towards their investigation in catalytic applications, yet. A second beneficial feature of ordered mesoporous oxides in catalysis could be the sharp pore size distribution which is reminiscent of zeolites and thus suggests applications in shape selective reactions. However, the pore sizes realized in ordered mesoporous materials are so big, that simple molecules will not be processed shape selectively. Large molecules, on the other hand, are typically so flexible, that the discrimination between differently sized molecules will not be as effective as, for instance, for differently substituted benzene derivatives in zeolites. Therefore, only few publications have appeared, where a clear advantage of ordered mesoporous materials in catalytic applications has been demonstrated which would justify their more expensive and complicated synthesis. In addition, often a good benchmark, such as a high surface area precipitated silica was lacking for comparison, so that the relevance of published data are difficult to judge. Therefore only three examples for the use of surfactant templated mesoporous oxides in catalytic applications shall be highlighted here. More encompassing reviews on their catalytic properties can be found in two review articles [31,32] The first study elegantly used the combination of a suitable acid site strength and the influence of the regular mesopore system for the preparation of acetals from aldehydes [33]. MCM-41 was found to be superior to zeolites and amorphous

aluminumsilicates, if bulky reagents exceeding the size of the zeolite pores shall be converted. The regular mesopore size of the MCM-41 type materials allows the whole pore system to be used even with bulky reagents or products, while zeolitic pores and part of the smaller pores of the amorphous aluminumsilicate are inaccessible and the catalysts are thus less active. It can be envisaged, t h a t other reactions in fine chemistry would benefit from the use of ordered mesoporous materials as well. However, in fine chemistry catalysts are often not tuned to the process, but rather a standard catalyst off the shelf is used. Ordered mesoporous silicas and substituted silicas will have to compete with such s t a n d a r d catalysts. The second example where ordered mesoporous materials were clearly superior to conventional catalysts is a very old process, the oxidation of sulfur dioxide [34]. Nowadays, part of the sulfuric acid is 10( ....... 4--. produced from the sulfur dioxide 90 / "'.~quilibriumconversion released during roasting of sulfidic E 8o V4-111 MCM-41""" ores. Since the smelters tend to use = 70 /SyFeS:l 0 oxygen instead of air in modern "~ 60 ~ . ."" processes, the resulting gas is very ~ 50 ~ "~'. sulfur rich and can not be processed u~ 40 over the conventional vanadium c7 3o v 16os based catalysts. Iron oxide on r 20 surfactant templated silica was found lO to be a suitable, stable catalyst for o . . . . . . . . this reaction and clearly 6oo 700 8oo 9oo looo Temperature [K] advantageous compared to a commercial iron-on-silica catalyst, Fig. 7:SO2 conversion vs. temperature Fig. 7. Also iron oxide deposited on a over v a n a d i u m reference catalyst (V4conventional silica was substantially 111), Fe/MCM-41, and commercial iron less active. The process is ready for catalyst (V1605), from ref [34]. commercialization and a commercial plant would probably use a catalyst based on an adapted mesoporous silica. In the last example the mesostructure has been used essentially as a support for the iron, which is the active component. Another quite spectacular example was published recently, where a single site polyolefin catalyst was anchored in the pore system of ordered mesoporous fibers, and the pore system itself was used as a "nanoextruder" [35]. The resulting polymer consists of crystalline fibers with a diameter of 30 to 50 n m and a very high molecular weight of 6.200.000 Dalton. However, since the real structure of the fibers is circular (see above) the nanoextrusion process claimed is difficult to envisage. The results of the authors are indeed very remarkable, but they seem to have not been confirmed so far. Outside of catalysis, other application fields seem to be quite promising. Feng et al. [36] modified the internal surface of MCM-41 with mercaptopropyl groups. The resulting materials had excellent binding behavior for heavy metals which was far superior to commercial adsorbents [37]. Such modified mesoporous silicas could find applications for water remediation. 9e

Still relatively unexplored, but potentially a large application field of ordered mesoporous materials is optics and electronics. Marlow et al. succeeded in the synthesis of ordered mesoporous silica fibers doped with a rhodamin laser dye [38]. Upon laser irradiation the waveguide effect reported earlier [27] led to amplification by stimulated emission along the fiber axis. The light emitted from the ends of the fibers was spectrally narrowed and highly directional. The effect observed can be described as a mirrorless lasing which can be useful in the construction of optical circuits. A first step in this direction was taken by Yang et al. who produced a prototype optical circuit with waveguides and mirrorless lasers by soft lithography [39]. The decisive step to realize the waveguide on a support was the use of an ordered mesoporous silica thin film. For waveguiding to occur, the waveguide needs to have a higher refractive index t h a n the surrounding. This is a problem, if the silica waveguide is placed on glass or even on silicon, because there the refractive index of the support is similar or even higher t h a n t h a t of the mesostructure. However, a mesoporous silica has, due to the high porosity, a very low refractive index of only 1.15. This allowed confinement of the light in the structure placed on this support and enabled the construction of the optical circuit board. The low refractive index also corresponds to another highly attractive feature of ordered mesoporous materials, i.e. a low dielectric constant. The search for low k dielectrics is very intense in m a n y laboratories in the world, since the semiconductor industry is targeting for dielectric films with k substantially below 2.5. First reports on the dielectric constant of ordered mesoporous silica films by Zhao et al. [40] gave values between 1.45 and 2.1, depending on the exact nature of the film. In a subsequent more extensive study these data were essentially confirmed [41]. Recently the group of Brinker has introduced several highly innovative methods for structuring mesoporous silica thin films, for instance by incorporating a photoacid generator which upon UV-exposure leads to generation of the acid which catalyzes silica condensation. Thus, using masks during UV exposure, thin films of mesoporous silica can be patterned [42]. Also "printing" techniques have been developed by this group to prepare micropatterned structures of ordered mesoporous silica [43]. Due to the easy processability and the variety of different pathways available to prepare [44] and structure films of ordered mesoporous silica, the optical and dielectric properties could indeed lead to their use in technical devices in the electronics industry. 6. P R O S P E C T S

A predicition of future developments is very difficult in any field, but especially so in a fast moving field such as ordered mesoporous materials. Such prospects can only be of a very general nature, partly due to the fact t h a t for any specific interesting idea we would be already working on the realization! The work published so f a r - and one should realize t h a t ten years ago this field of research did not even exist! - suggests, t h a t there are virtually no limitations with respect to the structures and compositions, which can be synthesized as

10 more or less mesostructured compounds. With respect to the compositions, the successful synthesis of metals and mesostructured carbon by the "nanocasting" process suggests a very general pathway to produce ordered mesoporous materials. One will certainly try to load the mesoporous silica templates with various other precursors and then remove the silica structure. If the material which shall be casted is not stable against the conditions used for silica removal (HF or NaOH), one could go one step further and first cast a carbon structure from a silica mold and then, after silica removal, use the carbon negative as a new mold to cast the desired material. The carbon structure can then be removed, for instance, by calcination. It is no great risk to predict exciting developments in this area. With respect to applications, there will certainly be more and more investigations where ordered mesoporous materials are used as catalysts or catalyst supports. However, the more skeptical note of the section on catalysis shall be repeated here: In many cases, much cheaper and simpler alternatives exist, and the properties of ordered mesoporous materials are not so much superior to justify the higher effort of their synthesis. On a longer time scale, non-siliceous compositions will probably be used more frequently in catalysis. If one analyzes the catalytic processes implemented today, the majority is not based on silica as catalyst or support, and the single most important area of aluminumsilicates, acid catalysis by zeolites, seems to be less attractive for ordered mesoporous aluminumsilicates, unless a crystallization of the walls to zeolitic structures or the assembly of such materials from colloidal zeolites to enhance the acid strenght becomes possible. Good opportunities, however, lie in applications outside of catalysis. There are already very promising initial results, such as the adsorbents for heavy metals or the low dielectric constant applications. The big advantage for applications in optics and electronics is the high compatibility of ordered mesoporous silica with the existing technology, since the chemistry is almost perfectly adapted for use with silicon, which is covered by a thin silica layer anyway. Also the methods available for processing, such as spin-coating or dip-coating are well established techniques, and thus relatively small adaption problems are foreseen, although they should certainly not be underestimated. First commercial applications will possibly emerge rather in these fields than in catalysis, but many factors influence decisions to go commercial with a product, so that the future will show, whether and where ordered mesoporous solids will find their first practical uses. 7. A C K N O W L E D G E M E N T S

Research of my group in this field was continuously supported by the FCI and grants from the EU and the DFG which are gratefully acknowledged.

11 8. R E F E R E N C E S

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12 26. U. Ciesla, F. Schfith, Micropor.Mesopor.Mater. 27, 131 (1999) 27. Q. Huo, D. Zhao, J. Feng, K. Weston, S.K. Buratto, G.D. Stucky, S. Schacht, F. Schfith, Adv. Mater. 9, 974 (1997) 28. F. Marlow, B. Spliethoff, B. Tesche, D.Y. Zhao, Adv.Mater. 12, 961 (2000) 29. F.Kleitz, F. Marlow, G. Stucky, F. Schfith, Chem.Mater., submitted 30. F. Marlow, I. Leike, C. Weidenthaler, C.W. Lehmann, U. Wilczok, Adv.Mater., in print 31. J.Y. Ying, C.P. Mehnert, M.S. Wong, Angew.Chem.Int.Ed.Engl. 38, 56 (1999) 32. A. Corma, Chem.Rev. 97, 2373 (1997) 33. M.J. Climent, A. Corma, S. Iborra, M.C. Navarro, J. Primo, J.Catal. 161, 783 (1996) 34. A. Wingen, N. Anastasievic, A. Hollnagel, D. Werner, F. Schfith, J.Catal. 193, 248 (2000) 35. K. Kageyama, J. Tamazawa, T. Aida, Science 285, 2113 (1999) 36. X. Feng, G.E. Fryxell, L.Q. Wang, A.Y. Kim, J. Liu, K.M. Kemner, Science 276, 923 (1997) 37. J. Liu, X. Feng, G.E. Fryxell, L.Q. Wang, A.Y. Kim, M. Gong, Adv.Mater. 10, 161 (1998) 38. F. Marlow, M. D. McGehee, D. Zhao, B. F. Chmelka, G. D. Stucky, Adv. Mater. 11, 632 (1999) 39. P. Yang, G. Wirnsberger, H.C. Huang, S.R. Cordero, M.D. McGehee, B. Scott, T. Deng, G.M. Whitesides, B.F. Chmelka, S.K. Buratto, G.D. Stucky, Science 287, 465 (2000) 40. D. Zhao, P. Yang, N. Melosh, J. Feng, B.F. Chmelka, G.D. Stucky, Adv.Mater. 10, 1380 (1998) 41. S. Baskaran, J. Liu, I~ Domansky, N. Kohler, X. Li, C. Coyle, G.E. Fryxell, S. Thevuthasan, R.E. Williford, Adv.Mater. 12, 291 (2000) 42. D.A. Doshi, N.K. Huesing, M.C. Lu, H.Y. Fan, Y.F. Lu, K. Simmons-Potter, B.J. Potter, A.J. Hurd, C.J. Brinker, Science 290, 107 (2000) 43. H.Y. Fan, Y.F. Lu, A. Stump, S.T. Reed, T. Baer, R. Schunk, V. Perez-Luna, G.P. Lopez, C.J. Brinker, Nature 405, 56 (2000) 44. Y.F. Lu, R. Ganguli, C.A. Drewien, M.T. Anderson, C.J. Brinker, W.L. Gong, Y.X. Guo, H. Soyez, B. Dunn, M.H. Huang, J.I. Zink, Nature, 389, 364 (1997)

Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

13

Clinoptilolite-heulandite: applications and basic research Thomas Armbruster Laboratorium fur chemische und mineralogische Kristallographie, Universitat Bern, Freiestr. 3, CH-3012 Bern, Switzerland Structural peculiarities of clinoptilolite and heulandite are reviewed. Special attention is given to partial Si, A1 ordering within the tetrahedral framework structure. There is strong evidence that the Si, A1 ordering pattern depends on the size, charge, and placing of the original extraframework cations. Even if exchanged to homoionic forms clinoptilolite and heulandite may display different properties depending on the degree and type of Si, A1 ordering. In some cation-exchanged heulandites symmetry lowering from the topological symmetry C2/m to Cm or C1 has been observed due to partial Si, A1 ordering and low symmetry site preference of extraframework cations. Major applications of clinoptilolite are reviewed. In the field of pollution abatement not only the natural product but also surface modified clinoptilolites gain importance. 1. INTRODUCTION Clinoptilolite with the simplified formula (Na,K)6Si30A16072 "nH20 is the most common natural zeolite found mainly in sedimentary rocks of volcanic origin. Such deposits aroused strong commercial interest because clinoptilolite tuffs are often rather pure and can be mined with simple techniques. Approximately 25 years ago ca. 300,000 tons of zeolitic tuff were mined per year [1]. In 1997 ca. 3.6 Mio tons of natural zeolites (mainly clinoptilolite and chabazite) were worldwide produced [2], ca. 2/3 alone were stoped in China. Demand for natural zeolites has increased rapidly over the past decade, particularly in agricultural applications. Growth rates as high as 10% per year are forecasted [2]. A typical zeolite mining company in the USA, Canada, and Europe has less than 50 employees and produces in open pits 20,000 to 50,000 tons per year. Characteristic clinoptilolite rocks consist of 60-90% clinoptilolite with the remaining being mainly feldspars, clays, glass, and quartz. Depending on quality and specification the prize ranges between 50 and 300 US$ per ton. In North America and Europe a large portion of the production goes into the area of animal hygiene including cat litter and other animal bedding products. The rest is divided among applications in animal feed, fertilizer, environmental absorption, and building materials. Zeolitic building material includes dimension stones, pozzolanic cements and concrete, and lightweight aggregates. Some of the pioneering zeolite research has been carried out on heulandite with the simplified formula Ca4A18Si28072 9nH20 because large crystals of this species are available in limited quantities from cavities and vugs in volcanic rocks, e.g. in the Deccan Trap basalts of Western India [3]. Already in 1934 Tiselius [4] studied the temperature, pressure, and concentration dependence of the anisotropic H20 diffusion in heulandite single-crystals. Other

14 recent pioneering studies like atomic force microscopy (AFM) and application of heulandites as electrodes will be discussed below.

1.1. Mineralogical nomenclature Zeolite minerals species shall not be distinguished solely on the basis of the framework Si/A1 ratio. An exception is made in the case of heulandite and clinoptilolite; heulandite is defined as the zeolite mineral series having the distinctive framework topology of heulandite (HEU) and the ratio Si/A1 < 4.0. Clinoptilolite is defined as the series with the same framework topology and Si/A1 > 4.0. The exception is based on entrenched usage of the names heulandite and clinoptilolite, and their convenience for recognizing an important chemical feature [5]. Note that in older studies thermal stability has been used to distinguish clinoptilolite from heulandite. This is a derivative property as an aid to identification, and it is not appropriate as the basis for definition. Individual species in a zeolite mineral series with varying extraframework cations are named by attaching to the series name a suffix indicating the chemical symbol for the extraframework element that is most abundant in atomic properties, e.g. heulandite-Ca, heulandite-Na, clinoptilolite-K, clinoptilolite-Ca etc. [5]. 2. CRYSTAL STRUCTURE The structural topology of the tetrahedral HEU framework [6] is well understood and possesses C2/m space group symmetry with oblate channels confined by ten-membered (7.5 x 3.1 A) and eight-membered tetrahedral rings (4.6 x 3.6 A) parallel to the c-axis. Additional eight-membered ring channels (4.7 x 2.8/~) running parallel to [100] and [102] cross-link the former channels within (010), giving rise to a two-dimensional channel system parallel to (010) responsible for a layer-like structure (Fig. 1).

Fig. 1. Columnar model of the twodimensional channel arrangement parallel to (010) in HEU frameworks. The dark gray columns parallel to [001] represent eight- and ten-membered ring channels. These channels are cross-linked by the light gray eight-membered ring channels running parallel to [100] and [102].

15 There is still doubt about the true symmetry of clinoptilolite and heulandite. Ventriglia [7] determined heulandite to be piezoelectric but none of the subsequent studies on natural samples could confirm this low symmetry (either space group Cm or C1). The possible reason for acentricity is partial Si, A1 ordering within the various tetrahedral sites which is difficult to resolve by analytical or structural techniques. Thus C2/m is the maximum symmetry which may be lowered to C2, Cm, C1, and C1. In addition, multiple polymorphs, distinguished by different distributions of partially Si, A1 ordered tetrahedra, exist in each space group. In a review of C2/m heulandites and clinoptilolites it was found that: (i) in all cases the tetrahedron T2 had the highest A1 concentration but below 50%, (ii) the tetrahedron with the second richest A1 occupation (below 25% A1) could either be T1, T3, T4, or T5 depending on the sample [8]. In analogy to alkali feldspars it can be postulated that each clinoptilolite or heulandite may be structurally different, even if a constant Si/A1 ratio is maintained. This problem is not only of academic interest but has also strong influence on cation diffusion, cation exchange, gas sorption, and catalytic properties, etc.

2.1. Examples of inconsistent properties Gunter et al. [9] used three different natural HEU samples of the following composition, HI: Ca3.6Ko.8A18.sSi27.4072 926.1 H20, H-II: Ca2.1Mg0.3Na2.sK0.3A18.0Si28.2072 925.5 H20, and HIII: Ca3.7Nal.3K0.1A18.9Si27.1072 921.4 H20 to study Pb 2+ exchange. The crystals were crushed to 100-500 Ixm and stirred for 4 weeks in 2 M solution of NaC1 at 100~ to obtain standard conditions (Na-exchanged varieties). After this time only sample H-III was completely Naexchanged whereas samples H-I and H-II stilled revealed significant concentrations of the original extraframework cations in the core of the crystals. In a second step Na-exchanged crystals were treated in a similar way for 3 weeks in 2 M solution of lead acetate to obtain pbE+-exchanged varieties. However, only sample H-III completely exchanged. In particular, sample H-I with a tetrahedral framework composition almost identical to sample H-In revealed only Pb 2+ exchange in a very narrow seam on the rim and around cracks. The reason for this different exchange behavior was not understood [9]. Tarasevich et al. [10] performed K § and Pb 2§ exchange experiments on Na-exchanged forms of two different natural clinoptilolite samples and noted different selectivity for these samples although the difference in the SIO2/A1203 ratio was insignificant and the cation exchange capacities were virtually the same. It should be noted that the selectivity was only different on a quantitative scale. The characteristic exchange sequence of low-field strength zeolites [11, 12] remained uninfluenced. Tarasevich et al. [10] speculated that some specific features of the clinoptilolite structure are responsible for the difference in selectivity. One of their sample formed in nature as Ca-rich variety whereas the other as clinoptilolite-Na. It was suggested [10] that an originally Ca2§ clinoptilolite crystallizes for effective charge balance with a different Si, A1 distribution compared to a Na+-rich clinoptilolite with similar Si/A1 ratio. Thus even in its Na-exchanged form both clinoptilolites have a 'memory' in the sense that the originally Ca 2+ rich sample has a stronger selectivity for Pb 2+ (of similar charge and size) than the originally Na + rich sample which is more selective for K +. This memory effect is imprinted by the Si, A1 distribution. Additional exchange isotherms Pb 2§ (solution) ~ 2Na + (clinoptilolite) were recorded [13, 14] under comparable conditions as in [10]. However, a maximum exchange level of ca. 80% [13, 14] is in contrast to ca. 95% for two different samples [10]. Such discrepancies in the exchange behavior were discussed by Langella et al. [ 14] concluding that the cation exchange

16 selectivity of clinoptilolite is markedly dependent on its original cationic composition, as not all the cationic sites in the structure can be made available for exchange. The pronounced differences in the exchange isotherms (Fig. 2), reported by various research groups [10, 1316], are mainly due to assumption of different cation exchange capacities (CEC) for clinoptilolite. The CEC values are either experimentally determined by different methods or calculated from the chemical composition of clinoptilolite [13, 17]. In most cases, a so-called Na-exchanged clinoptilolite is not completely Na-exchanged but still preserves additional extraframework cations [13, 16]. Furthermore, surface analytical investigations on cationexchanged heulandite have demonstrated that metal accumulation on the crystal surface due to adsorption of soluble and surface precipitation of insoluble hydrolysis products must be considered [ 18].

2.2. The memory effect in HEU frameworks Support for the hypothesis of imprinted Si, A1 distributions during crystal growth depending on the environment and conditions [10] comes from three different approaches: (i) study of growth texture of natural crystals [19], (ii) structure modeling applying lattice energy minimization techniques to HEU frameworks with Na and Ca as extraframework cations [2023], and (iii) synthesis of HEU frameworks prepared from aluminosilicate gels at 180~ in the presence of alkali hydroxides [24].

1.0 .....__..... ....

0.8

/f

-

. . . . . . . . . .

"='---.---==.----

__ .

""'"

iS

........................

/

..7..I

~ o.6ti;

./" ~

/

/

II/ 0.2 0

0.0

.

0.2

0

0.4

~

0.6

0.8

1.0

Xpb (solution)

Fig. 2. Experimentally determined exchange isotherms for Pb 2§ ---, 2 Na § in different natural clinoptilolites at 20 - 25~ and at 0.1 total solution normality: intermediate and long dashed curves [ 10], dotted curve [13], solid curve [14]. The discrepancies of the curves are explained by differences in CEC, extraframework cation distribution, and partial Si, A1 ordering.

17 Akizuki et al. [19], using optical and X-ray techniques, found within one macroscopic 'single crystal' of heulandite domains of triclinic and monoclinic symmetry. The symmetry is different from growth sector to growth sector. The two-dimensional atomic arrangement exposed on a growth-step surface of a tetrahedral (Si, A1) framework differs on each surface. Depending on whether an extraframework cation is adsorbed on the surface, A13§ (for charge balance) o r Si 4+ will be incorporated into the adjacent tetrahedron. Thus the degree of partial Si, A1 ordering is different from growth sector to growth sector depending on its crystallographic orientation and type of extraframework occupant [19]. In other words, each crystal is composed of various polymorphs intergrown in a twin-like relationship. Channon et al. [20] and Ruiz-Salvador et al. [21-23] calculated the minimum energy Si, A1 arrangement for H20-free clinoptilolite-Na, heulandite-Ca, and solid solution members and determined different A1 site preferences depending on type and placing of extraframework cations. Characteristic of such models is that for each bulk composition there are always several possible extraframework cation distributions leading to different Si, A1 arrangements. Although these calculations were performed for anhydrous species, at least a corresponding difference in A1 preference may be expected during crystal growth in a natural hydrous system. Zhao et al. [24] noticed during HEU framework synthesis that for a given aluminosilicategel composition the Si/A1 ratio in the zeolite framework strongly depended on the applied alkali hydroxide. Na and K produced HEU zeolites with an Si/A1 ratio significantly higher than the one in the starting gel, the opposite was found for Li, whereas clinoptilolite-Rb had a composition close to the gel. These results may be interpreted that depending on the alkali cation, a different crystal growth mechanism operates. Thus during crystallization different growth surfaces are exposed leading to a different distribution of A1 tetrahedra [ 19]. 2.3. Low symmetry HEU frameworks There is also direct experimental evidence for low symmetry HEU frameworks. In a series of exchange experiments (K, NH4, Rb, Cs, Cd, and various alkylammonium ions) using as starting material the same Na-exchanged heulandite from Nasik (India) with the original c o m p o s i t i o n Nao.96Ko.09Ca3.54A18.625i27.51072 9 nH20, different space groups (C2/m, Cm, and C1) were analyzed for the exchanged products [25-28]. The differences in symmetry were also reflected in different patterns of Si, A1 ordering. There are two explanation for this observation: (i) The large single-crystals (up to 0.5 mm in maximum dimension) from Nasik were structurally inhomogeneous [19], (ii) the crystals were all triclinic, space group C1, and the observed space group depended on whether the exchanged cations occupied a position on a special position of local 2/m, or m, or 1 symmetry enhancing the symmetry information of the Si, A1 distribution in the framework. The difference of partial Si, A1 ordering alone (deviating from C2/m symmetry) is not sufficiently pronounced to be resolved from an X-ray single-crystal experiment. Notice that not necessarily the 'true' Si, A1 distribution will be resolved in such a diffraction experiment but only the contribution from the Si, A1 arrangement that is in resonance with the 'signals' from the extraframework occupant. Probably a combination of both inhomogeneity and low symmetry enhancement is the reason for the observation of different space groups. Yang and Armbruster [25] studied the structure of two Cs-exchanged crystals both had C1 symmetry but one crystal displayed a more pronounced Si, A1 ordering pattern than the other one. This example suggests an

18 inhomogeneous starting material [19]. For all hitherto analyzed triclinic HEU frameworks the deviation of the tx and ~ angles from 90 ~ was below 0.5 ~ [19, 25, 28, 29].

2.4. Consequences for further research The above observations and discussions indicate that HEU frameworks behave differently compared to most synthetic zeolites with disordered or partly disordered Si, A1 distribution. Even for a given Si/A1 ratio the exact exchange behavior of a HEU framework can not be predicted based on the existing knowledge. One of the reasons is the low topological symmetry (C2/m) of the HEU framework compared to the cubic frameworks of e.g. LTA or FAU. In low symmetry structures the distribution of Si and A1, or the existence of numerous polymorphs, plays a much more important role than in a high symmetry framework. In summary, we have to accept the conclusion [14] that for any 'sophisticated' practical application of natural clinoptilolites specific studies on representative samples from the deposit that is being examined for its exploitation potential have to be carried out. Even exact knowledge of the exchange behavior of well defined synthetic HEU frameworks [24] would not circumvent this problem. For a natural sample we never know its original formation condition and extraframework composition. It could well be that subsequent penetrating fluids in the deposit altered the original composition. The positive aspect of the structural complexity of HEU frameworks is that it offers the chance to learn more about tailor-made design of synthetic tetrahedral framework structures with only partly ordered Si, A1 distribution. 2.5. The Si, AI distribution in 'activated' clinoptilolite For most catalytic applications 'activated' zeolites are required. There are two standard routes how this activation can be achieved. Fairly well understood is ion-exchange to clinoptilolite-NH4 with subsequent release of H20 and NH3 upon heat treatment above 843 K leading to anhydrous clinoptilolite-H with BrCnsted centers [e.g. 30, 31]. Upon dehydroxylation at higher temperature the concentration of BrCnsted sites (acidic hydroxyl groups) decreases and Lewis sites are formed. Heat treatment of clinoptilolite-NH4 above 673 K leads also to partial dealumination of the framework and migration of A1 to extraframework sites [32, 33]. The second mechanism is based on acid treatment of the 'raw' zeolite [e.g. 34]. It was hitherto believed that the extraframework cations are replaced by H30 + and the tetrahedral framework is altered by loss of A1. According to Sychev et al. [34] 27A1 and 29Si NMR spectra of acid treated clinoptilolite-Na indicated that tetrahedral fragments consisting of SiO4 tetrahedra connected to two A104 tetrahedra are attacked, decreasing (for 2M HC1) the A1 concentration from originally 5.9 to 4.1 pfu. Misaelides et al. [35] leached natural heulandites for 48 h with HC1 solution of varying concentration (0.001 to 2 M) and noticed for samples treated with 1 and 2 M HC1 partial surface amorphization and decreasing A1 concentrations from the interior to the rim. The rim approached characteristics of amorphous silica gel [3537]. Yamamoto et al. [38] imaged by atomic force microscopy the (010) surface of heulandite leached with 0.2 N H2SO4 and found pits caused by layer-to-layer dissolution. Heulandite-Na exposed for 15 weeks at 423 K to 0.5 M REEC13 solution (pH 2.8) led to surface erosion and almost complete extraction of Na also in the center of heulandite crystals [39]. The loss of A1 in the center of the crystals was low. Subsequent X-ray single-crystal structure analysis [39] indicated partial rearrangement of framework A1 to hydrated extraframework A1, where A1

19 preferred octahedral coordination. Thus not only H30 § but also A13§ appeared as extraframework cations. In other words acid leaching of heulandite causes (i) A1 and extraframework cation depletion on the surface leading to an amorphous silica layer and (ii) depletion of extraframework cations in the core of the crystals where the HEU framework is still intact. In extreme cases all extraframework cations are lost and for charge balance two different exchange mechanisms operate: Na8A18Si28072 + 8 H30+ ----~[H30+]8A18Si28072 + 8 Na §

(1)

Na8A18Si28072 + 2 Si 4+ ~ [A13+]2A16Si30072 + 8 Na +

(2)

These data indicate that the structural state of acid leached heulandite or clinoptilolite is only poorly defined. The acidity of the solution, the time and temperature of leaching, crystal size, original crystal structure and composition have a strong influence on the leached structure. Variation of any of these parameters may cause variations in the structural state and in the associated catalytic behavior of the leached material. 3. RECENT P I O N E E R I N G STUDIES 3.1. Atomic force microscopy (AFM) Selective catalytic reactions occur also by molecular recognition on the external surface of zeolite crystals and therefore surface-structural information is vital for understanding catalytic mechanisms [40]. Large natural crystals of heulandite are available from various deposits and for this reason some of the pioneering AFM imaging of zeolite surfaces has been performed on these minerals [41-45]. 'Molecular resolution' was obtained for the heulandite (010) face that is densely packed without giving access to the two-dimensional channel system. This face was selected because it is prominent in natural crystals and (010) is also a perfect cleavage plane. In contrast, the resolution of the (100) surface, characterized by channel mouths of the eight-membered ring channels, was considerably poorer. Channel in- or outlets could not be resolved but appeared as undifferentiated grooves. Yamamoto et al. [45] argued that the lower resolution is caused by the tip-sample interactions on corrugated surfaces due to the channel mouths. In addition, it must be considered that faces like (100) are always decorated by traces of the perfect (010) cleavage and have therefore a rough surface. Corresponding lowresolution results were obtained for channel mouths in natural stilbite and mordenite. However, the ordered pore structure characterized by 12-membered tings could be imaged on the (001) face of a synthetic mordenite after scrapping off amorphous coatings [46]. Crystal growth induced steps (n x 9/~) on the heulandite (010) surface are either one or multiple tetrahedral layers thick [45]. Similar features have previously been observed on (010) cleavage plates [42]. In addition, growth spirals [44] and etch pits [38] on heulandite (010) faces were imaged. Adsorption of pyridine bases is generally applied to test the surface acid properties of zeolites. Adsorbed pyridine base molecules interact with the surface acid site and the strength of the interaction can be monitored by spectroscopic methods. Komiyama et al. [47] obtained in situ molecular AFM images of well ordered arrays of pyridine and I]-picoline on the (010)

20 surfaces of heulandite and stilbite and examined their orientation by semi-empirical molecular orbital calculations.

3.2. Clinoptilolite- heulandite electrodes for analytical application A carbon paste electrode modified with Cu2+-doped clinoptilolite powder has been evaluated as an amperometric sensor for non-electroactive NH4 + in flow injection analyses [48]. The conductivity of heulandite single crystals parallel to [ 100] has been studied under isothermal conditions as a function of the H20 content, small polar organic molecule concentration, and charge compensating cations. Results indicate that heulandite electrodes will be applicable for analytical purposes in aqueous solution [49]. 4. APPLICATION

4.1. Ion exchange and adsorption Clinoptilolite and heulandite are low field strength zeolites for which the cation specivities Cs + > R b + >NH4 + > K + > N a + > L i + >I-V, andBa 2+ > S r 2+ > C a 2+ > M g 2+ are predicted[ll, 12]. Corresponding theoretical estimates yielded Ba 2+ > Pb 2+ > Cd 2+ > Zn 2+ > Cu 2+ [16] but experiments revealed Pb 2+ -~ Ba 2+ >> Cu 2+ , Zn 2+ , Cd 2+ . Using clinoptilolite-Na as reference N H 4 + > P b 2+ > Na + > C d 2+ > C u 2 + _= Z n 2+ [ 14] and P b 2+ > N H 4 + > C u 2+ ___-C d 2+ > Z n 2+ ~ C o 2+ > Ni 2+ > Hg 2+ [15] has been determined. Charge-balancing cations present on the surface of very fine-grained clinoptilolite can be replaced by high-molecular-weight quaternary amines [50], such as hexadecyltrimethylammonium (HDTMA) whereas the intemal zeolite cavities remain accessible for small cations. Surfactant modified zeolites (SMZ) absorb CrO42-, benzene, and perchloroethylene (PCE) suggesting that a stable HDTMA bilayer (Fig. 3) formed on the external surface of the zeolite. Nonpolar organic solutes are sorbed by the organic phase whereas anions (CrO42) are retained on the outward pointing positively charged headgroups of the surfactant bilayer [50]. Various types of surfactants on clinoptilolite were applied to extract benzene, toluene, and xylenes from petrochemical spills [51]. HDTMA modified clinoptilolite exhibits enhanced sorption of U 6+ [52, 53].

Fig. 3. Sketchy drawing of HDTMA forming a bilayer (tail to tail) on the surface of clinoptilolite [50]. Nonpolar organic molecules (PCE) partition into the bilayer, anions (CrO42) exchange with the counterions of the suffactant, cations (Pb 2+) bind to the zeolite surface.

21 ~i-MnO2 precipitated on the clinoptilolite surface was successfully applied for removal of Mn 3§ from surface and deep-well water [54, 55] and for the treatment of paint-shop effluents [56].

4.1.1. Pollution abatement Pilot studies of NH4+ removal from municipal wastewater by using clinoptilolite-containing tuff were reported from various countries. After exchange and subsequent regeneration of the zeolite with NaC1/KC1 solutions ammonia was stripped from the solution and an ammoniumphosphate fertilizer was produced. The Tahoe-Truckee Sanitation Agency, California, treated between 1978 and 1993 8.107 m 3 wastewater applying a clinoptilolite tuff for ammonia exchange. The system was designed to accommodate a flow rate of 26,100 m3/day of wastewater and to extract 19.5 mg NH4/liter (507 kg) from a feedwater containing ca 25 mg/liter [57]. Ca-saturated clinoptilolite is used for ammonia removal from NASA's advanced life support wastewater system [58] to establish long term human presence in space. Natural zeolites are also produced for Pb 2§ and Cd 2§ removal from wastewater [e.g. 59, 60] and many other environmental application [61 ]. Low-cost surfactant-modified zeolites (SMZ) have been prepared in multi-ton quantities for use as subsurface permeable barriers to ground-water contaminant migration [50]. Most other studies on SMZ comprise small-scale laboratory experiments [e.g. 62, 63]. 4.1.2. The 1986 Chernobyl disaster In the USA and Great Britain phillipsite-, clinoptilolite-, and chabazite-rich tufts are routinely applied for the decontamination of radioactive wastewater to remove Cs and Sr radioisotopes [e.g. 64]. However, these are small-scale operations compared to the extensive use of natural zeolites at Chernobyl. During the Chernobyl disaster thirty to forty times the radioactivity of the atomic bombs dropped on Hiroshima and Nagasaki were released. The main radioactive isotopes from the Chernobyl accident were ~37Cs, 134Cs, 9~ and 89Sr. The details of zeolite applications at Chernobyl remain rather obscure because of a secrecy problem still remaining after disintegration of the former Soviet Union. About 500,000 tons of zeolite rocks, mainly containing clinoptilolite, were processed at various deposits in Ukraine, Georgia, and Russia specifically for use at Chernobyl [65]. The majority of the zeolites was used for the construction of protective barriers and for agricultural applications in polluted areas. Decontamination of potable water of the Dnieper fiver by using a combination of dust-like clinoptilolite and aluminum sulfate followed by filtration through clinoptilolite layers led to a drastic decrease of radioactivity [66, 67]. In addition, filters of clinoptilolite tufts were suggested to extract radionucleides from the drainage water of the encapsulated Chernobyl nuclear power plant. Filtration reduced 137Cs by 95% and 90Sr by 50-60%. After one year the filters carrying a radioactivity of 10.5 Ci/kg were exchanged and buffed [66]. To reduce Cs radionucleides in cow milk in Bulgaria 10% clinoptilolite was added to the cow feed resulting in 30% Cs reduction in the milk [68]. For Cs decontamination of children chocolate and biscuits were prepared containing 2-30 wt.% pure and powdery clinoptilolite [68]. In Western Europe clinoptilolite was tested to reduce radionucleide levels in soil [69], plants [70], sheep [71], broiler chicken [72], and fruit juice [73]. 4.1.3. Agronomic and horticultural applications The purpose of zeolite application in this field is slow-release fertilization or a combination of ion-exchange and mineral dissolution reactions. Mainly K- or NH4-saturated clinoptilolites

22 are used [74]. The term zeoponics can be applied to the cultivation of plants in any artificial soil in which zeolite minerals constitute an important component, e.g. in microgravity environments or lunar outposts [75]. The first zeoponic space vegetables grown from seeds were tiny radish roots produced on MIR OS in 1990 [76].

4.1.4. Animal hygiene and bedding products Application of clinoptilolite in this area is favorable because of its high NI-I4+ exchange capacity and surface absorption of odors (e.g. ethylene, aldehydes, mercaptans, ketones, H2S). Cat litter is sold in small bags yielding a profitable prize of ca. 800 US$ per ton [77]. Clinoptilolite occupies only a small niche in this market. The majority of cat litter is produced from clays. The annual volume of cat litter worldwide consumed equals about the annual production of natural zeolites. 4.1.5. Nutrition and health The physiological effects of clinoptilolite appear to be related to their high cation-exchange capacity, which affects tissue uptake and utilization of NH4+, Pb 2+, Cd 2+, Cu 2+, Cs +, and other cations in animals [78]. Clinoptilolite appears to be stable in the gastrointestinal tract and reduces ammonia toxicity in pigs and sheep. In ruminants clinoptilolite alters rumen fermentation, thereby modifying volatile fatty acid production by rumen microbes and changing milk and body fat content. Pigs, chickens, and turkeys are protected from mycotoxins in contaminated grains. The aflatoxin concentration in milk is reduced if cows are fed aflatoxin-contaminated feeds. The details of this protection mechanism is not yet understood but adsorption on the zeolite-surface may play an important role. In general, addition of 1 to 5 wt.% clinoptilolite to the diet of animals has been shown to improve growth and feed utilization and to reduce the incidence and severity of diarrhea in pigs, cattle, sheep, and chickens. Ag-exchanged clinoptilolite eliminates the microorganisms E. coli and S. faecalis from water after 2 h of contact time [79]. Clinoptilolite application is not restricted to animals but an anti-diarrheic drug (ENTEREX) has also been developed for humans [80]. Preliminary studies have been performed to test the potential use of clinoptilolite as a matrix for slow drug release [81, 82]. 4.1.6. Gas separation The gas adsorption characteristic of clinoptilolite strongly depends on the extraframework cations [83]. Nitrogen uptake, relative to methane, increases significantly away from the either pure Ca- or K-exchanged form. It is suggested that a specific K-Ca distribution within the structural channels may act as hydration controlled nano-valve [84] permitting diffusion of N2 but repelling CH4. Partly exchanged clinoptilolites applied for N2 and 02 separation from air yielded increasing separation rates for the sequence K > Rb > Na > Cs > Li [85]. There are several patents describing separation of CI-I4 from N2, hydrocarbons from CO2 and N2, 02 enrichment in air, and SO2 separation from air. 4.2. Catalysis As examples, xylene isomerization, toluene hydrodemethylation, n-butene isomerization, dehydration of methanol to demethyl ether, hydration of acetylene to acetaldehyde [31], catalytic reduction of NO [86] have been described to be successful if applying different varieties of treated clinoptilolite (cation exchanged or 'activated'). For a rough estimate about the importance of clinoptilolite for catalytic applications a search in the Chemical Abstracts

23 was performed (clinoptilolite and catalysis) leading to 413 hits between 1966 and 1999 (1-32 papers per year). Due to the low number of publications per year the histogram (Fig. 4) reveals a fairly coarse structure but a maximum in the early eighties and a minimum in the early nineties with a subsequent increase to recent times is recognized. If the statistical clinoptilolite data are normalized to the total number of papers dealing with zeolite and catalysis (31,034 hits) the maximum in the early eighties (ca. 3 % of the papers on zeolite catalysis) becomes even more prominent (Fig. 4). A closer look at research subjects in the statistical peak area does not indicate any specific invention that could be responsible for the increased scientific activity at this time. However, during increased activity (early eighties) more than 70% of the listed papers were written in Russian. In contrast, in 1998 ca. 60% were written in English (20% in Russian) but ca. 40% of the research institutions still belonged to countries of the former Soviet Union. The shallow minimum in the early nineties is characterized by a decreased publication activity in the former Soviet Union. Thus the statistical pattern is governed by the political development in Eastern Europe. During the cold war East European countries had no excess to the major producers of synthetic zeolites thus they developed technologies to use their abundant natural deposits for catalytic applications. The disintegration of the Soviet Union, accompanied by a political and economic crisis, led to a decrease of research activity in this field. The slight recovery of this trend in recent time is associated with an increased number of English papers written by East Europeans (lift of the iron curtain). One may extrapolate that in the future natural zeolites will become less important for catalytic applications.

Fig. 4. Histogram of papers listed in the Chemical Abstracts dealing with clinoptilolite and catalysis. The inlet displays a histogram of papers on zeolite and catalysis. This histogram is used to normalize the clinoptilolite and catalysis histogram. Notice the maximum in the early eighties caused by an increased research activity in the former Soviet Union.

24 5. OUTLOOK The highest profits for clinoptilolite seem to be achieved in the field of cat litter, animal bedding, and odor absorbents. With increasing environmental conscious applications in pollution abatement gain importance, in particular, if large amounts of ion exchanger or absorber are needed. The versatility of surface modified clinoptilolite is not fully explored yet. As the recent example of U 6§ sorption [52,53] on the surfactant indicates, many other applications seem possible where the advantages of the porous bulk structure are combined with specific properties of well-chosen surfactants. Most of the basic research work concentrated on ion exchange behavior studied in form of exchange isotherms. Nevertheless kinetic aspects are equally important [9, 87, 88] and there is a lack of knowledge, in particular for structurally and chemically well-defined clinoptilolites. Structure modeling has to be expanded to hydrous systems [89] to provide better understanding of H20 interactions with extraframework cations and the inner cavity or channel surface. HEU frameworks are interesting research subjects because of the only partly ordered Si, A1 distribution, the low symmetry of the framework, and the different types of channel systems. In this respect understanding of structure and properties of clinoptilolite provides a key for zeolites in general.

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27 71. M. Phillippo, S. Gvozdanovic, D. Gvozdanovic, J.K. Chesters, E. Paterson and C.F. Mills, Vet. Rec., 122 (1988) 560. 72. M. P6schl and J. BaltiC, Radiat. Environ. Biophys., 38 (1999) 117. 73. E. Breithaupt, M. Gahlmann, K.D. Buehler and K. Gierschner, Fluess. Obst, 56 (1989) 454. 74. E.R. Allen and D.W. Ming, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, 1995, p. 477. 75. D.W. Ming, D.J. Bata, D.C. Golden, C. Galindo and D.L. Henninger, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, 1995, p. 505. 76. T. Ivanova, I. Stoyanov, G. Stoilov, P. Kostov and S. Sapunova, in: G. Kirov, L. Filizova and O. Petrov (eds.), Natural Zeolites - Sofia '95, Pensoft, Sofia, 1997, p. 3. 77. G.S. Austin and C. Mojtabai, Bull. N. M. Bur. Mines. Miner. Resour.,154 (1995) 267. 78. W.G. Pond, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 449. 79. M. Rivera-Garza, M.T. Olgufn, I. Garcfa-Sosa, D. Alc~intara and G. Rodrfguez-Fuentes, Microporous and Mesoporous Mater., 39 (2000) 431. 80. G. Rodriguez-Fuentes, M.A. Barrios, A. Iraizoz, I. Perdomo and B. Cedr6, Zeolites, 19 (1997) 441. 81. A. Lam, L.R. Sierra, G. Rojas, A. Rivera, G. Rodriguez-Fuentes and L.A. Montero, Microporous and Mesoporous Mater., 23 (1998) 247. 82. A. Rivera, G. Rodriguez-Fuentes and E. Altshuler, Microporous and Mesoporous Mater., 40 (2000) 173. 83. M.W. Ackley and R.T. Yang, Ind. Eng. Chem. Res., 30 (1991) 2523. 84. D. O'Connor, P. Barnes, D.R. Bates and D.F. Lander, Chem. Comm., (1998) 2527. 85. I.M. Galabova and G.A. Haralampiev, in: The Properties and Applications of Zeolites, Spec. Publ. Chem. Soc. London, 33 (1980) 121. 86. H. Mishima, K. Hashmoto, T. Ono and M. Anpo, Appl. Catal. B: Environmental, 19 (1998) 119. 87. P. Yang, J. Stolz, Th. Armbmster and M.E. Gunter, Amer. Miner., 82 (1997) 517. 88. A. Dyer and K.J. White, Thermochim. Acta, 340-341 (1999) 341. 89. Y.M. Channon, C.R.A. Catlow, A.M. Gorman and R.A. Jackson, J. Phys. Chem., B, 102, No. 21 (1998) 4045.

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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

29

Evolution of extra-large pore materials Mark E. Davis Chemical Engineering, California Institute of Technology, Pasadena, CA 91125

The history of extra-large pore, crystalline materials is briefly reviewed. Relationships between extra-large pore molecular sieves and ordered mesoporous solids are outlined and the difficulties in creating crystalline, mesoporous materials discussed. The possible importance of three-membered rings in the preparation of extra-large pore microporous and/or mesoporous structures is described. The dichotomy between the high cost of production of extra-large pore materials via large, organic structure-directing agents and the low cost of the inorganic solid for typical commercial applications is enumerated and a new synthetic strategy provided to circumvent this problem. Keywords: extra-large pore materials, ordered mesoporous materials, zincosilicates, three-membered rings, large organic structure-directing agents

1.

Introduction

It has been slightly over a decade since the first publication on the existence of an extra-large pore molecular sieve; namely VPI-5 [1]. We suggested at that time the use of the term extra-large pore to describe crystalline materials having pores comprised of greater than 12 tetrahedral atoms (> 12 MR) [2]. This area of scientific endeavor has grown substantially in the past ten years and was certainly one of the factors contributing to the discovery of the ordered, mesoporous materials [3,4]. Here, I will review the brief history of extra-large pore materials, discuss the search for new extra-large pore materials, describe the relationships between extra-large pore materials and ordered, mesoporous materials and end by outlining a new strategy for the preparation of extra-large pore materials.

2.

History of extra-large pore materials

Richard Barrer and his collaborators were the first to publish (in 1969) on the idea of extra-large pore, crystalline materials [5]. Barrer and Villiger presented a series of hypothetical structures related to zeolites L, cancrinite, offretite and gmelinite that had 24 MR pores with free diameters of approximately

30 15 * [5]. Some of these networks consist of known, local atomic arrangements that do not violate crystal chemistry constraints, e.g., bond lengths and angles. The following passage is taken directly from the Barrer and Villiger paper: "Structures of the kind illustrated in Fig. 8 and Table 4, column 5, if they can be synthesized, may be of special significance. Both in respect of accessibility of intracrystalline pores and of total porosity (-- 0.6 of crystal volume) they would be well above any crystal hitherto known." Clearly, Barrer and Villiger set the stage for what was to come. However, what is surprising is that it took over a decade before significant discussions of extra-large pore materials appeared in the literature. In 1984, Smith and Dytrych described nets with channels of unlimited diameter and in particular a series of nets denoted 81 (n) [6]. Nets 81 and 81 (1) later turned out to be the topologies of A1PO4-5 and VPI-5, respectively [1]. Smith and Dytrych realized the significance of this net: "The 81 (n) series of nets is particularly rigid, and might prove useful in engineering design." Additionally, they suggested that large organic species, including chains and helices, should be considered as structure directing agents to prepare extra-large pore materials, e.g., 81(n) where n > 1. It is clear that Smith and Dytrych also anticipated the synthesis of extra-large pore, phosphate-based materials since they discussed the existence of the large channels (15 * ) in the phosphate-based mineral cacoxenite [7]. In the mid-1980's we began a program with the specific goal of synthesizing extra-large pore materials. Using the aforementioned literature as models, we initiated the exploration using large organic structure directing agents (including low generation dendrimers) with both silica and phosphate-based chemistries. In 1986, we prepared the material now denoted as VPI-5. It is not surprising that extra-large pore materials can be phosphate-based because of the existence of cacoxenite. VPI-5 was an unusual extra-large pore molecular sieve since it did not require a large organic structure directing agent for synthesis [8]. After the discovery of VPI-5, numerous phosphate-based, extra-large pore materials were prepared, e.g., see Table 1 of ref. 9, [10], etc. All of these materials require an organic component as part of the synthesis mixture (as does VPI-5 when preparing highly stable, good quality crystals). However, only VPI-5 does not contain organic components filling the pore space in the as-synthesized form. As expected, silica-based extra-large pore materials have also been prepared, i.e., UTD-1 [11] and CIT-5 [12]. UTD-1 requires an organometallic structure directing agent while CIT-5 uses more traditional quaternary ammonium compounds. Thus, the preparations of UTD-1 and CIT-5 follow the reasoning outlined by Smith and Dytrych with regard to the organic phase. The phosphatebased, extra-large pore materials are not consistent with the idea of using large organics since they tend to contain a high volume fraction of smaller organics (that is, they do not structure direct) or none at all (VPI-5).

31 Since the phosphate-based, extra-large pore materials do not reveal stability that is likely sufficient for many commercial applications, I will limit my discussions below to silica-based materials. As I have discussed elsewhere, the lack of stability in phosphate-based materials may not be due to the presence of extra-large rings, but rather to the nature of the structural units [9]. With silicabased, extra-large pore materials, it appears that bulky structure directing agents will be required for their preparation. I will make this assumption in further discussions below.

3. From extra-large pore crystalline materials to ordered, mesoporous materials The announcement of VPI-5 proved that extra-large pore molecular sieves could exist. This report encouraged significant further work. In addition to stimulating research on crystalline materials, VPI-5 played an interesting role in the discovery of the ordered, mesoporous materials. The paper by Kresge et al. in 1992 [3] opened the way for the vast amount of effort that has now been performed on ordered, mesoporous materials. The Kresge et al. report clearly showed the ordering that could occur in these types of materials and some of their properties. They also suggested how these materials may be formed. The solid with hexagonal symmetry was identified early on and several groups suggested that it may be one of the members of the 8 l(n) series for which VPI-5 is 81(1). However, we clearly showed that these types of materials are not crystalline, but more like amorphous oxides since dehydrated samples had Raman bands indicative of planar 3 MR stretching vibrations [ 13]. Crystalline frameworks with 3 MR do not reveal these vibrations [14] as only 3 MR at the surface of amorphous oxides reveal planar 3 MR vibrations [15]. Thus, it was absolutely clear from our results that the ordered, mesoporous materials were not crystalline frameworks [13]. Knowing this, it is expected that the mesoporous materials can be formed from any element combination making amorphous solids (including organic-inorganic materials [16]). Thus, it is not surprising that the ordered, mesoporous materials can be prepared to contain numerous element combinations and ones not available to crystalline solids. Since many properties of crystalline oxides, e.g., acidity, hydrothermal stability, etc., are the essential features exploited in commercial applications of these oxides, it is not unexpected that the ordered, mesoporous materials have not yet found much commerical use. The large void volumes, pore sizes and surface areas of the ordered, mesoporous materials provide advantages over microporous solids in certain areas of application but issues such as stability remain. Thus, if crystalline, extra-large pore solids could be prepared in the pore size and void volume ranges of the mesoporous materials, they would be immediately commercialized. The question remains as to why crystalline materials of this size range have not been synthesized. Navrotsky et al. have shown that pure silica, ordered, mesoporous silicas are energetically very close to pure silica, crystalline

32 molecular sieves [17]. For example, pure silica FAU has an enthalpy of 13.6 + 0.7 kJ/mol relative to quartz while MCM-41 has a value of 14.5 + 0.5 kJ/mol. Since the thermal energy at 373 K is 3.1 kJ/mol, these two structures are well within the available thermal energy of one another. Also, I predicted that if the materials were to be synthesized from aqueous solutions, they would have void fractions of approximately 0.8 or below [9]. There are ordered, mesoporous materials that conform to this limit. Thus, one is left to ponder why crystalline mesoporous materials have not yet been synthesized. The ordered, mesoporous materials can be prepared by many synthetic routes. This is not surprising since the lack of crystallinity does not place as many demands on the assembly process as with zeolites. By following the assembly process with in situ NMR, we were able to show that the high temperature construction of MCM-41 involved the formation of organic aggregates that subsequently ordered silica to form the final composite [18]. At other conditions, the assembly process can be different and involve layered phases [ 19]. Since it is now established that layered materials can be transformed into crystalline solids, e.g., MCM-22 [20], FER [21], VPI-5 [22], ERB-1 [23], the lack of crystalline mesoporous materials is not likely due to the inability to form layered intermediates. A possible reason for the lack of a crystalline mesoporous material could be related to the nature of the building units used for assembly. In 1989, Brunner and Meier [24] published a correlation between the framework density, FD (number of tetrahedral atoms per nm3), and the minimum ring size in the structure (MINR). For structures where the smallest ring for certain T-atoms is variable, the MINR value would have a + associated with it, e.g., MINR = 4+ for structures with some T-atoms in 4 MR whereas for others it is larger. I articulated some of the implications of this correlation at the time of the Brunner-Meier publication [25]. Of importance, I mentioned the possible synthesis of MINR = 3 or 3+ structures using elements other than beryllium because of its toxicity. If the Brunner-Meier correlation is correct, then the highest void volume, crystalline silica likely already exists. Since 3 MR are not synthetically feasible with crystalline silicas, a MINR = 4 framework will contain the highest void volume. From the Brunner-Meier correlation, the FAU topology is near the maximum void volume for MINR = 4 structures. To achieve the higher void volumes like those of the mesoporous materials, MINR = 3 or 3+ structures may need to be prepared. Berylosilicate chemistry does promote the formation of 3 MR as evidenced by a number of berylosilicate minerals, e.g., lovdarite, phenakite, euclase, and a synthetic analogue of lovdarite does exist [26]. However, the use of beryllium renders berylosilicates to be commercially unacceptable because of toxicity issues. Thus, in 1989, we began a program to prepare MINR = 3 or 3+ materials using zincosilicate chemistry since there are many zincosilicate analogues to 3 MR-containing berylosilicates. Listed below are the new zincosilicates prepared in our group.

33

Table 1. New Zincosilicates Material

Structure

Si/Zn

Pore Size

M I N R = 3+

Re f.

VPI-7

VSV (FD= 17.1)

3.5

9 MR

yes

27

VPI-8

VET (FD=19.8)

> 20

12 MR

no

28

VPI-9

VNI (FD= 16.7)

4

8 MR

yes

29

VPI- 10

no code (FD= 15.3)

3.5

9 MR

yes

30

Zn-ANA

ANA (FD= 18.6)

4

8 MR

no

31

Zn-SOD

SOD (FD= 17.2)

6

6 MR

no

32

CIT-2

no code (FD=15.8)

4

9 MR

yes

33

CIT-6

*BEA (FD=15.0)

> 15

12 MR

no

34

Additionally, Rohrig and Gies [35] have synthesized a zincosilicate denoted RUB-17 (RSN, FD = 16.8, MINR = 3+). Zinc is a relatively inexpensive, nontoxic element and as shown above, can be used to prepare MINR = 3+ materials. Additionally, there is a MINR = 3 zincosilicate mineral giving precedence for the existence of MINR = 3 micro and/or mesoporous, crystalline solids. Thus, the use of silica-based frameworks containing zinc could in principle lead to commercially viable extra-large pore materials that may be near the porosity of the ordered, mesoporous materials. A new strategy for synthesizing extra-large pore materials It is clear that crystalline, extra-large pore materials would be of significant commercial interest. The problem is their preparation and ultimately control of their properties. Based on the known extra-large pore materials, silicabased systems would be preferred over phosphate-based ones when dealing with issues such as stability and acidity. Another critical item is cost. For numerous applications, e.g., cracking and other refinery processes, the materials cannot be expensive. If one assumes that large organic moieties will be necessary for the preparation of extra-large pore, silica-based materials, the costs of the organic components are not compatible with the ultimate application of the porous solid. Thus, this issue must also be resolved. In some cases, the organic can be extracted from the molecular sieve. For pure-silica *BEA, Jones et al. [36] were able to extract the tetraethylammonium fluoride that was used as the structure directing agent (SDA). In that case, a small organic was used to prepare a 12 MR material. In some aspects, this situation is 4.

34 like that of the small organics used to prepare some of the extra-large pore, phosphate-base materials. The major difference of course is the stability of the inorganic portion; *BEA has very good stability while the phosphate materials do not. In principle, the small organics could organize and pack into ordered arrangements to yield large void spaces upon their removal. However, in practice, this type of organization has yielded only non-crystalline mesoporous materials (organics can also be extracted from mesoporous materials [13]). Thus, if a single large, bulky organic is necessary to structure direct extra-large pore, crystalline materials and the cost of the final product is somewhat limited, then how does one achieve the goal of producing such a material? In Fig. 1 a schematic of a new concept for the synthesis of extra-large pore materials is shown and illustrates how the previously posed question may be answered. component A + component B

ble

extra-large f pore z ~ l i t e / /

~~~)

+ [component A + component B] extra-large ~ [or precursors to] pore zeolite ~

disassemble ~ component C, ~ e.g., at low pH

~

bulky component C (SDA)

.

ynthesis,

( component )~_...-~

~

e.g., at high pH extra-large pore zeolite

Figure 1. New Concept for Extra-Large Pore Zeolite Synthesis [37] The idea is to combine two or more components into a large, bulky organic structure directing agent. The assembly can be via the formation of covalent bonds and/or through non-covalent interactions. The assembled SDA must remain stable to synthesis conditions, e.g., high pH with zeolites, in order to structure direct an extra-large pore material. Upon formation of the organicinorganic composite, the organic component now is disassembled at conditions that are not sufficient to harm the inorganic structure. The key to this concept is that the organics formed from the disassembly of the SDA can be re-assembled to make again the SDA. Thus, a large, bulky SDA is used to prepare the inorganic

35 structure and the components of the SDA are recycled in order to make the cost of the synthesis low. Numerous strategies can be employed with this idea. The concept is not unlike what happens in the assembly of the ordered, mesoporous phases. However, for the synthesis of extra-large pore crystalline materials, the assembly most likely will involve a small number of molecules (likely 2 or 3) to form the SDA and covalent linkages may also be exploited.

5.

Summary

The areas of extra-large pore, crystalline solids and non-crystalline, ordered mesoporous materials both continue to flourish. By investigating further the fundamental rules involved in their syntheses, it may be possible to make new solids with the advantageous properties of both existing classes of materials. Some of the issues of concern when performing such syntheses have been outlined here and several new suggestions for research provided.

REFERENCES [ 1] M.E. Davis, C. Saldarriaga, C. Montes, J. Garces and C. Crowder, Nature, 331 (1988) 698. [2] M.E. Davis, P.E. Hathaway and C. Montes, Zeolites, 9 (1989) 436. [3] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck, Nature, 359 (1992) 710. [4] T. Yanagisawa, T. Shimizu, K. Kuroda and C. Kato, Bull. Chem. Soc. Jpn., 63 (1990) 988. [5] R.M. Barrer and H. Villiger, Z. Kristallogr., 128 (1969) 352. [6] J.V. Smith and W.J. Dytrych, Nature, 309 (1984) 607. [7] P.B. Moore and J. Shen, Nature, 306 (1983) 356. [8] M.E. Davis, C. Montes and J.M. Garces, ACS Syrup. Ser., 398 (1989) 291. [9] M.E. Davis, Chem. Eur. J., 3 (1997) 1745. [10] G.Y. Yang and S.C. Sevov, J. Am. Chem. Soc., 121 (1999) 8389. [11 ] C.C. Freyhardt, M. Tsapatsis, R.F. Lobo, K.J. Balkus Jr. and M.E. Davis, Nature, 381 (1996) 295. [12] M. Yoshikawa, P. Wagner, M. Lovallo, K. Tsuji, T. Takewaki, C.Y. Chen, L.W. Beck, C. Jones, M. Tsapatsis, S.I. Zones and M.E. Davis, J. Phys. Chem. B, 102 (1998) 7139. [13] C.Y. Chen, H.X. Li and M. E. Davis, Microporous Mater., 2 (1993) 17. [14] M.J. Annen and M. E. Davis, Microporous Mater., 1 (1993) 57. [15] C.J. Brinker, R.J. Kirkpatrick, D.R. Tallant, B.C. Bunker and B. Montez, J. Non-Cryst. Solids, 99 (1988) 418. [16] S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna and O. Terasaki, J. Am. Chem. Soc., 121 (1999) 9611. [17] A. Navrotsky, I. Petrovic, Y. Hu, C.Y. Chen and M.E. Davis, Microporous Mater., 4 (1995) 95.

36 [181 [19]

[20] [21] [22] [23] [24] [25] [261 [271 [28]

[29]

[30] [311 [321 [33] [34] [35] [36] [37]

C.Y. Chen, S.L. Burkett, H.X. Li and M.E. Davis, Microporous Mater., 2 (1993) 27. A. Firouzi, D. Kumar, L.M. Bull, T. Besier, P. Sieger, Q. Huo, S.A. Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D. Margolese, G.D. Stuckey and B.F. Chmelka, Science, 267 (1995) 1138. M.E. Leonowicz, J.A. Lawton, S.K. Lawton and M.K. Rubin, Science, 264 (1994) 1910. L. Schreyeck, P. Caullet, J.C. Mougenel, J.C. Guth and B. Marler, J. Chem. Soc. Chem. Commun., (1995) 2187. M.E. Davis, C. Montes, P.E. Hathaway and J. M. Garces, Stud. Sur. Sci. Catal., 49 (1989) 199. R. Millini, G. Perego, W.D. Parker Jr., G. Bellussi and L. Carlussio, Microporous Mater, 4 (1995) 221. G.O. Brunner and W.M. Meier, Nature, 337 (1989) 146. M.E. Davis, Nature, 337 (1989) 117. S. Ueda, M. Koizumi, Ch. Baerlocher, L.B. McCusker and W.M. Meier, 7th IZC, Tokyo, Poster Paper 3C-3 (1986). M. Annen, M.E. Davis, J.B. Higgins and J.L. Schlenker, J. Chem. Soc. Chem. Commun. , (1991) 1175. C.C. Freyhardt, R.F. Lobo, S. Khodabandeh, J.E. Lewis Jr., M. Tsapatsis, M. Yoshikawa, M. Camblor, M. Pan, M.H. Helmkamp, S.I. Zones and M.E. Davis, J. Am. Chem. Soc., 118 (1996) 7299. L.B. McCusker, R.W. Grosse-Kunstleve, Ch. Baerlocher, M. Yoshikawa and M.E. Davis, Microporous Mater., 6 (1996) 295. R.W. Grosse-Kunstleve, Ph.D. Thesis, Swiss Federal Institute of Technology, ZUrich (1996). M. Annen, Ph.D. Thesis, Virginia Polytechnic Institute, Blacksburg, VA (1992). M.A. Camblor, R.F. Lobo, H. Koller and M.E. Davis, Chem. Mater. 6 (1994) 2193. P. Wagner, unpublished. T. Takewaki, L.W. Beck and M.E. Davis, J. Phys. Chem. B., 103 (1999) 2674. C. Rohrig and H. Gies, Angew. Chem. Int. Ed. Engl., 34 (1995) 63. C.W. Jones, K. Tsuji and M.E. Davis, Nature, 393 (1998) 52. M.E. Davis and S.I. Zones, U.S. Pat. Appl. (2000).

Studies in SurfaceScienceand Catalysis135 A. Galarneau,F. Di Renzo,F. Fajulaand J. Vedrine(Editors) 9 2001 ElsevierScienceB.V.All rightsreserved.

37

E v o l u t i o n o f R e f i n i n g and P e t r o c h e m i c a l s . W h a t is the place o f zeolites Christian Marcilly Institut Franqais du P6trole, Division Cin6tique et Catalyse, 1 et 4 Avenue de Bois Pr6au, 92852 Rueil Malmaison, France.

Introduction Refining and petrochemicals are the industries where zeolites are by far the most frequently used for adsorption and catalysis. The earliest application goes back to the end of the fifties, after the discovery by the company Linde of the synthesis of the A-type zeolite (1) capable of separating normal and branched paraffins. The second, and certainly the most significant event was the introduction of X and Y-type zeolites in catalytic cracking at the beginning of the sixties, which generated some deep technological changes in the process and substantial gains in gasoline yield. The first use of shape selectivity properties for zeolites dates back to 1968 with selective hydrocracking on erionite for normal paraffins of gasoline cuts. Over the last 40 years, zeolites were introduced first in refining, and then in petrochemicals, and now hold what may be considered a key position. The future of zeolites in refining and petrochemicals is obviously for a large part, directly related to the evolution of these two sectors, and we will be looking at their development in the first part of this paper. In the second part, we will discuss the place occupied by zeolites among catalysts and adsorbents used in refining and petrochemicals, and will briefly discuss some possible potential application for the future.

1. REFINING AND PETROCHEMICALS: EVOLUTION AND CHALLENGES IN THE 21st CENTURY Obviously it is not possible to discuss the long term prospects of these two domains of the petroleum sector seriously without referring to that of the petroleum resources that supply them.

1.1. The future of petroleum resources At the end of 99, world proven reserves were estimated at some 145 Gigatons (Gt) (2). These proven reserves will be depleted in about 40 years at the present rate of consumption (3.4 Gt/year) (2) and in 29 years if the growth in world consumption is 2 % a year. The ultimate reserves are extremely difficult to assess, as there are many unknowns. The figures given, which depend on the nature of the reserves considered and the degree of specialists' optimism, vary considerably. For instance, the liquid hydrocarbon reserves (conventional and non-conventional crude and gas-associated liquids) are estimated at 370 Gt i.e. 2,700 Gb by the IEA (International Energy Agency) and at 645 Gt i.e. 4,700 Gb by the DOE/EIA (Energy Informatibn Agency) (3). Depending on which hypothesis is adopted at the outset, the world production in liquid hydrocarbons is expected to reach a maximum in about 2015-2035. Depending on the growth

38 scenarios, ultimate reserves of 370 Gt should cover 60 to 100 years requirements (4, 5) and those of 645 Gt over 150 years. So the liquid hydrocarbon reserves are still substantial but their mobilization will demand significant efforts of research to make them usable (2). Sometime in the middle of the 21 st century, we will be turning to natural gas as the principal source of energy, coal and new renewable energies should remain at a modest level (6). Although the present petroleum resources are quite sufficient to satisfy the requirements of the first half of the 21 st century, their many and varied locations do pose a problem. The major part (66.5 %) of the 145 Gt of proven petroleum reserves is to be found in a geographical zone (The Middle East) where the political climate is unsettled, and on which the world will be depending more and more in the coming decades. Moreover, most consumer zones are far from producing zones, which means a intensive transportation activity between the two.

1.2. The demand in refined and petrochemical products 1.2.1. The development of requirements from 1970 to the end of the 2 0 th century Over the last thirty years, refining and petrochemicals have known an unsettled time with two oil crises (causing an economic downturn on a world wide scale), the Gulf war and an awakening of awareness regarding the degradation of our environment. Table 1 (2, 7) shows the development of the world petroleum consumption structure between 1970 and 2000. The following landmarks stand out : 9 The heavy fuels sector dropped rapidly, from 30 % in 1970 to 13 % in 2000 (a sharp and massive drop in the demand of electric power stations). This decrease should continue but at a slower rate. 9 By contrast, the part of light products increased during this period; especially that of middle distillates (jet fuels and gas oils) which increased from 27 to about 35 % between 1970 and 2000 and is likely to continue to grow, mainly due to the increased number of diesel engines among the European automotive population, whereas the proportion of gasoline has remained fairly steady since 1970. Table 1" Evolution of the structure of the demand in petroleum throughout the world (market economy countries) between 1970 and 2000. 1970 1980 1990 2000 106 t o n s % 106 t o n s % 106 t o n s * % 106 t o n s % Gasolines 492 25.4 626 26.6 750 26.8 876 26.2 Middle distill. 530 27.4 721 30.6 950 33.9 1163 34.8 Heavy fuels 608 31.4 645 27.4 500 17.9 426 12.8 Others 307 15.8 363 15.4 600 21.4 875 26.2 Total 1937 100 2355 100 2800 100 3340 100 Middle distillates: jet fuels, heating oil, diesel-oil. Others: refinery gas, LPGs, naphtas, solvents, lubricants, wax, bitumen, petroleum coke ... * Approximate values At the end of 1999, the world refining capacities were a little below 4.1Gt, with a low growth rate of about 10 % over 10 years (3.74 Gt in 1989).

39 In petrochemicals, the demand in olefins stagnated between 1978 and 1982 and then picked up and has grown fairly steadily since then, a little over 5 % a year on average, increasing from 65 Mt to126 Mt approximately between 1983 and 1997 (8). This annual growth can be broken down as 5.3 % for ethylene, 6 % for propylene, 15 % for isobutene and 2.2 % for butadiene (9). At the same time aromatics were on the increase, with an average growth of slightly under 5 % between 1983 and 1997, increasing from 30 Mt to some 57 Mt (8). During this period, benzene and especially PX, had the strongest growth, especially in South-East Asia. In 1997, world production of benzene represented a little less than half of the production of monoaromatics (27 Mt) (10). In the past 30 years, in order to handle changes in both the quantity and quality of demand, European refining has become more complex (table 2 ), stepping up conversion capacity (FCC in particular) and installing new hydrotreatment (reduction of sulphur content in fuels), hydrocracking and gasoline production units (11). The trend is even more strongly marked in the Asia-Pacific region due to the fast development of certain countries in the zone (South Korea for instance). Figures were noticeably high in 1999 compared with 1989, and this was also due in large part to the fact that China has recently been taken into account (China has over one third of the FCC units in the Asia-Pacific region). In North America, hydrogenating processes (HDT and hydrocracking (HDC)) continue to progress, whereas the others (cracking and special processes) appear to be stagnating. On a global scale, world refining capacities showed a downturn in the eighties due to the petroleum crises of 1970 and the resulting economic slump. Refining capacities picked up again in the nineties under the stimulus of the reduction in the price of gasoline and the economic expansion of South-East Asia, among other things. Table 2 (12-16): Development in the structure of world refining capacities between 1979 and 1999 and for the main geographical zones in Mt/year (the zones that did not have a market economy in 1979 and 1989 are not included in these two periods but are integrated in 99 : Former Soviet Union, China, North Korea, several Eastern European countries etc.). N. Amer. 437 260 46 997

1979 W. Asia World N. Eur. Pacific Amer. 346 214 9 523 49 30 400 304 6 1 9 72 998 520 3210 870

1989 W. Asia World N. Eur. Pacific Amer. 311 240 1290 577 88 51 531 298 15 14 130 84 832 500 2840 923

1999 W. Asia Eur. Pacific 404 374 106 125 34 35 723 982

HDT FCC. HDC Atm. Dist. HDT : Hydrotreatments, FCC : Fluid catalytic cracking, HDC : Hydrocracking, Atm. crude in atmospheric distillation.

World 1835 688 201 4077 Dist.:

1.2.2. Development forecast in market demand for products in the year 2010. Without any major changes in the general trend of demand, the policies applied regarding energy and crude prices should mean that annual petroleum consumption will increase from 3.3-3.4 Gt/year to over 5 Gt/year in 2020. In the coming decades, refining and petrochemicals will probably be operating in a restrictive context marked, among other things, by the following political-economic requirements :

40 9 The Environment : more respect for the environment will be demanded, limiting the release of pollutant gases (NOx, SO• volatile organic compounds), or discharge of contaminating liquids and solids, as much as possible. 9 Consumption : master consumption of petroleum products in order to limit gases with greenhouse effect (CO2 in particular), which will also help to preserve non-renewable resources. 9 Growth : promote the development of developing and newly developed countries as much as possible, controlling pollution and consumption. Maintain minimum sustainable growth making it possible to absorb the technological mutations imposed by progress (policy of full employment). 1.2.2.1. Quantitative demand It is interesting to assess what world refining will look like in the year 2010, considering both a developed geographical zone and one being developed. Table 3 (2) shows the development between 1990 and 2000 and that forecast between 2000 and 2010 in the demand for various petroleum products (especially gasoline, middle distillates and heavy fuels) in Europe (East + West), in the Asia-Pacific region (excluding Japan) and world wide. The global consumption of petroleum products increases only very moderately in Europe (the same applies to the United States) but more significantly on a global scale due to the substantial contribution of developing countries, in particular Asia. As shown on Table 3, the least developed part of the Asia-Pacific region has caught up with Europe by 2000 and will be well ahead of it in 2010. The forecast for 2010 for global demand in petroleum products reaches the 1999 figure for global refining capacity (4.1 Gt approx.) which should therefore increase moderately in the coming years. Table 3: Expected development of the demand for various petroleum products in Mt/year, in the European Union (EU), Asia-Pacific and the world between 1990 and 2010) (2) Europe* Asia-Pacific ** World Years 1990 2000 2010 1990 2000 2010 1990 2000 2010 Gasoline 138 153 168 114 183 253 746 876 1047 Middle distill. 235 303 342 174 312 451 950 1163 1472 Heavy fuels 90 77 60 82 104 132 504 426 456 Others 134 183 207 93 227 291 600 875 1046 Total 597 716 961 463 826 1127 2800 3340 4021 * Western + Eastern Europe (countries of former Soviet Union excluded) (Eastern Europe 10-15 % of Western Europe) ** Asia-Pacific except Japan Others: refinery gas, LPGs, naphthas, solvents, lubricants, wax, bitumen, petroleum coke ... Regarding petrochemicals, the demand in olefins and aromatics is, and will remain steady. Between 1995 and 2005 the demand for olefins is expected to grow at a rate of over 4 % on average, and that for aromatics by 3.6 % (8). Among the olefins, demand will typically be in the region of 4 to 5% for ethylene, 5 to 6 % for propylene, 6 % for isobutene and 3.3 % for butadiene (9, 17).

41 Forecasts up to 2003-2005 for the global demand in aromatics shows a growth of all monoaromatics, but it will vary considerably according to the compound considered and according to information source (10): it is in the range of 3.5 to 4.5 % a year for benzene (10, 17), from 5 to 8 % for PX approximately and significantly lower for the other aromatics (2, 10). What stands out, is the lack of balance between the growth in demand for benzene and xylene. The overall demand for petrochemicals should reach about 250 Mt in 2005 (8).

1.2.2.2. Changes in product quality Specifications regarding product quality have been getting increasingly stringent since the seventies, and this trend is most probably going to continue during the coming decade. The known or estimated development of specifications for the principal petroleum products between 1996 and 2010 is shown in Table 4 (2). Table 4: Evolution of specifications for three major petroleum products between 1996 and 2005 - 2010 (2) Europe Specifications Gasoline S (ppm) Benzene (% vol.) Arom. (% vol.) Olefins (% vol.) Oxygen (% vol.) RON/MON Diesel fuel Density max. S (ppm) Cetane number Cetane index Dist. 95% vol. Polyarom. (% mass) Total Aromatics Domestic fuel S (% masse) Heavy FO S (% masse)

Average Califomia (4)

1996-99

2000

2005 (project) ....

2010 (z) (possibility)

500 5

150 1 42 18 2.7 95/85

50

MDILD

ratio

1.4.1.4. A stronger interaction between refining and petrochemicals in the future (5 l) Faced with the complexity of the demands and increasingly stringent constraints, the two industries, refining and petrochemicals, will gradually have to tighten the bonds which had become somewhat slack over the last two decades. They will have to strengthen their exchange of products and make the most of all opportunities of complementarity in order to adapt to the new economic context. The following points can be given as examples : 9 Evolution of steam cracking feeds. Less availability of light naphthas, more and more frequently used by refining for reformulated gasoline, will oblige petrochemicals to look towards lighter feeds (petroleum gas, C3-C4 cuts from refineries with the olefins eliminated as well as gas condensates which could become significant feeds in the future) or towards heavier petroleum cuts with higher aromatic contents. 9 Recovery of light olefins for the petrochemical industry from a certain number of refinery effluents : refinery ethylene gas, propylene from the FCC LPGs 9 Recovery of effluents rich in hydrogen for the refinery and of isobutene and isopentenes from the steam-cracking C4 and C5 cuts respectively, for the production of ethers if these are not prohibited in gasolines. 9 Recovery of aromatics extracted from gasolines. By the year 2005, there will be a surplus of aromatics on the European market. The problem is that the European and world markets for aromatics are small compared with the corresponding gasoline markets. (Figure 4 ) (18). Thus the 1998 European market of aromatics is 13 Mt which breaks down into 6.5 Mt of B, 2 of T, 2.5 of X (mixture) and 2 of isomers (OX+PX) (18). The 1998 European market (East + West) for gasoline was about 168 Mt and the world market of 975 Mt (2). Every % of benzene in world gasoline represents about 1.5 times the European benzene production i.e. -~ 9.7 Mr. It should be possible for the European petrochemical sector to

53 absorb the surplus of benzene and of the other aromatics created by the enforcement of the 2000 specifications ( 1 % and 42 % in gasoline respectively) (18). This sector at present produces some 13-14 Mt of aromatics. However the limit of 35 % for aromatics in gasoline expected for 2005 will probably mean a further excess of over 10 Mt on the market if all the aromatics were to be extracted. (18) Such a quantity of aromatics could not be absorbed by the market and would cause prices to collapse (18). In such a situation, only the refineries that are large enough with a good enough performance could allow themselves to produce low cost aromatics. The others would have to find other solutions. 9 Use by the refining sector of processes initially developed by petrochemicals such as steam-reforming of natural gas, partial oxidation of residues, Fischer-Tropsch synthesis etc. Figure 4 (18): 1998 markets of aromatics in Asia, North America and Europe compared with corresponding markets and world markets of gasoline

1.4.2. For catalyst manufacturers and holders of process licenses (2, 52-54) Refining and heavy petrochemical industries can, on average, be considered mature industries (2, 51) where the differences between catalysts and/or the technologies of various competitors decrease. Thus, catalyst manufacturers and license holders attach increasing importance to factors of cost and productivity in order to remain competitive and survive (52,

54 53). In difficult economic context, this leads to turbulent times when associations and company mergers proliferate, all the actors seeking to strengthen their positions regarding innovation, productivity and commercial activities. In the coming decades, for the catalyst manufacturers, and for process license holders, the purpose will be first and foremost to remain competitive regarding the performance of commercialised products and their costs. The need for technical or technological innovation, whether small or big, to improve products or introduce new ones, remains a fundamental requirement, and from this view point, the rapidity at which innovations can be produced becomes of major importance. New method are still appearing (increasingly sophisticated techniques for characterisation, combinatorial chemistry, molecular modelisation, rapid information access and analysis) which will make it possible to speed up the rate at which innovations occur in the near future. But innovation is not the only lever for success. Other levers are in fact increasingly important for keeping ahead of the competition : 9 Cost reduction (improved productivity); 9 Proposal for complete sets of processes and catalyst systems; 9 Improvement of the number and quality of services associated with the catalyst and/or the process (integrated set of services for sale, technical assistance, treatment of used catalysts or recovery of worn catalysts etc.). 2. C A T A L Y S T S IN THE INDUSTRY. IMPLICATIONS

REFINING AND PETROCHEMICALS AND OPPORTUNITIES FOR ZEOLITES

2.1. Catalysts: World market In 1999, the world market for catalysts (including precious metals) reached 9 G$ with 24 % for refining, 23 % polymers, 24 % chemicals and 29 % environment. Table 9 gives the refining catalyst market in tons and $ by application for 1999 and 2005 (2). Table 9 1999 2005 Processes 103 tons % G$) 103 tons % G$) Cracking 495 77 0.7 560 73.6 0.83 Hydrotreatments 100 15.5 0.72 135 17.7 0.96 Hydrocracking 7 1.1 0.10 9 1.2 0.12 Reforming 6 0.9 0.12 7 0.9 0.15 Others - 35 5.5 0.56 -~50" 6.6 0.64 Total solids - 640-650 100 2.2 -760 100 2.7 Alkylation .3100' 0.85 3700* . 1 ~r catalysts for H2 production, polymerization, isomerization, etherification., Claus, lubes etc... * approximate values. En 1999, North America accounted for about 30 to 40 % of the market in $ depending on the sources of information (2, 55, 56) and Western Europe for 20 %. In 2005, their respective shares will be about 35-38 % and 19 % of this market.

55 Regarding petrochemicals, the world market of catalysts represented 2.16 G$ and 630 Mt in 1999 and will probably account for 2.53 G$ and 735 Mt in 2005 (2). 2.2. Zeolites: applications and general trends of development 2.2.1. Zeolites: main fields of application and markets (2, 57, 58) The world zeolite market has developed strongly over the last decades and at present represents some 1.6 Mt per year (58), with about 290,000 t/year for natural zeolites (approximately l 8 %) used in ionic exchange and adsorption. Applications of synthetic zeolites concern three major fields of activity amounting to some 1.3 Mt : detergents (A-type zeolites), adsorbents and desiccators (A and X-type zeolites mainly) and finally catalysis (especially Y-type zeolite). In 1998, the world market for these synthetic zeolites was approximately 1.6 G$, of which catalysis represented a little over 50 %) (2). As shown on Table 10 which gives these fields of activity according to major geographical regions, the share of catalysis in tons is much less and only represents a little over 12 %:

Table 10: Consumption of synthetic zeolites in thousands of tons (1998)

Detergents Catalysts Adsorb/Desic Total

N. Amer. 275 80 43 398

W. Eur. 505 25 27 557

E. Eur. 55 15"5.5 75.5

Japan Other 85 130 10 30 6.5 18 101.5 178

TOTAL 1050 160 100 1310

The expected evolution over 5 years (up to the year 2003) is on average a moderate global growth in the order of 1 to 1.5 % per year approximately for catalysis, from 1 to 2 % for adsorbents and desiccators and, for detergents, a slight decrease on average (-~1-2 % per year) in the major developed countries (lower quantities of zeolite in detergents). Out of the 1.3 Mt of synthetic zeolites produced annually, the A-type zeolite, with 1.1Mt, is by far the most commonly used (58). Its principal field of application is in the detergent industry, where certain modern detergents contain up to 40 % weight. About 100,000 tons per year of synthetic zeolites go to the adsorption sector (58-60) : desiccation and purifying standard applications (insulating windows mostly, refrigeration, treatment of natural and industrial gas, purification of olefins, desiccation of alcohols) and separations (n-paraffins, xylenes, PSA/VSA systems for the production of oxygen or hydrogen etc.). Among the zeolites used, the A-type zeolite is in a large majority (58) for desiccation and separations in particular, followed by X-type zeolite for the elimination of traces of polar impurities, and to a lesser degree, by various zeolites with high silicon contents such as mordenite and ZSM-5 for desiccation of acid gases or the elimination of volatile organic compounds. Regarding catalysis, almost all the zeolites used in the world are used in refining and petrochemicals. In refining, the principal applications are cracking (FCC), hydrocracking, isomerization of C5-C6 cuts and dewaxing or isodewaxing. In petrochemicals, the principal use is in aromatic transformation (alkylations, isomerization, disproportionation/ transalkylation) which, in 1999 represented 8.4 % and 6 % respectively of the financial volume and tonnage of petrochemical catalysts, i.e about 2 % of the financial volume of

56 world catalysts. The Y-type zeolite present in the FCC catalysts alone accounts for almost 95 % of the world consumption. Speciality zeolites, which account for only a few % of the world consumption of zeolites in catalysis, are mainly Y-type zeolites modified for hydrocracking and ZSM-5 zeolite as FCC additive. The production of other zeolites remains marginal. In all, out of 126 known zeolitic structures, only about a dozen are used in industrial or pre-industrial applications (2, 61, 62); these are the following" 9 A : (detergents, desiccation and separation) ; 9 F A U : X (desiccation, purification, separation) and Y (separation, catalysis) ; 9 M O R : (adsorption and catalysis) ; 9 LTL : KL-type zeolite (catalysis: aromatization) ; 9 MFI : Silicalite and ZSM-5 (adsorption and catalysis) ; 9 B E A : Beta-type zeolite (catalysis: cumene) ; 9 MTW : zeolite MCM-22 (catalysis: ethylbenzene, probably cumene ?) ; 9 CHA 9SAPO-34 (methanol to olefins or MTO process- demonstration unit ); 9 F E R : Ferrierite (skeletal isomerization of n-butenes- demonstration unit) ; 9 AEL and/or TON : SAPO-11 and possibly ZSM-22 (improvement of pour point for petroleum cuts by straight long paraffin isomerization) ; 9 Structures not revealed (for aromatic Cs isomerization) : one is certain (IFP) and the second is possible (UOP). 2.2.2. Openings

f o r z e o l i t e s in r e f i n i n g a n d p e t r o c h e m i c a l s

Zeolites have been present in refining since the beginning of the sixties (FAU cracking) and in petrochemicals of first generation intermediaries since the seventies ( transformation of aromatics on MOR). The success of zeolites in second generation intermediary chemistry and fine chemicals (63-73) are on the whole, more recent (63-70, 72, 73) and benefit from the zeolitic materials developed mostly for the first two industries. Significant improvements of these materials are still possible, and new applications using new materials or not yet used so far, will be emerging in the coming decades. However, it is very likely that from this point of view, fine chemicals will be more profitable than the mature industries like refining and petrochemicals for at least two reasons: (i) the variety of reactions is greater and the catalysts far from optimized (ii) the products have an added value that is greater and may make the high cost of certain zeolitic material acceptable. However, the quantities of products involved in the fine chemicals sector are small, and the volumes of zeolitic materials used will still be minor compared with those of refining. Considering the specifications imposed relating to petroleum products in general and fuels in particular, the refining industry and that of petrochemicals has, and will always have a need for more active catalysts and even more for more selective catalysts. On the latter point, zeolites will continue to hold a strong position to offer innovative solutions. The opportunity concerning the progress that they can provide must be sought first of all in existing processes or new processes aiming at producing the following hydrocarbons : 9 Light olefins from C3 to C5 as raw materials for petrochemicals or for the production of clean, good quality fuels. 9 Highly branched paraffins from C5 to C12 for the gasoline pool or longer and slightly branched paraffins for the kerosene and gas oil pools.

57 Specific molecules as first and/or second generation intermediaries in petrochemicals: alkylmonoaromatics in particular. From this point of view, the development of processes of inter-transformation of these aromatics can certainly be expected. More precisely, the following few opportunities for zeolites can be mentioned : 9 FCC : although it is not likely that the Y-type zeolite will be replaced as principal active agent, there may be room for additives enabling selective production of light olefins ranging from propylene to pentenes as long as these additives are competitive with the ZSM-5 regarding costs, activity and stability. 9 Hydrocracking (HDC) : the main factor for progress here would be to find a zeolitic catalyst dedicated to the production middle distillates, associating both the activity and the stability of zeolites and the selectivity of amorphous catalysts. 9 Aliphatic alkylation : the best zeolite found to date is the Beta-type zeolite, which does not contribute any octane gain compared with existing processes. A three-dimensional zeolite, more open than the Beta and at least as active, would be needed for this application. 9 Isomerization of paraffins : in the domain of middle paraffins from 7 to 9 carbons of the gasoline fraction, there is a need for a catalyst making it possible to achieve a thorough isomerization selectively (2 branches or more) while minimizing the cracking. However this is a difficult challenge for a bifunctional acid catalyst. 9 Dewaxing (gas oils, HDC residues, lube oils) : recent innovations in this domain (dewaxing by hydroisomerization) represent a significant breakthrough compared with classic processes by hydrocracking (on MFI structure). Progress is still possible in particular to further limit loss through cracking of isomerized products at high conversion. 9 Hydrodecyclization of polyaromatics of middle distillate cuts (LCO in particular) remains a significant challenge. The difficulty which acid catalysis comes up against is that the cycle opening is generally slower than the consecutive cracking of open products. 9 Transformation of aromatics : nearly all catalysts used are zeolitic. New zeolites can still provide gains in selectivity and stability. Also, the alkylation of aromatics other than benzene is of interest (ethyltoluene, isopropylbenzene, disopropylbenzene, paraethyltoluene, alkylnaphtalenes et dialkylnaphtalenes etc.). 9 Hydrotreatments : several studies have made it possible to detect some interesting potential among certain metal sulphides dispersed in the zeolites to desulphurize and denitrogenate certain refractory heteroatomic molecules (certain alkyldibenzothiphenes for example). One of the difficulties that has to be solved is to avoid excessive cracking of the hydrocarbons to be purified. 9 In the field of adsorption/separation, significant progress can be expected with the optimization of materials that are already known (crystalline defects, Si/A1 ratios, nature and position of cations, external surface properties, crystal size etc.) and the discovery of new materials.

58 Zeolitic membranes. In spite of many studies carried out since the eighties, the penetration of zeolitic membranes in industry has been very slow and has still not been integrated in refining and petrochemicals activities. These do however, represent an important application potential in the long term in the domain of molecular separation for certain catalytic separations. Considerable progress remains to be made regarding manufacture of these membranes (74).

Conclusion The global demand for petroleum products and therefore the capacities of refining and petrochemicals will continue to grow for many years to come. Refining and petrochemicals are mature industries that are constantly changing. For the last three decades, refining schemes have indeed evolved considerably. They continue to change to adapt to numerous constraints which are not likely to decrease in the foreseeable future, and which are due to the need to limit consumption of petroleum products (in particular CO2-related issues), to have greater respect for the Environment and minimize refining costs. In this context, zeolites have an important role to play. The contribution of zeolitic catalysts to refining and petrochemicals is already substantial. We can hope for further achievements in the future through improvements to existing catalysts and the development of new catalysts, as the association of the properties of acidity and shape selectivity offered by zeolites is unique. These achievements could occur in a wide variety of domains, affecting not only the major processes of hydrorefining and conversion, but also smaller capacity, more specialized processes. But the development of any new process always comes up against the unavoidable need to be profitable and competitive, which is often a difficult obstacle to overcome in mature industries like refining and petrochemicals.

Acknowledgement I would like to extend my gratitude to a number of people at IFP for their help in providing technical and economical information: M. Baraqu6, O. Clause, L. Cuiec, G. Fournier, L. Kerdraon, J. Larue, A. Methivier,, X. Montagne, I. Prevost, and more particularly to J.B. Sigault. Additionnally, I would like to thank Mrs E. Ubrich for its precious assistance in library information searches.

References 1. D.W. Breck, W.G. Eversole, R.M. Milton, T.B. Reed, T.L. Thomas, J. Am. Chem. Soc., 78, 5963, 1956. 2. IFP source. 3. J. Laherr~re, P6trole et Techniques, 416, 61-79, Sept-Oct. 1998. 4. P6trole et Techniques, 421, 35-39, juil.-AoOt 1999. 5. N. Jestin-Fleury, P6trole et Techniques, 414, 37-41, Mai-juin 1998. 6. O. Godard, P6trole et Techniques, 421, 97-99, juil.-Aofit 1999. 7. J. Masseron, ~,Warrendale (Pa.), Soc. Automot. Eng., 125p., 1999.

60 45. t~ Oil Information 2000 )),IEA Statistics, OECD/IEA, Paris, 2000. 46. J. Heinwood, A. Schafer, S6minaire Totalfina tt changements climatiques )), IPIECA, Paris,11-12 mai 1999, dans P & T, 421, p. 27, juil.-Aof~t 1999 47. M. Moret, P6trole et Techniques, 422, 68-73, Sept.-Oct. 1999. 48. J.B. Sigaud, P6trole et Techniques, 422, 89, Sept.-Oct. 1999. 49. J.B. Sigaud, Congr6s SIA 2000, Lyon (France), 14p., 10-11 Mai 2000. 50. J.P. Vettier, Conference at the ~ CEC-SAE Spring Fuels and Lubricants Meeting ~, Paris,19-22 june 2000. 51. C. Belorgeot, X. Boy de la Tour, A. Chauvel, S6minaire ~ Vers le 21 e si6cle avec les technologies de I'IFP ~), Paris, juin 1994. 52. G. Martino, C. Marcilly, Petrofina Chair, Leuven Summerschool on catalysis, Brugge, Belgium, Oct. 12-15, 1997. 53. C.A. Cabrera, CatCon 2000, Houston (TX), USA, June 12-13, 2000. 54. I.E. Maxwell, Cattech, 5-13, March 1997. 55. W. Weirauch, Hydroc. Process., 79 (2), 23, Feb. 2000. 56. Oil Gas J., p 53, Feb. 28, 2000. 57. Source CECA 58. A. Pfenninger, Proceed. Symp. on ~ Industrial Applications of Zeolites )), Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 73-82, 2000. 59. C.G. Coe, Presentation at Symp. On ~ Industrial Applications of zeolites ~), Brugge, Belgium, Oct. 22-25, 2000. 60. M.T. Grandmougin, R. Le Bec, D. Plee, G. Dona, Proceed. Symp. on ~ Industrial Applications of Zeolites ~>,Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 93104, 2000. 61. M.W Schoonover, M.J. Cohn, Topics in Catal., 13,367-372, 2000. 62. C.R. Marcilly, Topics in Catal., 13 (4), 357-366, 2000. 63. K. Tanabe, W.F. HOlderich, Appl. Catal. A : General, 181,399-434, 1999. 64. R.A. Sheldon, R.S. Downing, Appl. Catal. A : General, 189, 163-183, 1999. 65. M.G. Clerici, Topics in Catal., 13 (4), 373-386, 2000. 66. W. Htilderich, H. van Bekkum, in ~ Introduction to Zeolite Science and Practice )), H. van Bekkum, E.M. Flanigen, J.C. Jansen, Eds, Elsevier, Amsterdam, Stud. Surf. Sci. Catal.,, 58, 631, 1991. 67. P.B. Venuto, in ~ Progress in Zeolite and Microporous Materials, H. Chon, S.K. Ihm, Y.S. Uh, Eds, Elsevier, Amsterdam, 811-852, 1997. 68. M. Spagnol, L. Gilbert, R. Jacquot, H. Guillot, P.J. Tirel, A.M. le Govic, 4th Intern. Symp. Heterog. Catal. And Fine Chemicals, Basel, Switzerland, 1996. 69. S. Ratton, Chimica Oggi, 33-37, March-April 1998. 70. P.B. Venuto, Microp. Mater., 2, 297, 1994. 71. P.B. Venuto, P.S. Landis,, Adv. Catal., 18,259-371, 1968. 72. B. Coq, V. Gourves, F. Figueras, Appl. Catal A : General, 100, 69, 1993. 73. C. Moreau, F. Fajula, A. Finiels, S. Razigade, L. Gilbert, R. Jacquot, S. Spagnol, Catal. Org. React.,Dekker, p.51, 1998. 74. M. Noack, P. K61ch, R. Sch~ifer, P. Toussaint, J. Caro, I. Sieber, Proceed. Symp. on ~ Industrial Applications of Zeolites >~,Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 25-34, 2000.

Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

61

Is Electron Microscope an Efficient Magnifying Glass for Micro- and Meso-porous Materials ? Osamu TERASAKI a'b'* and Tetsu OHSUNA ~ a: Deptartment of Physics and CIR, Tohoku University, Sendai 980-8578, Japan_ b: CREST, JST, Tohoku University, Sendai 980-8578, Japan c: Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan * Corresponding Author: [email protected]

Using electron microscopy(EM), we can solve three dimensional structures of microand meso-porous materials through newly developed methods based on electron crystallography. The underlying principle among diffraction, image and Fourier transformation for the methods, and a resolution of the method are discussed in terms of structure details we are interested in. An example of structure analysis for SBA-6 shows power of the methods, and future tasks will be discussed at the Conference.

1. INTRODUCTION

1-1. Microscope and Resolution The optical microscope is an instrument that uses lenses to produce enlarged images of small objects especially too small to be seen by the naked eye In an optical microscope, the spatial distribution of absorption or reflectance of light is enlarged. It is seldom, as far as we know, an optical microscope is used to obtain diffraction information except a conoscope. Big effort was paid to improve the resolution of optical microscope to observe smaller objects. However, the resolution of perfect lens(theoretical), Rth, is given from Rayleigh criteria as Rth =1.22 X/ct, (eq. 1) where ct and X are angular aperture size and wavelength. Necessary resolution comes from what kind of structural information we are interested in. The resolution of optical microscope is far below to resolve structure in atomic scale, as X is 3000-8000A for visible light and a is order of 1 (most of text books used semi-angle, or/2). Although the wavelengths of characteristic X-ray for ka radiation of 3d-transition metals are suitable range of 1.5-2.5 A for atomic resolution, we can not make a reasonable lens.

62 Electron has charge, and we can make an electromagnetic lens through the Lorentz force and hence an electron microscope(EM). Applying the de Broglie relation, the wavelength of electrons is determined by (A) = h/~/(2meV) -- ~/{150/V(volts)},

(eq. 2 )

where h, m, e and V are Planck's constant, electron mass, electron charge and accelerating voltage, respectively. ~, is 0.037 A at 100 kV and looks small enough to resolve structure in atomic scale if we can keep o~ to be order of 1. Is the resolution of electron microscope enough to resolve structures in atomic scale? In case of

electromagnetic lens, lens is not perfect with different kinds of aberrations. From geometrical optics, a point source will be imaged as not a point but a disk by a lens with spherical aberration. Disk diameter of confusion, R~ph,is given by Cs(ct/2) 3, where C, is a spherical aberration constant of the lens. Taking the effect of the aberration into account, the resolution R can be expressed as R = ~/{(Rth2+ R~ph2)}

(eq. 3)

as Rth and P~phare independent event each other. R~in = 0.9 (X3/4Cs1/4)

R takes minimum value

(eq. 4 )

at optimum angular aperture size t~opt - 1.54 (L/Cs)TM

(eq. 5 )

In other words, an effective value of t~ in eq. 1 for the electromagnetic lens is essentially given by a spherical aberration as 1.54(2qC~)TM, and is order of 10 -3.

The

attainable resolution is given by 0.9 (X3/4CsTM)and is 1.8 - 2.5 A range for most of 200 and 300 kV EMs. However, it is very hard to reach the resolution mentioned above for a case of zeolites(microporous materials), because they are so electron beam sensitive that we can not irradiate enough number of electrons onto them for taking HREM images. Therefore HREM is not enough to resolve atomic arrangement for zeolites[ 13]. Diffraction study is another and principal approach for structural study. It is well known that X-ray diffraction(XRD) can give average structural information with very high resolution and XRD has been used to solve structure of zeolites in atomic scale and also to show long range order in mesoporous materials. Using EM, however, we are able to observe both electron diffraction(ED) patterns and images. ED is free from the aberration effect and provides like XRD structural information with much higher spatial resolution than HREM images, and we can obtain ED data with much smaller

63 number of electrons. Electrons are scattered through the interaction with the electrostatic potential formed by the electrons and nucleus of the constituent atoms. The scattering power of atoms for electrons is called as the atomic scattering factor and is approximately 104 times as large as that for X-rays. This suggests that compared to X-ray scattering, smaller scatterers can provide sufficient structural information and thus much smaller objects(ca. 10-8 times) can be studied with electrons. It is to be noted here that we could choose a proper small crystalline area in image mode and obtain single crystal diffraction information only from the same area, and that EM is very powerful for micro- and meso-porous materials as they are mostly synthesized as panicles of c a . 1 lam in size. In this paper, we will give general background of electron crystallography to solve micro- and mesoporous structures and show EM is unique and powerful technique by a few examples. At the Conference, other relateds will be also discussed. 1-2. Diffraction, Image and Fourier Transform

Figure 1 shows a schematic drawing, which gives length scale of our interests. Crystal is a three-dimensional (3-d) periodic array of unit cells, each of which contains a same arrangement of atoms. Therefore to solve atomic arrangement, that is, to determine distribution of scattering density, V(r), in a unit cell is a central problem for Resolution of Electron Mkroseopy I

I'

I

Wave length

Wave length of X-ray

Wave length of light

of eleclron

V lOOA t

2 A,

I

+

0.1.~

lit

I

I

v

Structures of Mesoporous Diameters of Pore & Cage are 20-500 A

Framework Strueture of Zeolites Bond di st~ces, T-O = 1.6 A T- (O) -T= 3 A

Fig. 1

Atomic Coordinates Atomic coordinates are obtained by statistical treatment from many rdlecti ons up to large scattering vectors.

Schematic Length Scale

d (X)

64 structure analysis. V(r) can be obtained from analysis of crystal structure factor(CSF), F(h), for h (h,k,1) reflection, which are Fourier coefficient of V(r) as F(h) =

~ V(r) exp 2hi h r d r = [ F(h) [ exp{ i 0(h)},

(eq. 6)

where 0(h) is phase of CSF. CSF is complex in general. A position r in the unit cell can be given by fractional coordinates with lattice vectors a, b, c, as r = xa+yb+zc.

(eq. 7)

Reciprocal vector h is given by a set of (h,k,l) and reciprocal lattice vectors, a*, b*, c*, h=ha*+kb*+lc*

.

(eq. 8)

Once, 3-d data set ofF(h) is obtained then structure V(r) can be determined by an inverse Fourier transform straightforwardly as V(r) = ~ F(h) exp(- 2rcir h) dh

(eq. 9)

.

Diffraction intensity I(h) for h reflection is given by I(h) = F(h)* F(h) = [I F(h) I ]2

(eq. 10)

and looses phase information. Therefore we can obtain only absolute value, moduli, I F(h) I from diffraction intensity. For a centrosymmetric crystal, we can make F(h) real, that is phases of F(h) are either 0(+) or ~(-)by taking an origin at inversion centre for eq. 7.

Hereafter, we will treat only centrosymmetric crystals for simplicity. In

order to show an importance of the phases of CSFs for obtaining correct

ceelxl

~.

,

"~_~.f

f

structure V(r), one dimensional model system is shown schematicaly in Fig. 2. Two structures among a

i[

0=0

]

"?

-t

number of possible ones, (a) and (b), cod3xl

give exactly the same diffraction intensities, only difference between

$=0

/-\ f \ ,/~x / v \./ \ ~=g

the two is phases 0(h) in F(h), that is, phases of g, 2g, 3g reflections are +,

(a) cos[x] + cos[2x], cos[3x]

(b) cos[x]- cos[2x]- cos[3x]

4

+, + for case of (a) and + , - , - for case of (b). After determining space group,

,

2

_(a) 9

(b

r O -I

two major approaches to solve the

-Z

Fig. 2 Importance of phases in CSFs is shown schematically for one dimensional case.

65

Fig. 3 Flow chart of Structure Solution structure by tackling phase problem are schematically shown in Fig. 3. (1) Through ED patterns: Attempts to find phases have been based on a trial-and-error process. CSFs were calculated for a trial structure and compared with intensity I(h) under the measure of agreement, so called reliability index Reac-Patterson function method or heavy-atom method helped greatly to reduce number of trial structures by giving information of interatomic vectors of main scatterers or of heavy-atom positions. Direct method opened new fields for the process in estimate of the phases ab initio from

66 the magnitudes of the structure factors. In order to apply this method, intensities for many independent reflections must be measured. (2) Through HREM images: HREM images carry phase information, and in this case we can determine phases uniquely without pre-assumed structure models. Now, let us think by Figs..2 and 3 a relation between diffraction and image, and information limit for phases by EM image. Electrons are incident to a crystal as a plane wave. We will take the direction of incident electrons to be z-axis. The role of the objective lens is to transfer Fourier transform of wave field at the exit of the sample for a set o f g reflections with CSFs of F(g) as shown in Fig. 2, i.e., Franhoufer diffraction, to the back focal plane of the lens. The lens further (inverse) Fourier transforms the diffraction to image at the image plane. ED patterns and EM images are observed as an intensity distribution in reciprocal space and real space, respectively. From this procedure, it is obvious EM images carry phase information of CSFs, but the information of CSFs within a range given by Ctopt (eq. 5) is transferred (see Fig. 3).

2. Mesoporous materials: The local structure variations in mesoporous materials are common and produce a small number of reflections and large peak widths in powder XRD patterns, even though the materials show nice crystal morphology. This situation can be shown by an example for MCM-48 in Figure 4. Two structural characteristics of the meoporous materials are clearly observed in the powder XRD pattern(Fig. 4a), where (i) disorder on the atomic scale (short-range) can be seen as diffuse intensity at medium range of scattering angles and (ii) distinct order on the mesoscopic scale (long-range) can be seen

Fig. 4 Powder XRD pattern and SEM imageof MCM-48.

67 as a few sharp diffraction peaks at small scattering angles. SEM image of MCM-48(Fig. 4b) clearly shows nice crystal morphology which is commensurate with point symmetry ofm-3m. By noticing 3-d mesoporous material as crystalline, we have developed a new method for solving the structures with meso-scale ordering without assuming any structural models based on section 1-2. The resolution for the structure is primarily limited by the quality of the HREM images, which depends on the long-range meso-scale ordering and the treatment of the EM image processing.

Further progress may give better

Fig. 5 HREM images of SBA-6 and corresponding Fourier diffractograms

68 resolution, but no change in conclusions will be necessary about structure because the validity of a solution does not depend on the resolution[4,5]. Figure 5 shows a set of HREM images of SBA-6 together with Fourier diffractograms. From image we can choose thin areas

which

dynamical

are

scattering

free and

from the

Fourier diffractograms from thin regions are also shown in Fig. 5. From observations in extinction conditions from the diffractograms and in point group symmetry from SEM image, the space group of SBA-6 was uniquely determined to be Pm-3n. Basic structure of SBA-6 can be obtained only from two HREM images of [100] and [110] incidences. The images of [ 111 ]

and

[210]

incidences

improved fine details of structures

Fig. 6

Structure solution of SBA-6. Pm-3n.

of cages and tunnels between them[5]. The cages are arranged in A3B type, where the A-cage is the larger with a diameter of 85 ,/~ at (1/2,0,1/4), (1/2,0,3/4), (0,1/4,1/2), (0,3/4,1/2), (1/4,1/2,0) and (3/4,1/2,0), and the B-cage is the smaller with a diameter of 73 fit at (0,0,0) and (1/2,1/2,1/2). A B-cage is surrounded by 12 A-cages that are connected through openings of 20/k, while the openings between A-cages are about 33 x 41 A. The materials synthesized in the spaces of mesoporous throw us new challenging problems to solve their structures by EM, and it will be discussed at the conference.

3. Zeolites:

Now we can measure ED intensities easily by using CCD camera or imaging plate as they have larger dynamic range and better linearity of output to input electrons than photographic film. Applying "Direct method" to collected ED intensities of 326 independent reflections from 11 zone axes, we could solve unknown structure of

69 zeolite SFE(SSZ-48) from very small crystal[6]. As zeolites have low density, kinematical treatment in diffraction is a good approximation for analysis of ED intensity distribution, if specimens are thinner than a few hundreds A. This is not so difficult conditions for zeolites if we can obtain as a single(pure) phase, Therefore this method is very powerful.

Fig. 7 HREM images of ETS- 10

70 Once a high quality HREM image is obtained, we can build important structural units and geometrical relations between them by making plastic bond-models. A clear example is shown here for ETS-10, which contains many different types of defects. It was confirmed from ED patterns and HREM images that ETS-10 has 4-fold symmetry in projection along z-axis and that the projected structures along x- and y-axes are identical. An HREM image(Fig.7a) gives important pore arrangement and the framework connectivity, and hints to build a primary structure unit(Fig.8 a). Fig. 7b shows surface structure suggesting that a rod is a secondary building and is growth unit in ETS-10(Fig. 8b). An ideal structure was determined from the observations as shown in Fig.8c[7,8,9]. This analysis requires deep knowledge of both structure and EM.

Fig. 8 Schematic drawings of framework structure of ETS-10

Recently we have developed a new powerful method for obtaining structure solutions of zeolites by combining HREM images and ED intensity data[ 10]. This will open up new field for the structure analysis of zeolites, however, we should continue to develop the method of solving structures further in order to make E M better magnifier towards atomic resolution.

4. Acknowledgments The authors greatfully acknowledge CREST, JST for financial support. We thank P. Wagner, A. Carlsson, Y. Sakamoto, M. Kaneda, Z. Liu, K. Hiraga and T. Tsubakiyama for their contributions.

71 References and Notes

[1] O. Terasaki. Molecular Sieves, Science and Technology. Vol. 2, pp71-112., Eds by H.G. Karge & J. Weitkamp, Springer-Verlag, Berlin, 1999. [2] O. Terasaki & T. Ohsuna. Catlysis Today 23(1995), 201-218. [3] O.Terasaki, T.Ohsuna, N.Ohnishi & K.Hiraga. Current Opinion in Solid State & Materials Science 2(1997), 94-100. [4] A.Carlsson, M. Kaneda, Y. Sakamoto, O. Terasaki, R. Ryoo & H. Joo J. Electron Microscopy. 48 (1999), 795-798. [5] Y. Sakamoto, M. Kaneda, O. Terasaki, D.Y. Zhao, J.M. Kim, G. Stucky, H.J. Shin & R. Ryoo. Nature 408 (2000), 449-453. [6] P. Wagner, O. Terasaki, S. Ritsch, S.I. Zones, M.E. Davis and K. Hiraga. J. Phys. Chem. B103 (1999), 8245-8250. [7] M.W. Anderson, O. Terasaki, T. Ohsuna, P. Phillppou, SP MacKay. A. Ferrelra, J. Rocha & S. Lidin: Nature 367(1994), 347-351. [8] T. Ohsuna, O. Terasaki, D. Watanabe, M.W. Anderson & S. Lidin: Studies in Surface Science and Catalysis, Vol 84, 1994, 413-420. [9] M.W. Anderson, O. Terasaki, T. Ohsuna, P.J.O Malley, P. Phillppou, SP. MacKay. A. Ferrelra, J. Rocha & S. Lidin: Phil. Mag 71(1995), 813-841. [ 10] T. Ohsuna et al., in preparation

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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

73

Delaminated zeolites as active catalysts for processing large molecules A. Corma* and V. Forn6s Instituto de Tecnologfa Qufmica, UPV-CSIC, Universidad Polit6cnica de Valencia, Avda. de los Naranjos s/n. 46022 Valencia, Spain Zeolite nanolayers have been obtained by delaminating the lamellar precursors of four zeolites. These materials present very high well structured extemal surface areas larger than 600 mZ.gl. Catalytic active sites can be introduced during the synthesis or by post-synthesis treatments, yielding active and selective catalysts for processing large size molecules of interest in oil refining and for the production of fine chemicals. 1. INTRODUCTION Zeolites have shown great utility as catalysts in the field of oil refining, petrochemistry and in the synthesis of chemicals and fine chemicals (1-3). In some cases shape selectivity effects are highly desired when using zeolites, while in others the main objective is to replace liquid acids using instead the environmentally more friendly solid acids. In this second case, there is a continuous interest to find molecular sieves with large and ultra-large pores that can convert bulky reactant molecules. If this could be achieved, the impact of zeolites would be even more important in processes such as fluid catalytic cracking (FCC), hydrocracking, hydrotreating, and in the production of chemicals and fine chemicals. Up to now, zeolites with 14 member ring (MR) pores are the ones with the largest pore synthesised (4,5). However, in these structures the pores are unidirectional and offer little advantage with respect to the tridirectional 12 MR Y and Beta zeolite for processing large molecules (6). Recently, mesoporous molecular sieves with different topologies have been synthesised (7-9). They show no short range order and the catalytic behaviour is closer to that of an amorphous silicaalumina with a narrow pore size distribution, than to a zeolite. There is then incentive to develop zeolitic materials that while keeping the short range crystallinity of zeolites, can have the accessibility of silica-alumina towards very large reactant molecules. One possibility along this direction is to synthesise small zeolite crystals (nanocrystalline zeolites) (10) that show a high ratio of external to internal surface, with enhanced possibilities to adsorb large reactant molecules on the external surface of the crystallites. While we have seen that this, can be an interesting approach in some cases (11), we have recently explored another direction (12,13) which involves the preparation of lamellar zeolites whose structure is subsequently delaminated, making accessible through the external surface all the potential active sites. The main difference between these type of materials and the mesoporous molecular sieves of the

74 MCM-41 type is that in the nanocrystalline and delaminated zeolites there is short-range order and consequently the active sites are of zeolitic nature. 2. DELAMINATED Z E O L I T E STRUCTURES Up to now, we have delaminated four different lamellar zeolitic precursors which have generated the materials named as ITQ-2, ITQ-6, ITQ-18 and ITQ-20 (12,13). The first one, ITQ-2, was obtained by delaminating a MWW zeolite precursor (14) while ITQ-6 and ITQ-20 were prepared by delaminating laminar precursor of ferrierite (15) and MCM-4"7 (16,17), respectively, while the structure of ITQ-18 is still unknown to us. The artist view of the structure of the two first material is presented in Figure 1.

Fig. 1. Artistic view of the structure oflTQ-2 and ITQ-6 delaminated zeolites. As a general procedure, the lamellar precursors of zeolites are swelled, at the adequate pH, using an alkyl ammonium bromide, or even an amine or an alcohol can also be used, to separate the layers. After this the swelled material can be delaminated by means of ultrasound, freezdrying, or by vigorous stirring. The "in situ" delaminated material can form an slurry or a paste with a matrix component and a binder, and the final product can be spry dried or extruded, respectively. If desired, the pure delaminated materials can be recovered by centrifugation. Activation is carried out by extracting the organics in liquid phase, or by decomposing them by calcination in air at 500~ It has to be noticed that these materials are stable upon calcinations at 700~ As one can expect, the X-Ray diffractogram of delaminated zeolites, show a small number of peaks, which are due to the reflections along the two main dimensions of the layers, while those due to the regular ordering of layers one above the other have disappeared owing to the delamination. More specifically (Fig. 2), in the case of ITQ-2 the XRD does not show the 001 and 002 peaks at 20=3-7 ~ while in the case of ITQ-6 the hOe reflections have practically disappeared.

75

,

,

,

,

,

10

0

20 20

,

,

30

,

,

.

40

0

.

.

.

.

.

10

.

.

20 20

.

30

40

Fig. 2. XR diffractograms of MWW and ferrierite (a,a'), their precursors (b,b'), and the delaminated ITQ-2 and ITQ-6 (c,c').

140 '

9

]-]

120 9

g

[ D

~

12MR

cavities

140

!/

120

[ 60.

10MR pores

k k ==

9

," ." ==

9ITQ6 9FER

100 -

80'

I

100'

10MR pores

&&

i

9

< 40-

40'

;.-'.." 0

1E-06 0.00001 0.0001 0.001 0.01

0.1

P/Po (logarithmic scale)

0 0.000001 0.00001 0.0001

0.001

0.01

0.1

PIPo (logarithmic scale)

Fig. 3. Argon isotherms of MWW and ferrierite (a,a'), their precursors (b,b'), and the delaminated ITQ-2 and ITQ-6 (c,c').

76 While the IR and 29SiMAS NMR spectra are consistent with the delaminated structure of ITQ-2 and ITQ-6, the Argon isotherms represented as a function of log P/P are highly informative on the changes in topologies experienced during delamination (Fig. 3). It can be seen there that ITQ-2 does not show the adsorption corresponding the large 12 MR cavities characteristics of the MWW structure, while preserves that of the intralayer 10 MR circular channels. Meanwhile, in the case of ITQ-6, the adsorption at the 10 MR pores of ferrierite has practically disappeared. It appears then that during the delamination of lamellar zeolitic precursors we have produced disordered individual sheets of crystalline zeolitic material that may be forming a "house of cards" type of structure, leaving mesopores in between them and allowing accessibility of reactants to the external active sites. This gives to delaminated zeolites extremely large external surface areas (Table 1) that are highly desirable for many catalytic processes. Notice that the area remains stable at high calcinations temperatures and even after steaming at 650~ Table 1 Surface area determined by N2 adsorption after calcination at 550~ for 3 hours. Material SBET(m2g"l) SEXT(m2g"1) MWW 452 97 ITQ-2 841 776 Ferrierite 278 53 ITQ-6 620 575 The resultant delaminated materials, when are prepared in a silica-alumina form, show strong Brtinsted acidity of the zeolitic type, which are much stronger than those of MCM-41 and accessible to large molecules, as indicated by the adsorption of 2,6-di-tert-butylpyridine. 3. CATALYTIC P R O P E R T I E S

3.1. Oil refining and petrochemistry The accessibility to acid sites of large oil molecules is shown by comparing the relative rates of MWW and ferrierite with respect to the corresponding ITQ-2 and ITQ-6 for cracking diisopropyl- and triisopropyl-benzene, and vacuum gasoil (Table 2). The results clearly show, that despite the fact that the delaminated zeolites have a lower number of total acid sites, as measured by pyridine adsorption, due to some dealumination occurring during the preparation, their activity is much higher, owing to a better accessibility of the reactants to the acid sites.

77 Table 2 Cracking activity of non delaminated and delaminated zeolitic materials Kinetic rate constants (s "l) Material DiisopropylTriisopropylVacuum Benzene Benzene Gasoil MWW 0.10 -0.025 ITQ-2 0.18 -0.050 Ferrierite -0.03 -ITQ-6 -0.14 -a Brrnsted acidity measured by pyridine, after desorbing at 523 K and 10 -2 Tor.

Acidity a 24 15 19 9

One may reasonably think that these materials are probably too costly and probably not enough stable to be commercially used in FCC units, but they may have a possibility as a component of hydrocracking catalysts. In this case, it would be highly desirable to have a material which could combine the good selectivity for diesel of amorphous silica-alumina, with the high activity of zeolites. It appears then, that delaminated zeolites could accomplishes these two objectives. Thus, we present here (Fig. 4) the results obtained during mild hydrocracking of vacuum gasoil on NiMo/ITQ-2, NiMo/USY, NiMo/ASA, NiMo/7-A1203, all catalysts containing 12 wt% MoO3 and 3 wt% NiO.

Fig. 4. Hydrocracking (HC) conversions obtained for the different catalysts as a function of the reaction temperature. Reaction conditions: 3.0 MPa. 2 h l WHSV and 1000 H2 (stp)/feed ratio: ( 9 ) NiMo/ITQ-2. (m) NiMo/USY. (A) NiMo/ASA. ( v ) NiMo/),-A1203. Figure 4 presents hydrocracking conversion at 3.0 MPa, 2 h -1 ~rHSV, 1000 H2 (stp) feed ratio, and different reaction temperatures. It can be seen there that NiMo/ITQ-2 shows the highest activity, closely followed by NiMo/USY, and in any case the activity of the former is much higher than that of NiMo/SiO2-A1203. The product selectivity at 50-55% of HC conversion is compared in Figure 5. As expected, NiMo/ITQ-2 presents a selectivity

78 behaviour which is intermediate between NiMo/SiO2-A1203 and NiMo/USY. In this way, NiMo/ITQ-2 it produces more diesel and less gases than NiMo/USY, showing promise as a hydrocracking catalyst, since it combines the high activity typical of zeolite-based catalysts with the good selectivity of amorphous catalysts.

Fig. 5. Selectivity to the different hydrocracked fractions obtained at ca. 55% hydrocracking conversion over NiMo-containing catalysts: (m) NiMo/ASA. ~ )NiMo/USY. (Fq)NiMo/ ITQ-2. Gases: C~-C4. Naphtha: C5-195~ Middle distillates: 195-360~ 3.2. Delaminated zeolites for fine chemicals

There are cases in where the production of fine chemicals involves the use of large reactant molecules or the formation of bulky products. In both cases, zeolites show limitations either for the reactants to penetrate into the pores, or for products to diffuse outside of the pores. In this case one can certainly decrease the crystallite size of the zeolite or even to use mesoporous materials to favour diffusivity. However, will show some cases in where there is a clear benefit of using delaminated zeolites over the other two types of materials. There is an important number of acetals that are used as fragrances. The synthesis of acetals is generally carried out by reacting aldehydes with alcohols. These are reactions which involve mild acid sites as catalysts. Here, we present firstly the synthesis of acetals from aldehydes of different molecular sizes on three catalysts, i.e. Beta zeolites with different crystallite sizes, mesoporous MCM-41, and the delaminated ITQ-2 material. The results presented in Table 3 clearly show that for small size acetals that can penetrate inside the micropores of Beta, this is the most active catalyst owing to its larger amount of acid sites, and also to concentration effects within the micropores that can favour bimolecular reactions. However, when the size of the aldehyde increases, the activity of Beta zeolite, even within crystallite sizes as small as 60 nm, is strongly diminished and is lower than that of MCM-41 and ITQ-2. In this case, the activity of the delaminated zeolite is clearly superior to either Beta of MCM-41 as a result of combining high accessibility to reactants with acid sites of zeolitic nature. More specifically, the synthesis of 2-methyl-2-naphthyl-4-methyl-l,3-dioxolane which has an orange blossom fragrance, was obtained by reacting 2-acetonaphthanone with 1,2propanediol at 419K in a batch reactor.

79 Table 3 Synthesis of acetals on different zeolitic materials

' II Rl u CH-C,,

H

R1

R20CH 3 Rn---- H - , I O C H 3 Solid Catalysts H

1-3

R2

1 CH3(CH2)4 H 2 Ph CH 3 Ph 3 Ph

(Eq. 1)

la-3a

Initial rates and conversion for the acetalization of aldehydes 1, 2 and 3 with trimethyl orthoformate ~TMOF) over different acid catal~,sts b. Catalysts

1

2

ro(h'l) Conversion a ro(h-1) Conversion a

3 ro(h-1)

Beta (~0.06) 200 78 120 65 (Si/Al=l 8) Beta(~0.86) 177 75 67 43 (Si/Al=18) Beta (t~ 0.1 ) 450 90 108 40 (Si/A1-50) MCM-22 (Si/A1= 50) 150 40 55 23 ITQ-2 (Si/AI= 50) 420 95 330 85 MCM-41 ~Si/A1 =40) 210 80 180 70 a)lh reaction time. b) Reaction conditions: aldehyde (2.5 mmol), TMOF (30 mg) in 25 ml CC14 at 78~

Conversion a

48

15

10

6

48

27

50 210 180 (12.7 mmol),

25 75 71 catalyst

Table 4 Synthesis of Blossom oranged. Reaction conditions: 7.4% wt/wt of catalyst respect to 2acetonaphthanone, 419 K, volume ratio: toluene/2-acetonaphthanone = 26.6.

Catalyst ITQ-2 MCM-22 HI32a H~3 b MCM-41

Si/A1 50 50 15 15 15

a Commercial sample, b Nanocrystalline zeolite

Yield of Blossom oranged Reaction Time lh 3h 32 80 5 12 4 5 24 45 9 24

80 The reaction was carried out using Beta, Beta nanocrystalline, MCM-41, and ITQ-2 as catalysts. The results presented in Table 4 show that ITQ-2 is more active than the nanocrystalline Beta, despite the fact that the number of acid sites is much smaller in the former, and much more active than MCM-41. The selectivity to the desired product on ITQ-2 is practically 100%. The synthesis of lactames has interest for the production of chemicals and fine chemicals. In the case of more bulky lactames derived from cyclodedecanone-oxime and cyclooctanone-oxime, they are used for producing nylon-12 and for the preparation of the precursor of azacycloalkanediphosphonic derivates which have pharmaceutical interest for the treatment of Ca 2+ metabolism disorders, respectively. In this case, the conversion of cyclododecanone and cyclooctanone oxime were done by the Beckman rearrangement in liquid phase, in a batch reactor at 403 and 433 K, respectively, with a catalyst to oxime ratio of 1:2 wt.wt ~, and chlorobenzene and sulfolane as solvent, respectively. The results reported in Table 5 show a higher activity for the delaminated ITQ-2 sample. Moreover, adsorbed products are easier to be removed from the surface of the delaminated material, as indicated by the smaller amount of organic left on the solid after reaction which was in the case of cyclododecanone-oxime, 2, 3 and 5 wt% for ITQ-2, MCM-41 and Beta, respectively. By optimising temperature and solvent, conversions higher than 95% with selectivities to the lactames > 98% can be obtained with ITQ-2. Table 5 Synthesis of the lactames of cyclooctanone and cyclododecanone oxime at 430~ minutes reaction time on various catalyst with a Si/AI ratio of 50.

Catalyst ITQ-2 MCM-41 Beta (0.1 lam)

and 90

Conversion (%) Cyclododecanone oxime Cyclooctanone oxime 98 82 67 60 32 26

3.3. Delaminated zeolites as catalysts supports Improving the quality of the Light Cycle Oil (LCO) produced in the FCC unit can be a necessary task to meet future diesel specifications. In order to improve the quality of LCO, polyaromatics should be hydrogenated and sulfur reduced. Owing to its high sulfur content, a dual-stage hydrogenation process has to be used where the feed is first hydrotreated to reduce the sulfur content, and then hydrogenated using a noble metal catalyst in the second reactor. A hydrotreated LCO which contained 400 ppm sulfur, and 68% aromatics with the distribution between mono, di and tri + aromatics given in Figure 6, was hydrogenated using Pt on different supports, i.e. amorphous silica-alumina, USY zeolite and ITQ-2. Acid supports were used here to increase the thioresistance of the catalysts. The results (Fig. 6) show that Pt/ITQ-2 gives the highest aromatics reduction, being mainly the tri +- and di-aromatics the ones reduced.

81

Fig. 6. Total aromatics content and aromatics distribution obtained in the hydrogenation of a hydrated LCO (HT-LCO) over the different Pt supported catalysts. Reaction temperature: 300~ The values corresponding to the HT-LCO feed are also included for comparison. ( D ) Mono-aromatics. (El) Di-aromatics. ( I ) Tri § The ferrierite delaminated ITQ-6 material has been successfully used as a support for enzymes (18). More specifically, ~-galactosidase from Aspergillus Oryzae, and penicillin Gacylase have been electrostatically and covalently immobilised on ITQ-6, resulting with enzyme catalysts highly active and stable. The advantage of delaminated zeolites as enzyme support is derived from the well structured external surface in where the silanol groups are regularly distributed. This allows a multipoint attachment between the enzyme and the supports, perhaps involving the most reactive groups of the protein surface. 4. CONCLUSION A new type of materials has been developed by delaminating the lamellar precursors of some zeolites. These materials show external surface areas > 600 m2.g"1 from where active sites can be accessible to very large molecules. If on one hand delamination eliminates geometrical shape selective properties of zeolites, it allows on the other hand to dispose of catalysts with the good reactant accessibility of mesoporous materials, but with the stability and active sites characteristics of zeolites. The very large and well structured external surface area can be specially suited for supporting different catalytic functions, which include, among others, metals, transition metal complexes and enzymes. 5. R E F E R E N C E S

1. A. Corma, Chem. Rev., 95 (1995) 559. 2. I.E. Maxwell and W.H.J. Stork, Stud. Surf. Sci. Catal., 58 (1991) 571. 3. R.A. Sheldon and H. van Bekkum (eds.), Fine Chemicals Through Heterogeneous Catalysis., Wiley-VCH, Weinheim (2001). 4. K.J. Balkus, Jr., A.G. Gabrielov and N. Saudler, Mater. Res. Soc. Symp. Proc., 368 (1995) 359. 5. P. Wagner, M. Yoshikawa, M. Lovallo, K. Tsuji, M. Taptsis and M.E. Davis, Chem. Commun. (1997) 2179.

82 J. Martinez-Triguero, M.J. Diaz-Cabafias, M.A. Camblor, V. Fom6s, Th.L.M. Maesen and A. Corma, J. Catal., 182 (1999) 463. J.S. Beck, J.C. Vartulli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgings and J.L. Schlenker, J. Am. Chem. Soc., 114 (1992) 10834. A. Monnier, F. Schilth, Q. Huo, D. Kumar, D. Margolese, R. S. Maxwell, G. D. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke and B. F. Chmelka, Science, 261 (1993) 1299. A. Corma, Chem. Rev., 97 (1997) 2373. 10. B.J. Schoeman, J. Sterte and J.E. Otterstedt, Zeolites, 14 (1994) 110. 11. M.A. Camblor, A. Corma, A. Martinez, V. Martinez-Soria and S. Valencia, J. Catal., 179 (1998) 537. 12. A. Corma, V. Fom6s, S.B. Pergher, Th.L.M. Maesen and J.G. Buglass, Nature, 396 (1998) 353. 13. A. Corma, U. Diaz, M. Domine and V. Fom6s, Angew. Chem. Int. Ed., 39 (2000) 1499; and J. Am. Chem. Soc., 122 (2000) 2804. 14. S.L. Lawton, A.S. Fung, G.J. Kennedy, L.B. Alemany, C.D. Chang, G.H. Hatzikos, D.N. Lissy, M.K. Rubin, H.J.C. Timken, S. Stenemagel and D.E. Woessner, J. Phys. Chem., 100 (1996) 3788. 15. L. Schreyeck, P.H. Caullet, J.C. Mougenel, J.L. Guth and B. Marler, Chem. Commun. (1995)2187. 16. E.W. Valyocsik, US Patent N ~ 5 068 096 (1991). 17. A. Burton, R.J. Accardi, R.F. Lobo, M. Falcioni and M.W. Deem, Chem. Mater., 12 (2000) 2936. 18. A. Corma, V. Fom6s, J.L. Jordh, F. Rey, R. Fem6.ndez-Lafuente, J.M. Guis6.n and C. Mateo, Chem. Commun. (2001) in press. .

Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

83

Pentasil zeolites from Antarctica" from mineralogy to zeolite science and technology A. Alberti a, G. Cruciani a, E.Galli b, S. Merlino c, R. Millini d, S. Quartieri e, G.Vezzalini b, S. Zanardi a aDipartimento di Scienze della Terra, Universith di Ferrara, Italy. bDipartimento di Scienze della Terra. Universith di Modena e Reggio Emilia, Italy. CDipartimento di Scienze della Terra, Universit/l di Pisa, Italy. dEniTecnologie S.p.A., S. Donato Milanese, Italy. eDipartimento di Scienze della Terra, Universit/l di Messina, Italy.

SUMMARY In the course of a systematic investigation of zeolites from Northern Victoria Land, Antarctica, a large number of zeolitic species was identified in the Jurassic Ferrar Dolerites of Mt. Adamson. Noteworthy was the presence of three new zeolites: gottardiite, the natural counterpart of the synthetic NU-87, terranovaite, and mutinaite, the analogue of ZSM-5, as well as the two very rare zeolites tschernichite, the counterpart of zeolite beta, and boggsite. The chemical and crystallographic properties of these natural materials were compared with those of their synthetic analogues. The tetragonal and monoclinic polymorphic phases, intergrown in the beta zeolite, were isolated and structurally refined in tschernichite crystals, which differ by crystal size, morphology and chemistry. The occurrence of these natural zeolites demonstrates that the chemical existence field of their synthetic counterparts is larger than that argued up to now, and that their synthesis can be obtained in the absence of an organic template.

1. INTRODUCTION It is well known that zeolites containing a high proportion of five-membered rings of tetrahedra in their framework are widely used in heterogeneous catalysis; these include synthetic ZSM-5, ZSM-11, beta, theta-1, NU-87, the synthetic analogues of natural mordenite and ferrierite and the natural zeolite heulandite. During an investigation of zeolites from Northern Victoria Land, Antarctica, numerous zeolitic species, among which the pentasils are predominant, were found in the Jurassic Ferrar Dolerites of Mt. Adamson: heulandite, stellerite, stilbite, mordenite, erionite, levyne,

84 cowlesite, phillipsite, chabazite, epistilbite, ferrierite, analcime and, particularly interesting, the rare zeolites boggsite and tschernichite, the natural counterpart of zeolite beta [1]. Noteworthy is the presence of three new pentasil zeolites: gottardiite [2], the natural counterpart of NU-87, terranovaite [3] and mutinaite [4], the natural counterpart of ZSM-5. Very striking is the occurrence at Mt. Adamson of so many natural analogues of important synthetic zeolites and of two minerals (boggsite and terranovaite) still lacking their synthetic counterpart. The aim of this contribution is to highlight the impact that the study of mineral zeolites can have on zeolite knowledge. In particular: a) natural zeolites usually occur in crystals which are large enough for single-crystal X-ray diffraction studies; these investigations allow structural information to be obtained which is far more detailed and accurate than that gathered by powder diffraction data or other experimental techniques; b) the counterparts of synthetic zeolites found up to now in nature usually have significantly different Si/A1 ratios and extraframework contents. This shows that the chemical existence field of these topologies is wider than that up to now deduced from the compositions of the synthesised phases; it should also be borne in mind the extent to which chemical characteristics can influence the technological properties of the materials, and how much detailed structural information is essential for their comprehension. Below we describe the crystal-chemistry of the new and rarest zeolites from Mt. Adamson, with a particular emphasis on the most recent results conceming the structural features of the tschernichite-type mineral and a comparison with its synthetic analogue beta.

2. GOTTARDIITE The first of the new natural zeolites found at Mt. Adamson was gottardiite [2]. The crystals occur as thin lamellae, pseudo-hexagonal in shape or elongated along the a axis. The crystals, transparent and colorless, rarely occur in isolation; more frequently they form aggregates of a few individual crystals. The chemistry of gottardiite (unit cell content: Na2.sK0.zMg3.1Ca4.9Al18.8Sil17.zOzvz'93H20) is characterized by a high magnesium content and a very high Si/A1 ratio (6.2) compared with other natural zeolites. Gottardiite shows a high thermal stability and very high re-hydration capacity; the mineral quickly and completely regains its weight loss at temperatures of up to 800~ whereas at 1100~ its rehydration capacity becomes zero, probably due to the framework destruction occurring in this temperature range [2]. Its fast and complete rehydration suggests that no T-O-T bridge breaking occurs during dehydration [5]. The mineral is orthorhombic (a=13.698(2), b=25.213(3), c-22.660(2) A), with topological symmetry Fmmm and real symmetry Cmca [6]. In the Fmmm symmetry there are five non-symmetry-related sites on inversion centers. In this topological symmetry two oxygen atoms lie on two of these 1, causing energetically unfavourable T-O-T angles of 180 ~ In the Cmca sp.gr, these two inversion centers disappear, while the other three remain. This situation is common to all zeolites where, in the topological symmetry, framework oxygens lie on centers of symmetry [7].

85 The topology of gottardiite, which has not been found in other natural zeolites, is the same as that of synthetic zeolite NU-87 [8]. This is more evident if we describe the NU-87 unit cell not on the basis of the conventional monoclinic unit cell P21/c (a = 14.324 A, b = 22.376 A, c= 25.092 A, 13=151.52~ ), but in the pseudo-orthorhombic unit cell C l l 2 / / b (a = 13.663 A, b = 25.092 A, c = 22.376 A, ~/=90.37~ ). The framework of gottardiite can be described by the interconnection of the polyhedral subunits 5262, 5462 and 54. 5262 and 5462 units have also been found in other zeolites, whereas the unit 54 has been found here for the first time in zeolites. By interconnecting the 5462 and 54 units, a chain is generated which develops along the b axis. These chains are connected to form an impermeable sheet parallel to the ab plane. Each sheet is bonded to other parallel sheets through 4-rings of tetrahedra. The crystal structure is characterized by a two-dimensional channel system. Straight 10-ring channels run parallel to a, whereas 12-ring channels develop along b. These 12-ring channels are interrupted every 25 A (the value of parameter b) by the 4-ring between the sheets, and are connected to the 10-ring parallel to the a axis by a 10-ring window. Therefore these 12-ring channels are not straight, but "snake" in the b direction. 3. TERRANOVAITE The second new natural zeolite found at Mt. Adamson was terranovaite [3]. This mineral is very rare and frequently occurs in globular masses, sometimes in tabular, transparent, bluish crystals, closely associated with heulandite, from which it is barely distinguishable. Yerranovaite [(Na4.zK0.2Mg0.2Ca3.7)tot=8.3(Al12.3Si67.7)tot=80.0O160">29H20]is rich in sodium and calcium and has quite a high Si/A1 ratio (about 5.5). Its topological symmetry, hitherto unknown in either natural or synthetic materials, is orthorhombic, space group C m c m (a = 9.747(1), b = 23.880(2), c=20.068(2)A). However, the presence of a framework oxygen on an inversion center, with an unfavorable T-O-T angle of 180 ~ and the strong anisotropy of some framework oxygen atoms, indicate that the real symmetry is probably described by the acentric sp.gr. C2cm. The framework of terranovaite (Fig. 1), characterized by a pentasil chain, can be described by the interconnection of the polyhedral subunits 4264, 4254 and 5462. The 4264 unit has been found in laumontite and boggsite; the 4254 unit has been found in brewsterite, heulandite group zeolites and in synthetic SSZ-23 and SSZ-33; the 5462 unit has been found in gottardiite, boggsite and in synthetic EU-1. The net of terranovaite projected onto the bc plane (Fig. 1) is equivalent to that of many other pentasil zeolites (ferrierite, boggsite, ZSM5, ZSM-11, theta-1), while the net projected onto the ab plane is equivalent to that of A1PO441 [9]. A two-dimensional channel system parallel to the (010) plane is present in the terranovaite framework. Straight ten-membered ring channels run along [100] and [001]; the former is about circular in section (5.5 x 5.1 A), while the latter is strongly elliptic (7.0 x 4.3 A) (Fig. 1). These channels are connected through a 10-ring window.

86

Fig. 1. Perspective projection of terranovaite framework along [ 100].

4. M U T I N A I T E The third new natural zeolite found in the Ferrar Dolerites of Mt. Adamson is mutinaite [4], the natural counterpart of synthetic ZSM-5. The mineral [(Naz.76K0.11Mg0.21 Ca3.78)(All 1.20Si84.91)O192"60H20] occurs as subspherical aggregates of tiny radiating lath-like fibers or as aggregates of transparent tiny tabular crystals, with good (001) cleavage. This zeolite, very rich in calcium, has a Si/A1 ratio equal to 7.6, the highest found in natural zeolites; however, it is far lower than that of ZSM-5, where this ratio is always greater than 12. Moreover, mutinaite is characterized by a very high thermal stability and a high rehydration capacity. The mineral quickly regains more than 95% of its weight loss at temperatures up to 900~ [4]. The single-crystal structure refinement of mutinaite [ 10] was performed on a microcrystal of 0.03x0.03x0.015mm 3, collecting the data at the beamline ID 11 of the synchrotron radiation source of the European Synchrotron Radiation Facility (ESRF) of Grenoble. The mineral resulted orthorhombic with space group Pnma (a--20.201(2), b-19.991(2), c=13.469(2)A, V=5439 A3). This symmetry is consistent with the high aluminum percentage, and with the content and distribution of the extra-framework species. The structural refinement of mutinaite revealed the absence of order in the Si,AI distribution in the framework; this result is consistent with the conclusions of Toby et al. [ 11 ], who report the absence of highly occupied Br6nsted sites in the high-alumina ZSM-5. When mutinaite is compared with synthetic ZSM-5 phases (with Pnma symmetry) loaded with different molecules, we observe that the mean T-O-T angle is similar: 154 ~ in mutinaite, 155 ~ in TPA-ZSM-5 [12], and 154 ~ in PDCB (p-diclorobenzene-ZSM-5), PNAN (p-nitroaniline-ZSM-5) and NAPH (naphthalene-ZSM-5) [13]. On the contrary, many of the

87 single T-O-T angles of mutinaite strongly differ from the corresponding angles in the synthetic phases (by up to 19~ for T1-O1-T2 of mutinaite with respect to NAPH). These differences mainly affect the shape of the straight ring channel: in mutinaite it is strongly elliptical and, above all, the directions of minimum and maximum elongation are interchanged with respect to those of the synthetic phases.

5. BOGGSITE Boggsite was first described by Howard et al. [14]. This pentasil zeolite occurs in close association with tschernichite in Eocene basalts near Goble, Columbia County (Oregon), and was found for the second time at Mt. Adamson. Boggsite topology [ 15] was hitherto unknown in either natural or synthetic materials. The framework (topological and real symmetry Imma, a=20.25(2), b=23.82(1), c=12.78(1)A) can be described by the interconnection of the polyhedral subunits 4254, 4264, 5462 (found also in terranovaite), 5262 (present with 5462 in gottardiite) and 4262. A straight 12-membered ring channel runs along [100], and a straight 10-ring channel develops in the [010] direction. These channels are connected by a 10-ring window [ 15]. The chemical analyses of boggsite from Goble and Mt.Adamson indicate a constant value of the Si/A1 ratio (about 4.3), which is a usual value for the already known pentasil zeolites, but rather low when compared with that of the other pentasil zeolites from Mt. Adamson. Ca is always the most abundant extraframework cation, whereas Na is rather variable and can reach a content nearly equal to that of Ca. Minor quantities of K and Mg are present.

6. T S C H E R N I C H I T E Tschernichite was structurally defined as the natural counterpart of synthetic zeolite beta [ 16]. At Mr. Adamson the mineral occurs either as large, steep tetragonal dipyramids terminating in a basal pinacoid, or as radiating hemispherical groups of small crystals. Large and small drusy crystals were also reported from Goble tschernichite [17]. Microprobe chemical analyses [1] of large and small tschernichite crystals clearly show that large crystals are richer in A1 than the small ones (Si/A1 ratios 2.66 and 3.94, respectively), as applies also to tschernichite from Goble [17]. Due to the paucity of materials it was not possible to determine the thermal behaviour of tschemichite from Mt. Adamson, but a study on tschernichite from Goble [18] showed that its ammonium form is thermally stable to a temperature as high as 900~ It is known that synthetic zeolite beta can be regarded as a close intergrowth of two distinct, but related, structures [ 19] which can be described as consisting of (001) tetragonal layer-like building units [20]. According to the OD theory, these two structures represent the two maximum degree of order (MDO) topologies. The X-ray powder diffraction pattern of the large crystals of tschernichite-type mineral from Antarctica shows significant discrepancies, mainly in the low 0 region, with respect to those of Goble tschernichite [17] and beta zeolite [19]. These discrepancies, together with the different Si/A1 ratios between large and small crystals of tschernichite,

88

Fig. 2. Projection along [110] of the monoclinic polytype of tschernichite.

suggest that a different ratio of the two polytypes may be present in the crystals of this mineral, depending on their dimensions. We have recently used single crystal X-ray diffraction to study the structure of the two different morphologies of tschemichite from Antarctica, in order to verify if they are characterized by different structural features. Intensity data were collected on a fragment of a large crystal and on a small crystal, using an automatic four-circle Nonius KappaCCD diffractometer equipped with a CCD detector (radiation MoKot). A data collection performed on a large crystal indicated a monoclinic unit cell with a=17.983(3)A, b=17.966(2)A, c=14.625(2)A, [3=114.31(1) ~ V=4306.1A 3 and sp.gr. C2/c. A similar investigation on a small single crystal indicated a tetragonal unit cell with a=12.622(1)A, c=26.674(3)A, V=4249.6A 3 and sp.gr. P4122. The structure refinements of both samples were carried out starting from the DLS atomic coordinates of Higgins et al. [21]. Extraframework sites were located using Fo and AF Fourier maps. The diffraction patterns of both tetragonal- and monoclinic-dominant crystals have in common a set of sharp reflections, with h (and k) = 3n, which are related to the superposition structure. Due to layer stacking disorder, reflections with h (and k) = 3n + 1 show continuous streaks elongated in the c* direction. A detailed structural analysis of each polytype requires a 3-dimensional analysis of the diffuse peaks and an accurate intensity measurement, which can be obtained with an area-detector based diffractometer. For the two tschernichite crystals, the real symmetry was checked with the help of synthetic precession images constructed from the collected flames.

89 Figures 2 and 3 report the projection along [110] and [ 100] of the two polytype structures. The main results of the structure refinements are the following: a) regular T-O distances and partial Si/A1 ordering in both frameworks; b) identification of two Ca sites in the monoclinic structure; c) identification of two Ca sites in comparable positions in the tetragonal structure, but with lower occupancy; d) a further cation site probably occupied by Mg in tetragonaldominant crystals; e) the presence of many other extraframework sites characterized by low electron densities and large distances from the framework oxygens.

Fig. 3. Projection along [ 100] of the tetragonal polytype of tschemichite

90 7. CONCLUSIONS The discovery at Mt. Adamson of so many new and rare high-silica pentasil zeolites, most of which being natural counterparts of synthetic phases largely used in many technological applications, is of great interest as: a) it implies that organic templates, used as directing agents, may not be essential for their synthesis; b) the finding of the natural zeolites discussed above, with a Si/A1 ratio lower than that of the corresponding synthetic phases, suggests that the range of chemical composition required for the crystallization of their structural type is greater than that believed up to now; c) gottardiite, mutinaite and the ammonium form of tschernichite from Goble are stables to temperatures as high as 900~ We can argue that also terranovaite and boggsite are characterized by a similar, very high thermal stability, d) terranovaite and boggsite are interesting additions to the pentasil family, and the synthesis of their analogues should be of great interest to all those who work in the field of microporous materials. All the above described zeolites from Mt. Adamson are characterized by the dispersion of the extraframework ions over a large number of sites; they are usually characterized by weak electronic density and large distances from the framework oxygens which prevent (with the exception of tschernichite) an unambiguous site assignment of cations and water molecules. These features, together with the crystal growth structures of tschernichite, could suggest that these minerals grew very quickly, possibly during a rapid environment cooling, and that they could be metastable at room conditions. The defining of the genetic conditions of these phases, which are potentially useful as molecular sieves and catalysts, is the aim of our future research work. In conclusion, we believe that the results of this research well demonstrate how much natural materials can contribute to the knowledge of microporous materials. To stress this point again, we remind the reader of the recent occurrence of two natural zeolites analogous to previously synthesized phases, and two others lacking their synthetic counterparts: a) gaultite [22], a framework silicate unique in nature with zinc in tetrahedral sites, chemically and structurally analogous to VPI-7; b) pahasapaite [23], a berylloposphate with the same topology as the synthetic aluminosilicate RHO; c) maricopaite [24], an interrupted framework aluminosilicate with lead as dominant extraframework cation, forming Pba(O,OH)4 clusters; and d) tsch[]rnerite [25], characterized by a super-cage with 96 tetrahedra and 50 faces and by CuZ+12(OH)24-bearing clusters. ACKNOWLEDGEMENTS Italian PNRA, CNR and MURST ("Transformations, reactions, ordering in minerals" COFIN 1999) are acknowledged for financial support. REFERENCES

[1] E. Galli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 7 (1995) 1029.

91 [2] E. Oalli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 8 (1996) 687. [3] E. Galli, S. Quartieri, G. Vezzalini, A. Alberti and M. Franzini, Amer. Mineral., 82 (1997a) 423. [4] E. Galli, G. Vezzalini, S. Quartieri, A. Alberti and M. Franzini, Zeolites, 19 (1997b) 318. [5] A. Alberti and G. Vezzalini, in: Proceeding of the Sixth International Zeolite Conference, D. Olson and A. Bisio (eds.),Butterworth & Co., Guildford, UK, (1984) 834. [6] A. Alberti, G.Vezzalini, E. Galli and S. Quartieri, Eur. J. Mineral., 8 (1996) 69. [7] A. Alberti, in: New developments in zeolite science and technology. Y. Murakami, A. Iijima and J.W. Ward (eds.), Proc. 7 th Int. Zeolite Conf. Kodansha, Tokio, (1986) 437. [8] M.D. Shannon, J.L. Casci, P.A. Cox and S.J. Andrews, Nature, 353 (1991) 417. [9] R.M. Kirchner and J.M. Bennett, Zeolites, 14 (1994) 523. [ 10] G. Vezzalini, S. Quartieri, E. Galli, A. Alberti, G. Cruciani and ,4,. Kvick, Zeolites, 19 (1997) 323. [11] B. Toby, S. Purnell, R. Hu, A. Peters and D.H. Olson, in: Proceeding of the 12th International Zeolite Conference. Treacy, B.K. Marcus, M.E. Bisher and J.B. Higgins (eds.), Materials Research Society, (1999), 2413. [12] H. Van Koningsveld, H. van Bekkum and J.C. Jansen, Acta Cryst., B43 (1987) 127. [13] H. Van Koningsveld, and J.H. Koegler, Microporous Materials, 9 (1997) 71. [14] D.G. Howard, R.W. Tschernich, J.V. Smith and G.L. Klein, Amer. Mineral., 75 (1990) 1200. [15] J.J. Pluth and J.V. Smith, Amer. Mineral., 75 (1990) 501. [16] J.V. Smith, J.J. Pluth, R.C. Boggs and D.G. Howard, J. Chem. Soc., Chem. Commun., (1991) 363. [17] R.C. Boggs, D.G. Howard, J.V. Smith and G.L. Klein, Amer. Mineral., 78 (1993) 822. [18] R. Szostak, K.P. Lillerud and M. St6cker, J. Catal., 148 (1994) 91. [19] J.M. Newsam, M.M.J. Treaty, W.T. Koetsier and C.B. De Gruyter, Proc. Roy. Soc. London, A420 (1988) 375. [20] B. Marler, R. B6hme and H. Gies, in: Proceeding of the 9th International Zeolite Conference, Montreal 1992, R. von Ballmoos, J.B. Higgins and M.M.J. Treacy eds, Butterworth-Heinemann, (1993) 425. [21] J.B. Higgins, R.B. LaPierre, J.L. Schlenker, A.C. Rohrman, J.D. Wood, G.T. Kerr and W.J. Rohrbaugh, Zeolites, 8 (1988) 446. [22] T.S. Ercit and J. Van Velthuizen, Canad. Mineral., 32 (1994) 855. [23] R.C. Rouse, D.R. Peacor and S. Merlino, Amer. Mineral., 74 (1989) 1195. [24] R.C. Rouse and D.R. Peacor, Amer. Mineral., 79 (1994) 175. [25] H. Effenberger, G. Giester, W. Krause and H.J. Bernhardt, Amer. Mineral., 83 (1998) 607.

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Studies in Surface Science and Catalysis 135 A. Galameau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

93

Use of 1H NMR imaging to study the diffusion and co-diffusion of gaseous hydrocarbons in H ~ M - 5 catalysts" P. N'Gokoli-Kekele, M.-A. Springuel-Huet**, J.-L. Bonardet, J.-M. Dereppe, J. Fraissard aLaboratoire S.I.E.N.-Chimie des Surfaces, ESA-CNRS 7069, Universit6 P. et M. Curie, 4 place Jussieu, 75252 PARIS Cedex 05, France bLaboratoire de Chimie-Physique et Cristallographie, Universit6 Catholique de Louvain-laNeuve, 1348 Louvain-la-Neuve, Belgium I H N1V[R imaging has been used to study the diffusion of pure hydrocarbons (benzene, nhexane,) during their adsorption in or desorption from a fixed bed of zeolite crystallites. This technique is used to visualize the progression of the diffusing molecules in the zeolite bed and to determine their intracrystallite diffusion coefficients. In the case of competitive adsorption, it gives the time dependence of the distribution of the two coadsorbed gases.

I. INTRODUCTION NMR imaging (MR/) techniques were developed in the 70s mainly in the medical and biological fields, using essentially the ~H nucleus but also 3He, 19F ,31p, and more recently hyperpolarized 129Xenuclei, etc. The fact that this technique is non-invasive and non-radiative, coupled with the development of more and more powerful equipment and increasingly sophisticated numerical treatment of images, has tended to generalize magnetic resonance imaging in the medical field. However, medicine is not the only field of application of MR/, and the 90s saw considerable progress in this technique for the study of porous media. MR/has been successfully used to study solvent penetration and the dynamics of water in polymers [1,2], the structure and dynamics of polymer gels [3], the segregation of grains in blends [4], the permeation resistance of cement [5], pore size distribution mapping [6] as well as the drying kinetics of gels [7]. It can be also used in microporous systems to investigate the diffusion and molecular mobility of water in 4A zeolites [8] or hydrocarbon diffusion in deactivated Y zeolites [9]. We present here an application of this technique to the study of the diffusion of pure or mixed hydrocarbons (benzene, n-hexane) in a fixed bed of HZSM-5 zeolite during their adsorption at room temperature. In particular, we show for the first time that it is possible to visualize the *The oral presentation in the form of a keynotespeech will also mentionthe studyof diffusion by xenon NMR l~ublishedin this Proceedings to whom correspondenceshouldbe adressed. E-mail: [email protected].~

94 distribution of several gases adsorbed competitively, even if certain results are still essentially qualitative. 2 PRINCIPLE OF THE TECHNIQUE Figure 1 illustrates the principle of the technique. Magnetically equivalent spins in a homogeneous magnetic field B0 (Figure l-a) will give a single signal at a resonance frequency COo,the intensity of which depends only on their number and is independent of their distribution within the sample. However, if a field gradient, g, is superimposed on B0 in the z direction (Figure l-b), the effective field applied to the spins is of the form Bz = B0 + g z; the resonance frequency and the signal intensity depend then on the position and the density, respectively, of the spins at each point z of the sample. More generally, the application of pulsed field gradients during the NMR pulse sequence used for the detection of the resonance signal leads to concentration profiles of resonating spins in the direction(s) of the gradient(s). It is therefore possible to obtain images in one, two or three dimensions. It should be noted that the signal detected depends on the spin density p at each point of the sample but also, depending on the pulse sequence used, on relaxation. For example, in our studies we have used two sequences. In the sequence shown in Figure 2-a, the field gradient is applied during the n/2 pulse and (a) 13o (b) 13o + gz throughout the signal acquisition time, which makes it possible to avoid the problem of spin relaxation and to obtain the real spin concentration profile. In spin echo detection the --+------4 ......... ~-P Z --~-t .... ~ Z Zl 7,2 Z3 Zl Z2 Z3 intensity of the signal depends on relaxation. i i Figure 2-b details, in that case, the periods Acq uisition Acq uisition during which the gradient is applied depending on the pulses used. This sequence can be useful when there is a distribution of the spin relaxation times T2 in the sample, as we have too t~l o~ tt~3 shown in a study of Y zeolite deactivation during catalytic cracking [9] Fig. 1. Prizlciple of 1D NMR Imaging I. EXPERIMENTAL SECTION HZSM-5 zeolite consisting of crystallites, assumed to be spherical, of average radius R = 20 ktrn, was used in the form of a powder or compressed (at 103 bar) into cylindrical pellets 7 mm in diameter and between 5 and 15 mm long, either pure or with a binder (amorphous silica-alumina, SBET ~ 700 m 2 g-l, mean pore diameter 5 nm). Samples placed in the cell (Figure 3) were held under vacuum (10 -5 mbar) at 673 K overnight before the adsorption of gaseous hydrocarbon(s) at constant pressure at 293 K.

95

Fig. 2. Schematic representation of the 1D Imaging NMR sequence: a)Direct acquisition; b) Spin echo acquisition. At time t - 0 the sample is put into contact with the supply of liquid hydrocarbon (n-hexane or benzene) in equilibrium with the gas and is then placed quickly in the magnet. The liquid phase is either pure or consists of a mixture such that the two partial pressures of the gases are equal to 60 mbar (assuming that the mixture obeys Raoult's law). To distinguish the hydrocarbons when they are mixed, one is perhydro and the other perdeutero. The proton 1D NMR images, which represent the concentration profiles of the hydrocarbons along the NMR tube axis are recorded as a function of time with a MSL 300 Bruker spectrometer. They are obtained by applying a magnetic field gradient (Gz ~ 4 T m l) along the direction of the NMR tube axis during which a ~/2 r.f. pulse (RF) is applied and signal acquisition (AQ) is performed (Figure l-a). The length of the sample is small enough (5-15 mm) to permit the application of the excitation pulse during the magnetic gradient.

Fig. 3. Schematic representation of the cell containing the sample.

96 3. RESULTS AND DISCUSSION 3.1 Diffusion of pure gases

The diffusion equations are given by the hydrocarbon mass balance in macropores (eq. 1) and in micropores (eq. 2) [ 10, 11]" t~c c92c 3(1 ~Dintra( tgq] I~inter'~-t -- Dintereinter ~0z2-13inter s R ~ r=R

(1)

cOq ( t 9 2 q , 2 cOq/ cgt = Dint r~ ~ T r 2 "- 7--~r )

(2)

where c and q are the hydrocarbon concentrations in macropores and micropores, respectively; z (linear) and r (radial) coordinates in the bed (from the bottom) and in the crystallite (from the centre); Dinter and Din~ the inter and intracrystallite diffusion coefficients and einter the macroporosity of the sample. These experiments were conducted at pressures where the intercrystaUite diffusion is very rapid with respect to the intracrystallite diffusion. One can verify these conditions from the rectangular concentration profile of the images. In this case only equation 2 is used, with the following boundary conditions: q(r, t=0) = 0;

q(r=R, t) = qoo[1 - exp(-kt)];

aq(r = 0, t) = 0 tgr

where k is the transfer constant of molecules to the external surface of the crystallites, and qoo the hydrocarbon concentration in each crystallite at equilibrium adsorption; then we can use the solution of the diffusion equation (3), obtained by Cranck [ 12],

Mt _ 1- ~ e x p ( - k t ) Moo kR 2

[

1-

cot D intra

+ ~ D intra

)-',

exp

(3)

X2Dintra n = I n 2 (n 2/i;2 - kR 2 / Dintra)

where Mt is the total amount of adsorbed gas at time t (given by the integral of the NMR image signal) and Moo the corresponding value at equilibrium state. It should be pointed out first of all that the hydrocarbon concentration in the gas phase and in the macropores is always negligible compared to that in the micropores (even right at the beginning of adsorption). Consequently, the signal observed is due essentially to adsorption in the micropores.

97 3.1. L Benzene At the very beginning of adsorption, (0 < t < 0.1 h) the 1D images of benzene adsorbing in the powder HZSM-5 bed show a strong concentration gradient decreasing towards the bottom of the sample (Figure 4a). When t > 0.2 h rectangular profiles are obtained for the loose as well as for the compressed powder (Figure 4b) proving that after this time, under these experimental conditions (high pressure of the gas phase) the benzene concentration is the same in any part of the bed and that the diffusion of hydrocarbon is then controlled by the micropores, as discussed by Heink et al. [13]. This allows the determination of Dm~. The results appear to contradict those obtained by NMR of the xenon probe, which demonstrate the influence of intercrystallite diffusion, but in this latter case, the relative benzene pressure is lower a part of the zeolite free volume is already occupied by xenon.. Since compressing the powder increases the density of the sample, the NMR signal is better defined for the compressed sample. The signal intensity increases with the adsorption time. The total amount, M(t), of benzene adsorbed in the sample is directly proportional to the integral of the NMR profiles. The experimental kinetic curves of M(t) = fit) are simulated using equation 3. The simulation gives a Dmt~ value of about 1x 10-14 m 2 s"l whatever the form, powder or pellet, of the sample. This value agrees well with that obtained by 129Xe NMR [14].

a)

b)

Time (h)

~

............. ...... ............ .......... ........... ",---------',--------

Time (h)

15.3

~~

2.4

0.4 0.2

/.- . . . . 9 i. . . .

z=e

z=O

z=e

\_

'7. z=0

9 9

16.00 9.00 4.25 2.25 1.67 1.42 1.17 0.83 0.58 0.25

r--

gas flow

gas flow

Fig. 4. 1D-NMR profiles of adsorbed benzene: a) on powder ; b) on pellet When the sample is the powder zeolite mixed with silica-alumina (60% weight of zeolite, length 25 mm), the benzene concentration profiles (Figure 5-a) present an adsorption front which lasts more than 30 min. On one hand, the intercrystallite diffusion rate is decreased by the presence of the mesoporous silica-alumina, on the other hand benzene also adsorbs on the silicaalumina. In the case of a compressed mixed sample (length 12 mm) the profiles are rectangular as

98 of the first spectrum (Figure 5-b). The difference between the two cases is mainly due to the decrease in the macroporosity and the length of the sample. These results show that mass transport in industrial catalysts depends greatly on the binder, the dimensions and the compression of the sample.

a)

~ t"

Time (h) A

.,~___~

_ 1/'_" --'--'~-~k - - ~ / ~ \ ~ - ----J/ X~--=:=~// \~

b)

~

Time (h)

12.00 s.oo 5.40 4.00

11~

060 .

-J/~,,_--~-~~--

.

0.30 0.25

-~//-~ _J/

~~,~~ ~-~ z=0

z=~

0.20 o.15

-----~/~\~,

.

.

.

;!;; 0.25

0.08 z=e

z=0

gas flow

gas flow

Fig. 5.1D-NMR profiles in a mixture (zeolite/silica-alumina binder) during benzene adsorption: a) powder ; b) pellet 3.1.2. n-Hexane In the case of n-hexane adsorption on a powder sample, the concentration profiles (Figure 6) become perfectly rectangular after only t = 0.03 h. The value obtained for Dm~ (~10 -13 m 2 s -l) is of the same order of magnitude as that reported Time (h) in the literature using other techniques (zero length column, frequency response, etc.) [ 13].

17.80

----37 __--- l:~l __. 0.11 i

0.04

3.2. Diffusion of gas mixtures

Different types of experiments were performed with n-hexane and benzene. Here we report the gas flow results concerning" i) their competitive Fig. 6.1D-NMR profiles of n-hexane adsorbed adsorption, ii) variation of the distribution of a pre-adsorbed hydrocarbon during the in HZSM5 zeolite in powder form. adsorption of a second one. z=~

z=O

99

3.2.L Competitive adsorption. When the adsorption of n-hexane proceeds from a gas phase mixture of n-hexane C6H14and benzene C6D6 both at the same partial pressure, 60 mbar, the intensity of the profiles first decreases from the top to the bottom of the bed (Figure 7-a). Such a profile, which indicates a strong hexane concentration gradient in the sample, persists up to a time of 0.13 h, whereas the adsorption of pure hexane leads very rapidly to rectangular profiles (Figure 6). Several reasons can be proposed to explain this evolution: intercrystallite diffusion slowed, surface barrier lower for n-hexane than for benzene; etc. At intermediate time, there is a slight excess of n-hexane in the bottom of the bed before a homogeneous distribution all over the bed is reached at equilibrium. Whatever the reason, n-hexane adsorbs in the first layers before its pressure becomes equal throughout the bed. The benzene molecules, whose intracrystallite diffusion is much slower than that of n-hexane, progress along the bed and adsorb then on the subsequent layers whose crystallites are free of any adsorbate. As time increases, benzene also adsorbs on the first layers, displacing n-hexane towards the bottom where n-hexane displaces in turn the benzene molecules to finally obtain a distribution governed by thermodynamics. This scenario is confirmed by the evolution of the benzene concentration along the bed, recorded during an identical experiment in which benzene C6H6 and n-hexane C6D14 were used (Figure 7-b). These profiles clearly show that benzene first adsorbs preferentially in the bottom layers before displacing the n-hexane adsorbed in the top layers and finally the equilibrium is reached over the entire sample.

a) Time (h)

~ ~ ~ _ ~

ne (h) 5.88

8.70

4.58

5.08

2.53

4.33

0.83

1.02

0.47

0.57

0.22

0.32 0.25 0.08 0.02

0.13 ~.---__---

0.12

0.07

Z=s

z=O

z= s

z=O Ip

gas flow

gas flow

Fig. 7. 1D-NMR profiles ofn-hexane a) and benzene b) during their competitive adsorption in HZSM-5 zeolite.

100 The intermediate states of the systems are the result of competing kinetic and thermodynamic effects, the diffusion of n-hexane being faster than that of benzene while the latter is more strongly adsorbed inside the crystallite.

3.2.2. Distribution of pre-adsorbate during the adsorption of another gas. Figure 8-a shows the evolution of the distribution of n-hexane C6Hn4 pre-adsorbed at 2 mbar during the adsorption of benzene C6D6 at its saturation vapour pressure. At time t = 0, the concentration profile of pre-adsorbed n-hexane is rectangular. Immediately upon contact with benzene, hexane is seen to be desorbed but preferentially from the upper layers, as is shown in Figure 8-b. However, a practically rectangular concentration profile is obtained rapidly, in about 0.2 h. It should be noted that the amount of hexane desorbed between the beginning of the experiment and the attainment of a new equilibrium is about 40%. Figure 9-a corresponds to the case of benzene C6I-I6 being pre-adsorbed at equilibrium at 6.4 mbar and n-hexane C6Dl4 adsorbing at its saturation pressure. a)

b)

140 ~" 120 me (h)

~

100 80

0

3.90 9.00 ! 9

z =~

[

9

z=0

~

60

20 0 0.17

I

i

0.3

0.47

0.72

z/~

gas flow Fig. 8. a) 1D-NMR profiles of pre-adsorbed C6H14 during C6D6 adsorption, b) Signal intensity versus time for different values of z/g in the bed of the catalyst: II (t - 0 h), [2 (t = 0.02 h), x (t =0.13 h), A(t = 0 . 3 0 h ) , o (t = 1.16h), r (t= 3.90 h ) , * (t= 9.00 h) Time increases from the top to the bottom in figure 8a. We initially observe a rectangular profile corresponding to a uniform distribution of benzene. The total signal area decreases slowly with time. The decrease of the benzene concentration between the beginning and the end of the experiment is about 25 %. But its distribution in the sample is particularly inhomogeneous, as is shown in Figure 9-b. The intensity decreases at the top and increases markedly at the bottom of the bed, showing that the n-hexane adsorbs first in the upper

101 layers, "pushing" the benzene towards the bottom of the tube. The local partial pressure of benzene and, in parallel, its concentration in the bottom of the bed increase.

b~ i o e (h)

-----~~A~,,,

"--~---- 0.02

-~-~~A~"--

- 0.09

60 T ,-':,. gl 50

~4o ,Vo 20

.= -~--'-~ ~ ~ ' - ~

"~-----

-

-'-~~~~'~~----~

-

.-7

i.

.

Z=s

1.51 4.77

.! .~"7 - - - - 1 6 0 6 Z=0

tot 0

0.16

I

I

I

~

0.33

0.5

0.8

0.9

z/~

Fig. 9. a) 1D-NMR profiles of pre-adsorbed C6H6 during C6DI4 adsorption, b) Signal intensity versus time for different values of z/s in the bed of the catalyst. A (t = 0 h), O (t = 0.02 h), II (t = 0. 09 h), [] (t= 0.17 h), O ( t = 0 . 3 1 h ) , x ( t = l . 0 3 h ) , A(t=l.51h), r 9 (t = 16.06 h) Time increases from the top to the bottom in figure 9a. As the "wave" of n-hexane reaches the bottom, this latter gas adsorbs on the lower layers; the two partial pressures become uniform along the sample, and the benzene molecules can adsorb again in the upper layers until the thermodynamic equilibrium is obtained. The distribution of adsorbed gases is first determined by kinetics and then the system is governed by thermodynamics. The difference in the extent of displacement of one gas by another in the two experiments confirms, if this were necessary, the greater affinity of HZSM-5 zeolite for benzene. 4. CONCLUSION The application of ~H 1D-MR/ for the study of hydrocarbon diffusion gives two types of information. First, the variation with time of the surface area of the full signal (amount adsorbed as a function of time) during adsorption makes it possible to determine transport coefficients by simulation of the kinetic curves. For example, the intracrystallite diffusion coefficients of hexane and benzene in HZSM-5 determined by this technique are 10"13 and 10"14 m 2 s"i, respectively, in good agreement with data in the literature. Second, the shape of the instantaneous concentration

102 profiles reflects the variation of the local adsorbate concentration, and reveals a competition between kinetic and thermodynamic effects. In the case of competitive adsorption of several gases, this technique appears to be the only one capable of visualizing the relative distribution of each of the gases in the adsorbate and its variation with time. REFERENCES

1. S. Blackband and P. Mansfield, J. Phys. C: Solid State Phys., 19 (1986) L49. 2. N. Tanaka, S. Matsukawa, H. Kurosu and I. Ando, Polymer, 39 (20) (1998) 4703. 3. I. Ando, H. Kurosu, S. Matsukawa, A. Yamasaki, A. Hotta and N. Tanaka, Wileys Polym. Networks Group Rev., Ser. I (1998) 331. J. Wiley & Sons, Ltd. Publ. 4. P. Porion, N. Sommier and P. Evesque, Europhysics-Letters, 50 (3) (2000) 319. 5. G. Papavassiliou, M. Milia, M. Fardis, R. Rumme, E. Laganas, A. Sepe, R. Blinc, M.M. Pintar J. Am. Ceram. Soc., 76 (1993) 2109. 6. J.H. Strange, J.B.W. Webber and S.D. Schmidt, Magnetic Res. Imaging, 7-8 (1996) 803. 7. I. Koptyug, V.B. Fenelonov, MY. Khitrina, R.Z. Sagdeev and V.N. Parmon, J. Phys. Chem., B, 102 (1998) 3090. 8. M.R. Halse, Magnetic Res. Imaging, 7-8 (1996) 745. 9. J.-L.Bonardet, T. Domeniconi, P. N'Gokoli-Kekele, M.-A. Springuel-Huet and J. Fraissard, Langmuir, 15 (1999) 5836. 10. E. Ruckenstein, A.S. Vaidyanathan and G.R. Youngquist, Chem. Eng. Sci., 26 (1971) 147. 11 L.K. Lee, AIChE. J. 24 (1978) 531 12. J. Cranck, The Mathematics of Diffusion, Clarendon Press, U. K. Oxford, 1956. 13. W. Heink, J. K~ger and H. Pfeifer, Chem. Eng. Sci., 33 (1978) 1019. 14. P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L.Bonardet and J. Fraissard, Proceedings 13th International Zeolite Conference, in press. Elsevier Publ. 2001.

Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

103

Zeolite-based nanocomposites: synthesis, characterization and catalytic applications B.V.Romanovsky Chemistry Department, Moscow State University, Leninskiye Gory, Moscow, 117234, Russia The oxidative in-situ degradation of mono and polynuclear complexes of transition metals within the Y zeolite supercages has been employed to produce an array of oxide nanoclusters encapsulated in the intercrystalline voids of the matrix. The resulting materials were characterized by using a number of experimental techniques. The nanocomposites display extraordinary high activities in oxidation of CO and MeOH. 1. INTRODUCTION Nanocomposites in which one of constituent phases has at least one dimension smaller than 100 nm have recently attracted much attention as perspective functional materials of broad spectrum of applications. The growing interest to these novel systems is quite understandable since the bulk behavior of materials can be dramatically altered by controlling their cluster nanostructures, and this control can lead to greatly improved performance. Besides, the characteristics of nanomaterials could be purposely tuned not only by the variation of the chemical composition of the clusters but also by variation of their size and size distribution. One of the major difficulties in creating the nanosystems lies in the great excess of the surface free energy and as a result in their thermodynamic instability that causes an irreversible aggregation of nanoclusters into larger particles under kinetically favorable conditions. This urged the development of such a research branch as the creation of composite materials in which the nanosized particles are encapsulated in the internal voids of the microporous solids where the cluster size and their interaction to form large aggregates are strongly limited by the steric hindrance Zeolites and zeolite-like materials with their well-organized and regular systems of pores and cavities represent almost ideal matrices to host nanosized particles. The high thermal and chemical stability of zeolite-like matrices would afford the nanocomposites which could operate in a broad range of temperatures and in various media. The zeolite cavities can be considered as peculiar reaction nanovessels where the chemical processes carried out inside them and their products are affected by the confines in which they are being performed. This main principle was proven in mid-70's when the first synthesis of neutral phthalocyanine complexes encapsulated in Y zeolites via intracrystalline assembling was performed at Moscow State University [1,2]. Once formed within the bottle-shaped supercages of Y zeolite, the resulting electroneutral complexes cannon leave them because of spacial restrictions. Later, this new type of inclusion compounds was termed as "ship-in-a-bottle" systems [3].

104 The general strategy for preparing the zeolite-included composites is also based on the ability of restrictive void spaces of the zeolite to control growth of size-confined phases. The in-situ thermal or redox treatments of inorganic or organometallic precursors preloaded into the matrix internal voids yield the metal or oxide particles hosted inside the supercages. The major problems deal usually with the choice of appropriate precursors. Apart from meeting the obvoius geometric criteria, the optimal precursor should also display the substantial solubility in a selected solvent and be stable toward solvolysis or have a substantial vapor pressure and evaporate without essential dissociation or association. The in-situ transformation of the precursor molecules into oxide clusters should be performed under the mildest possible conditions. Otherwise, the elevated temperatures can cause the migration of primarily formed species to the outer surface of a matrix and their aggregation. The present paper reported below is a brief review of our recent advances in the synthesis and investigation of the zeolite-incorporated oxides of some transition metals. 2. PREPARATION OF ZEOLITE-INCORPORATED METAL OXIDES

2.1 Preeursor loading There exist two routes to load the zeolite matrix with metal-containing precursors. First one is the ion exchange of Na for complex cations. In an alternative way, the zeolite is loaded with neutral precursor molecules by utilizing the incipient wetness impregnation technique. Of course, the size requirements for precursor species and the matrix openings are evident to be the key factor in both cases. However, the impregnation technique has some advantages over ion exchange. In fact, the methods for preparing various homo and heterometallic, mono and polynuclear complexes or cluster compounds have been well developed so that the most of requirements to size, shape and solubility of a precursor can be satisfied. This factor becomes crucial when bimetallic oxide clusters should be prepared. Loading the zeolite matrix with discrete precursor molecules containing different metals affords incorporated products with much more predictable and controllable properties than those made via the ion exchange procedure In this respect, the variations of ionic forms of precursors are substantially restricted not to mention some specific limitations imposed on the ion exchange technique. In the present work, we applied a variety of both monometallic and bimetallic complexes to load the zeolite matrix with a precursor. They are listed in Table 1. Table 1 Transition metal complexes used as precursors Monometallic complexes (l.t4-O)L4Cu4C16*, CuPc, NiPc, CoPc, Fe3(CO)12, Fe(acac)3, Ru(acac)3, Zn3(acac)6, Ni3(acac)6, Ag2(FAcO)2**, Cu2(FAcO)4, NiE(FAcO)4, [RuE(AC)4]C1, Fe4(CO)I3(Et4N)2, FesC(CO)I4(Et4N)2, Fe6C(CO)I6(Et4N)2, [Fe30(AcO)6(HEO)a]AcO, [RuaO(AcO)6(H20)3]C104,

Bimetallic complexes Co2Ni2(acac)4(MeO)4(AcO)2, CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2, ReMoOffMeO)7

105 *L = N,N-diethylnicotinamide, **FAcO = CFH2COO- - monofluoracetate anion Of particular interest are two polynuclear precursors: (kt4-O)L4Cu4C16 and ReMoO2(OMe)7 complexes. The first adamantan-like complex has been shown by Davis et al. [4,5] to loose its diethylnicotinamide ligands on contacting the complex in methylene chloride with dry NaY so that only N-free bare (kt4-O)Cu4C16 units enter the zeolite pores. We obtained the similar result with ReMo oxomethoxide complex: after loading it into NaY zeolite since no traces of organic ligands as determined by elemental analysis were found in the sample. So that in this particular case, simple loading the NaY zeolite with these ReMo oxomethoxide complexes results in the ReMo oxide species molecularly dispersed in the matrix bulk. No additional treatment of the metal-loaded zeolite are required to obtain nanomaterial. On the other hand, this very important finding means that the polynuclear core species residing within the zeolite supercages are stabilized by the host framework that plays the role of a peculiar macroligand. Special attention should be paid to the selection of an appropriate solvent. Apart from an obvious requirement of good solubility, the complex precursor used must not dissociate in a selected solvent, e.g., in water. Otherwise, the impregnation may give not only the neutral precursor molecules loaded but also the ion-exchanged species unless the special precautions are taken. As a result, after removing solvent the zeolite cages will contain three types of particles, i.e., precursor molecules, precursor cations and some amount of Na compound. In this case, the outcome of subsequent thermal treatment of the material becomes rather uncontrollable. We faced this situation using the aqueous solution of copper (II) monofluoracetate (see Table 1) to impregnate NaY zeolite. In fact, the starting solid Cu(II) monofluoracetate consists of dimer Cu2(CFH2COO)2 molecules. However, on dissolving in water it gives the monomer species which in turn dissociate into Cu(II) and fluoracetate ions. After impregnation, the resulting sample exhibited some amounts of isolated Cu(II) ions as was evidenced by the characteristic signal of these paramagnetic centers in ESR spectra. This signal remains unchanged even after the treatment of the sample at 400~ in air while the DTA-TG data indicate complete oxidation of the precursor organic part by 250~ [6]. 2.2 Transformation of zeolite-loaded precursors into oxide species With the exception of two very specific cases mentioned above, subsequent in-situ oxidation of loaded precursors is required to convert them into oxide species. It should be kept in mind that by varying the nature of precursor ligands lower oxidation temperatures and therefore better dispersion and lover degree of aggregation can be obtained. As a rule, this procedure can be performed by simple calcination of the material in dry air or oxygen flow at 200-450~ depending on the precursor nature. Oxidation of the loaded precursor to corresponding oxide phase is easily monitored both qualitatively and quantitatively by the DTA-TG technique. In some cases, the GLC analysis of effluent gases can be utilized to control the oxidation of precursors. Another important factor of the oxidation step which must be well controlled during this procedure are eventual losses of the metal precursor compound due to its high volatility. If the rate of oxidation is inadequate, the loaded precursor can sublimate before its oxidation occurs. For example, we found that up to 50% of Zn acetylacetonate as determined by

106 elemental analysis could be lost when the sample with this loaded precursor is heated in a gas flow at about 400~ for 4 hr. 3. C H A R A C T E R I Z A T I O N OF Z E O L I T E - I N C O R P O R A T E D METAL OXIDES Various experimental techniques were employed to characterize the prepared samples. Often, several methods are required to be applied simultaneously to control the consecutive stages of preparation protocol. N__2-BET measurements. These measurements were performed with selected oxidized samples in order to ascertain whether blocking of matrix channels by forming oxide phase takes place. This can be judged on comparing the surface area of starting NaY zeolite with that of the sample after its high-temperature treatment. In fact, a few samples showed about two-fold decrease in surface area which indicates the formation of large particles of oxide phase out of the matrix bulk. X-ray diffraction. Appearance of diffraction peaks consistent with an individual nonzeolitic phase shows unambiguously the formation of oxide particles much more than nanosized [7]. Though the lack of such peaks does not mean the contrary. IR and UV-VIS spectroscopies. The use of IR method enables one to control the loading of precursors and their further transformation into the oxide moiety. At the metal loading as low as a few wt % (metal basis), the IR bands characteristic of metal oxides are too weak to judge on their formation. As to electron absorption spectra, this technique was successfully applied in [8] not only to identify the metal sulfide and solenoid nanoclusters encapsulated in zeolites but also to estimate their mean sizes basing on the blue-shift of absorption-edge in respect to bulk material. Unfortunately, this technique in studying the supported metal oxides turned out to be ineffective mainly because of too broad bands obtained for the samples subjected these investigation. Temperature-programmed reduction by H2. The H2-TPR experiments provide very important information concerning the distribution of metal oxide moiety between the bulk of zeolite support and its external surface. This distinction can be made basing on the positions of peaks in H2-TPR profiles obtained for a sample after the oxidation of loaded precursors and for the corresponding free oxide taken as a standard. For example, NiO/NaY sample gives two H2-TPR peaks centered at 410 and 575~ while bulk NiO exhibits only one reduction maximum at 390~ This result suggests that the hightemperature peak on the first H2-TPR profile could be ascribed to the reduction of intemal NiO species while the low-temperature maximum is very probable to arise from outer nickel oxide. In addition, the measurements of hydrogen uptake in H2-TPR experiments could be used to reveal the valent state of a transition metal present as oxide phase. In the case of Re system, the nominal content of metal was 3.7 wt % with corresponds to 0.74 mmole O/g as Re207 or 0.63 mmole O/g as ReO3. whereas the total amount of H2-TPR consumed between 100 and 1000~ was estimated as 0.72 mmole/g. Measurements of magnetic susceptibility. The zeolite-included oxide clusters obtained from their metallocomplex precursors may in their turn play the role precursor in preparing the materials including nanoscale metal particles. In a few cases of ferromagnetic metals, the measurements of magnetic susceptibility of reduced samples make it possible to establish the distribution of reduced metal between the surface and the bulk of support. Even though the precursor species are at the very beginning evenly distributed, the hightemperature reduction results inevitably in the formation of large metal particles on the

107 external surface of support. Experimental data on the measurements of magnetic susceptibility for a set of Ni containing sample are given in Table 2. On considering these data, it should to be taken into account that the experiments were performed in an apparatus allowing to determine the metal particles sized more than 2 nm, smaller particles are magnetically silent. Given that two-nanometer sized metal particles cannot reside within the zeolite supercages, we measured only the magnetic moiety of reduced nickel on the outer surface of zeolite matrix. It is seen from these results that the share of metal nickel present as small particles less than 2 nm in size decreases dramatically on diminishing the amount of metal loaded. Of course, these estimates correspond also the concentrations of oxide precursors initially hosted in the supercages but only their bottom limit, and the real content of oxide component present as the cage-hosted nanoclusters may be substantially higher. Table 2. Metal contents determined by elemental analysis and by magnetic measurements for nickel-containing samples reduced by H2 at 400~ Total nickel, wt % (EA)

External nickel, wt % (MM)

Internal nickel, %

1.89

0.60

68

1.68

0.91

45

0.81

0.69

15

ESR method. This technique can reveal the changes in coordination and valent state of the paramagnetic ions which may occur during the different treatments of the zeolite with loaded precursor. Also, ESR spectroscopy make it possible to discover any interaction between the paramagnetic centers of different nature when they present simultaneously in a catalyst [9]. Elemental analysis and XPS technique. Joint use of these methods give the important information about the distribution of in-situ formed species between the bulk and the outer surface of zeolite matrix [ 10 4. CATALYSIS BY Z E O L I T E - I N C O R P O R A T E D METAL OXIDES Two model reactions were applied to characterize the catalytic behavior of the zeoliteincorporated metal oxides: carbon monoxide oxidation and methanol conversion. As is clear from what follows, the catalytic activity turned out to be the most sensitive properties toward the minor changes in a catalysts "biography". Therefore, some disagreements may rise on comparing the activity of supposedly similar samples with the same composition but of different preparation history. 4.1 Carbon monoxide oxidation.

This reaction was studied using the zeolite-incorporated CuO catalysts; the samples were prepared employing tetranuclear (I.t4-O)L4Cu4C16 complex as a precursor [7,11]. For comparison, the activity of bulk CuO with surface area of 8.6 m2/g was also evaluated. The

108 process was carried out in a gradientless reactor with the stoichiometric CO+O2 mixture at 450~ and atmospheric pressure. The results are summarized in Table 3. Table 3. Oxidation of CO over the zeolite-incorporated and bulk CuO Cu content, wt % Reaction rate, mole/s.g

2.72

7.52

7.5x 10"2

18.4• 10.2

80 1.94x 10-2

TOF, molecule/s per atom 1.78x 102 1.55• 102 -~ 3• 10 2** * Pure CuO, ** Evaluated basing on the surface concentration of c.a. 1015 atoms Cu/cm 2 As seen, the reaction rates calculated per unit mass of catalyst for the zeolite-based samples are substantially higher than that for the bulk copper oxide regardless many times smaller content of the active phase. Any doubt, the extraordinary high dispersion of CuO explains this difference. In contrast, the TOF values seem to be of the same order of magnitude if one takes into account very approximate evaluation for the surface concentration of Cu atoms. On the other hand, some diminishing in the TOF values on increasing the metal loading suggests that the oxide particles agglomerate probably in neighboring supercages which effect cannot be revealed by any other way. These conclusions are fully supported by the results in which the oxygen storage capacities (OSC) was measured for the samples. The values of OSC were determined by titration of the samples at 450~ with consequent pulses of CO which were introduced into the dry nitrogen flow passing through the sample bed in a quartz reactor till the formation of CO2 ceases. The results obtained in this series of determinations are given in Table 4. Table 4. Oxygen storage capacities of zeolite-incorporated CuO Cu content, wt %

2.72

7.52

OSC, mmol O/g

0.40

1.04

Atomic Cu/O ratio

1.05

1.14

The ratio of copper and reactive oxygen contents which were determined by two independent ways is very close to CuO stoichiometry. This indicates near molecular dispersion of copper oxide moiety incorporated with in the zeolite matrix. 4.2. Methanol oxidation The reaction was carried out in a fixed-bed quartz reactor at 90-400~ The reaction products were analyzed by a GLC technique. Carbon dioxide and formaldehyde were found to be the only products of methanol oxidation; in no case the formation of CO was detected. In parallel to oxidation, the dehydration of methyl alcohol also occurs, dimethyl ether (DME) being a product. Fig.1 shows the results obtained with the Fe containing sample prepared using hexacarbonyl triiron (see Table 1) as a precursor. Similarly to the case of CO oxidation, TOF values for methanol oxidation are noticeably dependent of the total metal loading. This also could be due to the intracrystalline agglomeration of iron oxide nanoparticles that

109 decreases the efficiency of Fe active centers because of the changes of their mean coordination to oxygen atoms. An alternative explanation for these findings would be suggested such as influence of diffusion limitations inside the matrix micropores. In fact, a non-linear dependence of the measured reaction rates on active component concentrations is to be expected, provided the diffusion limitations would play a significant role (see $2 histogram series in Fig.l). However, this effect seems to be little possible since the difference in the measured values of reaction rates for CO and MeOH oxidation amounts to two order of magnitude which makes the Thiele modulus to vary ten times. This latter excludes the diffusion effects from consideration. On the other hand, the results of catalytic measurements could discover the effect of steric non-compatibility of precursor molecules and matrix pore openings that makes it impossible to load the matrix with a precursor compound. In Table 5, the total conversions of MeOH are compared for a set of iron-containing samples with about 1 wt % Fe prepared by utilizing the iron carbonyl complexes of various nuclearity - from 3 to 6 (see Table 1). In contrast to four-nuclear Cu and ReMo complexes that can readily loose their labile ligands before entering the zeolite channels as mentioned in the previous section, polynuclear Fe cluster compounds are too rigid and cannot penetrate the matrix pores unless the molecular size allows this. Table 5. Total methanol conversion over zeolite-incorporated Fe oxide Sample

NaY

Fe3/NaY

Fea/NaY

Fes/NaY

Fe6/NaY

Methanol conversion, %

11.7

54.1

2.6

2.2

2.9

NaY starting material, Fe3, Fe4, Fe5 and Fe6 - samples obtained from tri, tetra, penta and hexanuclear iron carbonyl complexes, respectively; reaction temperature - 400~ -

As seen from these data, the loading of parent NaY zeolite with iron oxide via trinuclear Fe carbonyl as a precursor increases greatly the total rate of methanol conversion because of the appearance of oxidative active centers. In contrast, the use of carbonyl complexes of four and more nuclearity resulted in a dramatic drop of MeOH conversion even in comparison to the starting material. It should be noted that all Fe-containing samples have the same amount of iron oxide (about 1 wt %, metal basis), and such an effect can be explained only on assuming the formation of multilayer oxide deposits that cover the outer zeolite surface including its pore mouths. This assumption was verified by measuring the surface area for this set of samples that decreases from about 700 m2/g for NaY down to a few tens m2/g for three last samples in Table 5. It should be added that these findings seem to be significant in one more respect. They allow to make some conclusions, though indirect, concerning the behavior of complex molecules other than iron ones as precursors upon reaction with microporous matrices like NaY material. In fact, the large complexes such as CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2 and C02Ni2(acac)a(MeO)n(AcO)2 are evident to be impossible to penetrate the Y zeolite channels of 0.7 nm in diameter. Nevertheless, the impregnation of NaY zeolite with acetonitrile solutions of these complexes yielded about 1% loading (metal basis) with a negligible decrease in the surface area. Even though there were no analytical measurements for organic residues in the samples prepared by such a

110 route, these multiligand polynuclear complexes could be expected to behave in a very similar way that analogous ReMoO2(OMe)7 and (kta-O)LaCu4C16 complexes do. As depicted previously, on contacting with parent NaY material, namely they loose their organic ligands stabilizing the polynuclear metal core and change them for an inorganic environment on residing within the supercages. Of course, this conclusion can by no means be generalized so that every particular case of a metallocomplex with polynuclear core as a potential precursor to be loaded into a micropore matrix required the special investigation. It would be of interest to compare the zeolite-based oxide catalysts prepared by loading the parent material with polynuclear metallocomplex precursors with those obtained via traditional impregnation with a metal salt. In Table 6, the experimental results on methanol oxidation we obtained for a series of Co and Ni containing samples are summarized. Although the samples (except for the first one) contains the same amounts of loaded metal oxide, the efficiency of those obtained via polynuclear precursors differs dramatically from that for the conventional zeolite-supported NiO. These data are well consistent with the results found for CO oxidation that was carried out over the analogous set of catalysts. Table 6. Methanol conversion over the zeolite-incorporated Co and Ni oxides Catalyst Metal, wt % Temperature, ~ Reaction time, min Conversion,% Selectivity b, % carbon dioxide dimethylester

Co2Ni2/NaY Co4/NaY 0.5 1 250 250 82 122 163 80 120 142 85 83 88 91 93 94 99 98 99 1 2 tr.

98 99 97 2 1 3

Ni4/NaY 1 250 84 131 242 73 79 72

Ni/NaY 1 350 60 120 5 4

98 99 97 2 1 3

3 4 97 96

Note: Co2Ni2/NaY, Co4/NaY and Ni4/NaY samples were obtained via four-nuclear complexes (see Table 1), Ni/NaY sample was prepared by the impregnation of parent NaY material with aqueous solution of Ni nitrate Lastly, the comparison of activities determined for monometallic and bimetallic oxide catalysts can provide an important information on whether two oxide components are independent active entities or they can interact with each other. This was illustrated by Fig.2 where the TOF values for monometallic Ru (S 1series) and Fe ($3 series) samples and bimetallic RuFe ($2 series) samples are depicted. It should be noted that in the mixed RuFe samples ruthenium and iron concentrations are close to their content in corresponding monometallic analogs. As seen, the activity of Fe-containing samples is significantly smaller than that of Ru-containing catalysts. From this result, the activities of mixed RuFe samples would be expected to be similar to those for Ru catalyst set provided the additive effect is operative. However, it is not the case, and the activity of ruthenium centers becomes inhibited in the presence of iron species. Such non-additive effect could be due to the chemical interaction of oxides which occurs within the nanosized internal voids of zeolite matrix and is enhanced by severe spatial restrictions. Similar effects we have observed [9] for Fe-containing Y zeolite. Upon loading this zeolite with Cu(II) acetate

111 complex, the Fe(III) centers becomes fully ESR silent because of interaction of neighboring paramagnetic atoms. The examination of zeolites modified with transition metals as catalysts of methanol conversion have revealed the close connection of redox and acid-base functions of these catalytic systems. In fact, methyl alcohol can react by two pathways that are supposed to be rather independent. The acid centers of zeolites are commonly believed to be responsible for dehydration of methanol to dimethyl ether while the oxidative sites account for the formation

Fig. 1. Activity in MeOH oxidation of Y zeoliteincluded iron(Ill) oxide: 1-0.18 wt% Fe; 2-0.39 wt% Fe; 3-0.76 wt%Fe. S 1 - TOF values, a.u. $2 - activity per unit mass

Fig.2. Activity in MeOH oxidation of Y zeoliteincluded ruthenium (S 1), rutheniun-iron ($2) and iron ($3) oxides per unit mass of metal as the function of Ru (1-4), RuFe (5,6) and Fe (7-9) loading

of formaldehyde and carbon oxides. In this connection, we have investigated more closely the simultaneous occurrence of both reactions using the zeolite-incorporated oxide catalysts [12]. The catalysts was obtained by oxidative degradation of Cu, Ni and Co phthalocyanine molecules (see Table 1) that were previously "ship-in-bottled" into NaY zeolite. Methanol conversion was performed in air or in nitrogen flow. Below 250-280~ the yields of dimethyl ether in air were found to be noticeably higher than in nitrogen. These somewhat unexpected results were explained by assuming the dual-site mechanism

112 of methanol dehydration. It was suggested that the transition state includes both basic and acid sites that further gives DME. Besides, the basic center can react with MeOH molecule yielding carbenoid-like surface intermediate. These intermediates are more or less stable in an inert media and thereby break the well-organized structure of dual sites which make it impossible to form the transition state of dehydration pathway. On the contrary, the carbenoid species are readily oxidized in air and this restores the active sites accounted for methanol dehydration. 4. CONCLUSIONS Faujasite-type zeolites with the bottle-shaped supercages are the most suitable matrices that provide good opportunities for preparation of the nanocomposite materials using mono and polynuclear metal complexes with organic ligands as precursors. The spatiallyhindered in-situ oxidation of these precursors preloaded into the cages yields the highly ordered systems of oxide nanoclusters. The migration of these clusters is strongly retarded within the matrix micropores so that their aggregation to form large particles on the outer surface is little probable. The highly dispersed oxides incorporated into the zeolite intracrystalline voids exhibits good catalytic performance in carbon monoxide and methanol oxidation. ACKNOWLEDGEMENT

This work was financially supported by Grant 99-03-3298 and Grant 00-15-97346 from the Russian Foundation for Basic Research. REFERENCES

Romanovsky B.V., Zakharov V.Yu., Borisenkova S.A., USSR Patent, No.552752, 1975. Zakharov V.Yu., Romanovsky B.V., Bull. Mosc. State Univ., Ser 2, 18 (1977) 142. Herron N., Stucky G.D., Tolman C.A., Inorg. Chim. Acta, 100 (1985) 135. Abdel-Fattah T.M., Davies G., In: Multifunctional Mesoporous Inorganic Solids (C.A.C.Sequeira and M.J.Hudson, Eds.,), Kluwet Acad. Publ., 1993, p. 121. 5. Davies G., Giessen B.C., Shao L., Mater. Lett., 9 (1990) 231 6. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Russian J. Phys. Chem., 75 (2001) 231. 7. Abdel-Fattah T.M., Davies G., Romanovsky B.V., Shakhnovskaya O.L., Larin A.M., Jansen S.A., Palmieri M.J., Catal. Today, 89 (1996) 1121. 8. Tolkachev N.N., Stacheev A.Yu., Kustov L.M. Abstr. Internat. Boreskov Memorial Conf., 2nd, "Catalysis on the Eve of XXI Century", Novosibirsk, 1997, p.256. 9. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Bull Mosc. State Univ., Ser 2, Chem., 41 (2000) 293. 10.Romanovsky B.V., Gabrielov A.G., Mendeleev Commun., 1 (1991) 14. 11.Berdanova E.I., Larin A.M., Shakhnovskaya O.L., Romanovsky B.V., Bull. of Russian Acad. Sci., Ser.2, Chem., (1997) 1761. 12.Kustov A.L., Moskovskaya I.F.,Romanovsky B.V., Zhilinskaya E.A., Aboukais A., Recent Reports at the lntern. Congr. on Catal., 12th, Granada, 2000.

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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

113

Application of Combinatorial Tools to the Discovery and Commercialization of Microporous Solids: Facts and Fiction Jennifer Holmgren, a David Bem, a Maureen Bricker, a Ralph Gillespie, a Gregory Lewis, a Duncan Akporiaye, b Ivar Dahl, b Arne Karlsson, b Martin Plassen, b Rune Wendelbo b a UOP LLC, 25 East Algonquin Rd., Des Plaines, Illinois, 60017, USA b SINTEF, P.O. Box 124, Blindern, 0314 Oslo, Norway

During the past three years, combinatorial tools and methods have received increasing amounts of attention as potentially enabling methodologies for the chemical industry. We have developed a combinatorial multiautoclave, which can be used to explore hydrothermal space efficiently and effectively. Our recent results illustrate the applicability of this capability to both the discovery and scale-up of microporous solids. 1. INTRODUCTION The chemical industry faces an extremely competitive business climate. In addition, innovation in this industry has slowed as catalyst and process technology has matured. 1 Despite the maturity of the catalyst industry, there is a continuing and growing need for improvements in catalyst performance, to increase the efficiency of industrial processes and reduce their environmental impact. Such increases cannot be obtained through incremental improvements using existing development methodologies. In order for the chemical industry to maintain a competitive advantage, a breakthrough in catalyst R&D methodologies is greatly needed. The pharmaceutical industry faced similar circumstances in the 1980s as the high cost of drug discovery became incompatible with downward pressure on drug prices. In that case, combinatorial chemistry, with high throughput screening and integrated informatics, provided a breakthrough methodology for the pharmaceutical industry to increase its innovation ability. We believe that the successful application of combinatorial methods to the chemical industry could have similar benefits: 1) an increase in the rate of catalyst innovation and 2) a decrease in commercialization cycle times. Because of this belief, UOP and SINTEF have developed their End-to-End T M combinatorial catalyst discovery system. This system includes the ability to perform all the critical catalyst processing operations combinatorially (Figure 1). We have validated each of these steps using commercially relevant catalyst examples. In addition, we have utilized the entire system to prepare and test catalysts for catalytic applications.

114

Figure 1. Unit operations in our End-to-End SMcombinatorial catalyst discovery system. An essential element of extending combinatorial methods to catalysis is the ability to synthesize libraries of inorganic materials. 2'3'4'5 Workers at SINTEF were the first to report the successful development and implementation of a combinatorial hydrothermal synthesis cell. This cell lies at the heart of our library preparation system. 2 Other workers have also reported methods to synthesize libraries of materials from hydrothermal reaction. 3'4 The successful implementation of a miniaturized hydrothermal multiautoclave requires dealing with a number of technical hurdles: 9 9 9 9 9 9

synthesis

Demanding experimental conditions related to high pressure and high temperature Chemically aggressive conditions such as high pH and HF High sensitivity to preparative procedures Complex heterogeneous systems including gel formation and phase separation Labour intensive work-up procedures, and Complex characterization

Our multiautoclave addresses the problems of parallel syntheses, parallel work-up and rapid screening and offeres a new tool for efficiently charting a variety of chemistries. Using this multiautoclave as its foundation, we have created an integrated, fully automated hydrothermal synthesis system, which includes the following fully integrated capabilities: 9 9 9 9 9

Statistical experimental design with chemical constraints Reagent transfer Data logging of all relevant process conditions Parallel work-up and isolation Automated X-ray and SEM analysis

115 We have successfully utilized our integrated system to synthesize and characterize zeolites, A1POs, microporous oxides and other relevant inorganic oxides. We find that although we are working with microliters of reagents, that the results in this multiautoclave are scalable to the laboratory scale (125 ml). In terms of applicability, we have utilized this system for the discovery, optimization, and the scale-up of new materials. We will present four examples throughout this paper to demonstrate this capability. 2. EXPERIMENTAL To illustrate the experimental procedures used, details regarding the experimental work for a Zn-Cu-V-O example are presented here. The compositional variables, reagents, and digestion parameters used for the Zn-Cu-V-O combinatorial experiment are given in Table 1. The aqueous reagents were delivered to a multiautoclave via a robotic pipetter with concurrent agitation of the reaction mixtures. After sufficient homogenization, the multiautoclaves were sealed and digested at the appropriate conditions. After the digestion, the samples were washed, pulverized, isolated and mounted for powder X-ray analysis. The recovery process was completed using parallel methods. X-ray diffraction data were collected on a Bruker AXS D8 powder diffractometer. The diffractograms were then analyzed using automated data handling methods. Table 1 Variables and Their Values in the Vanadate Combinatorial Experiment

Variable

Multiplicity

Zn-Cu Mixture (Zn + Cu)/V Ratio OH-/V H20/V Replicate Standards Temperature Time Reagents Total Experiments

5 2 4 1 8 3 2

Values ZnxCUl_x, x = 0, 0.25, 0.5, 0.75, 1.0 (Znx + Cul.x)/V = 1or 2; x as above 0, 0.33, 0.67, 1.0 200 Zn:V:OH:H20=2:l :0.33:200 100 ~ 150 ~ 200 ~ 38hr, 168hr Zn(NO3)2*25 H20, Cu(NO3)2*25 H20, H20, NaOH*5 H20, and Na3VO4*60 H20 288

3. RESULTS AND DISCUSSION In a conventional investigation, one often will prepare a homogenous reaction mixture, split the reaction mixture among several autoclaves, and digest these autoclaves for a variety of temperatures and times. Essentially, the conventional experiment explores digestion conditions for a specific synthesis gel. A combinatorial or multiautoclave experiment, on the other hand, is designed to study a variation of compositions across the multiautoclave assembly. The digestion study can be performed by preparing a series of multiautoclaves with a set of gel compositions and digesting each multiautoclave at a different condition. By using a specific multiautoclave assembly to explore gel composition space and a series of multiautoclaves to study digestion conditions, composition space can be mapped very efficiently.

116 K20 0.0

1.0

02/ . \o8 _" ~ \o~ 04/ , \o~ ~ .\o~ ~ ~o~ ~ 9 \o~ ~ , 9 \o~ ~ , \Ol

K20 Original Design Combinatorial Design__

~.o / . . . . . ," \ o.o TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Na20

~176 o.y'\og

0 .u~v ~ u.i8: 0 ~, " .8.7

o.~:',,\ .* ,,, \06

0~/,.,

~ ..'~o~ ~ V;,~4 0~--~~ : \0.3 0 ~ - , ; , , . \0.2 1.0# - v v v v v - ~" v ; ~ . ~" TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0"0Na20

Figure 2. Exploration of the xTEA20: yNa20: zK20: A1203:10 SiO2:150 H20 (x+y+z=3) system. The first phase diagram illustrates the experiments done in the conventional design of experiments (DOE); the second shows the experiments performed using the combinatorial approach.

3.1 Combinatorial Investigation of Al-Si-O Systems Figure 2 shows two phase diagrams. These represent the exploratory investigation of a zeolitic synthesis space at a 10:1 SIO2/A1203. In this experiment, the impact of varying the K20:Na20:(TEA)20 ratio was examined. The original experiment, done using conventional methods, explored 10 compositions while the combinatorial experiment explored 100 compositions. In order to validate that the multiautoclave effectively mimics the laboratory scale, the combinatorial experiment also included the 10 original gel compositions. In all cases, the laboratory results were reproduced. In addition, because oxide synthesis and crystallization is intrinsically an inhomogeneous process, to ensure reproducibility on the scale of the combinatorial experiment, replicates were used within and between the multiautoclaves. In all cases the experimental results were consistent with expectations. In this example, the work done to explore the original 10 compositions required approximately one man-month of labor during an elapsed time of six months. The combinatorial experiment, on the other hand, was done over a one-week period utilizing only two days of labor. In addition to the tremendous increase in productivity demonstrated here, the experiment also illustrates that the combinatorial approach can more effectively cover the entire reaction space. Because these synthesis systems are inherently discontinuous, a broader exploration will likely result in increased knowledge and a decreased probability of missing a critical result. The previous example illustrates the use of combinatorial methods to explore novel reaction space. This next example will illustrate the use of combinatorial methods to focus on the details and reexamine a "known" system: mixed alkali structure direction in the Si/A1 = 3 and 10 systems. The experiment consisted of 15 high symmetry alkali combinations of Li § Na +, K § and Cs § including four 1-way interactions, six 2-way interactions, four 3-way interactions, and a 4-way interaction. This design is shown in Figure 3. Including replicated reactions run for quality control, 960 reactions were run. This work is described in depth in the paper presented by Lewis at this conference. 6

117

Na Li

9 Single 4-way interaction 9 3-way interaction + 2-way interaction 9

K

Cs

mmm

Temp 125~

150~

Figure 3. Experimental design for alkali template combinations investigated displayed on a tetrahedral quaternary phase diagram, along with reaction stoichiometries and process conditions. The high-symmetry points selected to cover the experimental space include the four individual templates (o), the six 2-way combinations (+), the four 3-way combinations (A), and the one 4-way combination (m), yielding 15 unique alkali template combinations. This study mapped out the compositions and conditions leading to the major pure products, including BEA, ANA, MER, LTL, and pollucite (ANA-Cs). An assumption in this experiment, that TEA + would do little structure direction at Si/A1 = 3, proved valid as BEA was only observed at Si/A1 = 10. Pollucite, the Cs analog of analcime (ANA-Cs), was the only other major pure product observed at Si/AI = 10, forming at the higher hydroxide levels of OH-/(Si+A1) = 0.55 and 0.64, while BEA formed at 0.45 and 0.55. Cs + was the strongest structure director among the alkali at Si/A1 = 10; BEA did not form if the Cs level exceeded 0.67 Cs/A1. The low ratio materials LTL and ANA were also observed on several occasions at Si/A1 = 10, but only at the highest hydroxide level of OH/(Si+A1) = 0.64. Presumably the hydroxide concentration was high enough to dissolve sufficient silica to allow the lower ratio materials to form. Such a study can be easily done in a month's time using combinatorial methods and illustrates the value of the combinatorial tool in mapping compositional space. In addition, this experiment illustrates the difficulty in designing the experiment such that the key interactions of the variables can be understood in a minimum number of experiments.

3.2 Combinatorial Investigation of the Zn-Cu-V-O System The use of the multiautoclave assembly is not limited to the exploration of zeolitic synthesis gels. A study was carried out in the Cu-Zn-V-O system, a system that we had previously examined as part of an effort to prepare novel metal oxides. This study resulted in an increase in fundamental knowledge of a well-known system due to the increased density of the information collected using combinatorial methods. The conventional study yielded the material Zn3V2OT(OH)2*2H20, the structure of which was solved by ab initio methods on powder x-ray diffraction data. 7 The hexagonal structure consists of LDH- or brucite-like Zn oxyhydroxide layers separated by pyrovanadate groups. Since a similar monoclinic structure was known for the Cu analog, the mineral volborthite s, we explored the Zn-Cu mixed metal system. This study resulted in a new structure that was prepared at high temperature having

118 the stoichiometry CuZnVO4OH. 9 The LDH-like Zn and Cu layers are buckled in this structure giving rise to a more dense structure containing orthovanadate groups and 5-coordinate Cu and Zn between the layers. The structural evolution of the reaction composition given by Zn : Cu : V : H20 of 1.5 : 0.5 : 1 : 200 in temperature and time is shown in Figure 4. The crystallinity of the Zn3V207(OH)2*2H20 phase increases with time at 100 ~ and 150 ~ while conversion to the CuZnVOaOH-type structure is observed at 200 ~ An examination of the replicate composition as the Zn is systematically replaced by Cu, is shown in Figure 5. The figure clearly shows the hexagonal pattern associated with the Zn-rich compositions converting to an intermediate species when equal amounts of Zn and Cu are present. Further addition of Cu yields the more complicated monoclinic pattern associated with volborthite, Cu3V207(OH)2*2H20. These three structures were the dominant products in the 100 ~ and 150 ~ chemistry.

1250'

j/k

A200oc,

~

; :

;jr ~

i t.j

:,i ~ ,

li' i il i .:, ~1 ! ~ 150~

7d

2~o_ ~

i

!./ \

:~

! !

]/I

i ^ IA150~ ,

2d

i'

I'' t

I

I'

2d

I

'

i "~-

I 0

'

5

10

'

15

20

2-Theta(*)

'

25

30

!

100~

I

35

Figure 4. The structural evolution of the reaction composition given by 1.5 Zn: 0.5 Cu: 1.0 V: 200 H20 in temperature and time. There were several other interesting products observed at 100 ~ and 150 ~ over the course of this study. The layered intermediate Cu2(OH)3NO3 was observed in a number of preparations that usually included the higher levels of NaOH. Zn-containing analogs were also observed. These products were observed only after 38 hr; by 168 hr they were always converted to volborthite or one of the similar Zn-containing phases. The Cu2(OH)3NO3 structure has a similar LDH or brucite-like structure observed in the layers of volborthite and Zn3V207(OH)2*2H20. ]~ This intermediate had never been observed in the original conventional study, probably due to the fact that acetates rather than nitrates had been employed. It is not apparent whether these hydroxynitrates are precursors or just less stable competing phases.

119 Another material in this category had an unidentified x-ray diffraction pattern and was the major product in 11 of the reactions, often forming along with volborthite. A single formulation, Cu : V : O H : H20 of 1 : 1 : 0.33 : 200 digested at 150 ~ for 168 hr gave a pure material. This formulation was scaled up in a 125 ml autoclave. A comparison of the diffraction patterns from the combinatorial experiment and the scale-up show excellent agreement. Further characterization by elemental, thermal analysis and SEM showed this material to be a new copper vanadium oxyhydroxide with the empirical formula CUllVa(OH)8017 and a needle-like morphology. 1500

Cu3V207(OH)2

Monoclinic

0

1000

0.5

t.o r-o

1

ce--

500

-

1.5

=2 0

5

lO

15

20

2-Theta(*)

2~

3o

35

Figure 5. Impact of systematically replacing the Zn by Cu [(Znx Cu2_x)/V=2, OH-/V=0.33]. Phase transition from hexagonal to monoclinic observed with increased Cu incorporation. These data illustrate the value of combinatorial methods to elucidate fine details of the synthetic chemistry. We believe this is one of the key features of using a combinatorial experiment - the ability to carefully define the phase space of interest and develop a deep understanding of the chemistry. In addition, even in a well-studied system like this one, new materials were uncovered that had been missed in the previous conventional work.

3.3 Combinatorial Investigation of M-AI-P-O Systems As a final example, the preparation and characterization of a series of metalloaluminophosphates was performed by screening a diverse mixture of gels based on variation of the chemistry of the inorganic and organic components. This involved the introduction of cobalt, magnesium or silicon into gels formed using cyclohexylamine, cyclopentylamine, N-methylcyclohexylamine and 4-methylcyclohexylamine as the organic structure directing agents. A total of 200 gel mixtures were prepared, including a series of

120 selected replicates and controls to probe the reproducibility of the experimental procedures across the parallel format. Crystallization of the gels was carried out for 24 h at 200 ~ followed by parallel filtering and washing stages. A set of eight identical gel compositions all generating a major AFI phase, randomly distributed within and between plates, confirmed the level of reproducibility achievable across the parallel format, even at this miniaturized scale.

Figure 6. Distribution of the AFI (dark) and CHA phases obtained in the A1POsyntheses. Labelling defined as follows: CH = cyclohexylamine, CP = cylcopentylamine, NCH = N-methylcyclohexylamine, MCH = 4-methylcyclohexylamine. The inorganic composition is defined according to: A = aluminophosphate, AX = metalloaluminophosphate composition (e.g. ASi = SAPO). Within the compositions studied, two of the major known phases identified were the AFI and CHA topologies. A correlation of these two phases as a function of synthetic parameters has been analyzed, and is summarized in Figure 6. Under the conditions presented here, many of the products were, not surprisingly, dominated by the presence of the AFI phase. However, in the presence of cyclohexylamine and cyclopentylamine pure CHA phases were obtained. To our knowledge, the formation of a pure SAPO-34 in the presence of cyclopentylamine has not been reported previously. This example again serves to illustrate the value of using combinatorial methods to fully characterize well-known systems. New information and knowledge can be collected even when exploring well-known/characterized systems. 3.4 Combinatorial Chemistry as a Scale-up Tool

Materials manufacturing can also benefit from combinatorial methods. Libraries to optimize recipes and process conditions can be studied using many of the methods and assays developed for materials discovery. The ability to correlate the synthesis variables with materials properties is valuable in determining manufacturing specifications for a given

121 material and ensuring the robustness of its synthesis. These tools and the resulting information will decrease the cost of manufacturing development and speed delivery of new materials to market. We have demonstrated the applicability of combinatorial methods to accelerate the scale-up and commercialization of new materials. In a recent example, we worked on the scale-up of a novel zirconium silicate. ~2'~3 These proprietary materials have demonstrated excellent selectivity for ammonium cations and as such could be important ion exchange materials in medical applications. 14 To accelerate commercialization of these new materials, we used combinatorial methods to determine the most robust composition region for their synthesis. A relevant subset of the 144 distinct compositions that were prepared is shown in Figure 7. In this work, the impact of gel composition on the formation of two distinct zirconium silicate phases was studied: "Product 1" and "Product 2." In this particular case, "Product 1" was the desired product. In the experiment, the Na, Zr, water and seed levels were varied. The initial laboratory scale work was performed in the left upper quadrant: high water, low Na, low Zr, no seed. Note that in this region small changes in any of the parameters results in formation of "Product 2" and amorphous material. The combi experiment uncovered a more robust region: the right, lower quadrant. In this region, the desired product could be synthesized over a wide range of Na, Zr, and water levels. This region is more robust: formation of "Product 1" is relatively insensitive to synthesis conditions. Such a robust recipe can be transferred more quickly to manufacturing. This optimization work was done in a two-week period and resulted in a significant reduction of the commercialization timeline for this product. Low Na

High Na

9 9 9 9 9 ..~

9

m

9

9 Am

Low Na 1

1

I

H i g h Na 1

1

9 9 9 9 9 9 9

9

9

9

Low Na iI

9

9

[ 1

1

I,~

m

i II II ii

I

/

9 m m j .. .~ 9 lm

II IN

o .d

m

9

9

9

9

9 9

9 9

9 9

9 9

9 9

9 9

9

9

9

9

9

9

9

9

9

9

Iml

9 9

9 mm"mm

Product #1" 9 Product #2: Wk Amorphous: l

9

High Zr

Low Zr 9

High Zr

'.k ..

t t

Seed 2

Low Zr

9 mm-A mm 9- 9 ._.

I I

No Seed

9

J ,j .

I I

IroN IroN ImI Iml 9

9

]

IN 9

H i g h Na /

Seed

1

Identified Robust Region for Product 1

Figure 7. Combinatorial optimization study of a zirconium silicate synthesis. This data was used to accelerate the scale-up and commercialization of a new material.

122 4. S U M M A R Y

We have successfully applied combinatorial synthesis methods to 1) discover and 2) scale-up inorganic oxides. We find that the tighter control of reaction conditions, coupled with the ability to systematically vary gel composition, enables a broader exploration and results in an increase in the fundamental understanding of the space being studied. The suggestion that combinatorial methods are a degeneration of the scientific process to a "monkey approach" is inconsistent with our experience. In fact, we find that combinatorial chemistry presents a greater challenge in experimental design and can be used equally well for the gathering of fundamental information as for the discovery of new materials. Furthermore, the fully computer controlled system with online monitoring of every step in the process ensures quality control and reproducibility. Unfortunately, it is difficult to distinguish between truth and fiction at such an early stage in the implementation of combinatorial tools to heterogeneous catalyst processes. In the next few years, we will learn the value and limitations of the combinatorial tool through exposure and use of this new methodology. Our experience to date, however, does suggest that the possibilities for the application of combinatorial tools in the chemical industry are exciting. We look forward to the challenges and opportunities that this will present. REFERENCES

1. W. Rothwell, C. Shearer and G. Taylor, Chemtech, 1995, 25 (6), 6. 2. D. E. Akporiaye, I. M. Dahl, A. Karlsson and R. Wendelbo, Angew. Chem., Int. Ed., 1998, 37 (5), 609. 3. K. Choi, D. Gardner, N. Hilbrandt and T. Bein, Angew. Chem., Int. Ed., 1999, 38 (19), 2891. 4. J. Klein, C. W. Lehmann, H-W. Schmidt and W. F. Maier, Angew. Chem., Int. Ed., 1998, 37 (24), 3369. 5. E. Danielson, M. Devenney, D. Giaquinta, J. Golden, R. Haushalter, E. McFarland, D. Poojary, C. Reaves, W. Weinberg and D. Xu, Science, 279 (6), 837, 1998. 6. G. J. Lewis, D. E. Akporiaye, D. S. Bem, C. Bratu, I. M. Dahl, A. Karlsson, R. C. Murray, R. L. Patton, M. Plassen and R. Wendelbo, 13th IZC, July, 2001, in press. 7. R. Broach and G. Lewis, unpublished results, 1992. The structure has been published by Whittingham; Zavalij P. Y., Zhang F., Whittingham M. S.; Acta Crystallog., C53, 1738- 1739, 1997. 8. M. Lafontaine, A. Le Bail and G. Ferey, 3". Solid State Chem., 85, 220-227, 1990. 9. R. Broach and G. Lewis, unpublished results, 1993. The structure was solved from single crystal data. 10. A. Wells, Structural Inorganic Chemistry, FitCh Ed., Oxford University Press, New York, 1986, p. 650. 11. D. Akporiaye, Microporous and Mesoporous Materials, ZMPC 2000, Sendai, Japan, August 2000, in print. 12. D. Bem, J. Sherman, A. Napolitano, A. Leon-Escamilla, G. Lewis and R. Bedard, US Patent 5,888,472, 1997. 13. D. Bem, R. Bedard, R. Broach, A. Leon-Escamilla, J. Guisselquist and J. Pluth, Mater. Res. Soc. Symp. Proc., 1999, 549 (Advanced Catalytic Materials- 1998), 73-78. 14. J. Sherman, D. Bern, G. Lewis, US Patent 6,099,737, 2000.

Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.

123

The Local Structures of Transition Metal Oxides Incorporated in Zeolites and their Unique Photocatalytic Properties Masakazu Anpo* and Shinya Higashimoto Dept. of Applied Chemistry, Graduate School of Engineering,Osaka Prefecture University Gakuen-cho, Sakai, Osaka 599-8531, Japan. e-mail: [email protected] Zeolite catalysts incorporated or encapsulated with transition metal cations such as Mo 6§ V 5+, or Ti 4§ into the frameworks or cavities of various microporous and mesoporous molecular sieves were synthesized by a hydrothermal synthesis method. A combination of various spectroscopic techniques and analyses of the photocatalytic reaction products has revealed that these transition metal cations constitute highly dispersed tetrahedrally coordinated oxide species which enable the zeolite catalysts to act as efficient and effective photocatalysts for the various reactions such as the decomposition of NOx into N2 and 02 and the reduction of CO2 with H20 into CH3OH and C H 4 . Investigations on the photochemical reactivities of these oxide species with reactant molecules such as NO• hydrocarbonds, CO2 and H20 showed that the charge transfer excited triplet state of the oxides, i.e., (Mo 5+ -O-)*, (V 4+- O')*, and (Ti 3+ - O-)*, plays a significant role in the photocatalytic reactions. Thus, the present results have clearly demonstrated the unique and high photocatalytic reactivities of various microporous and mesoporous zeolitic materials incorporated with Mo, V, or Ti oxide species as well as the close relationship between the local structures of these transition metal oxide species and their photocatalytic reactivities. 1. INTRODUCTION It is hopefully expected that mankind will strive for the recovery and preservation of a better greener environment with the establishment of environmentally-friendly, clean, safe, and sustainable technologies for the 21 st Century. However, up until now, environmental pollution and destruction on a global scale as well as the lack of sufficient clean energy supplies have drawn much attention and concern to the vital need for ecologically clean chemical technology, materials, and chemical processes, the most important challenge facing chemical scientists today. Although we are moving in a positive direction in the development of such clean and safe chemical systems using photofunctional materials such as titanium oxide photocatalysts, we have yet to gain a complete understanding of the reaction mechanisms for the design of highly efficient and selective photo-induced reaction systems. In recent years, increasing attention has been focused on studies concerning the production of new zeolite materials such as microporous and mesoporous molecular sieves due to their very unique and interesting physicochemical properties such as a pore structure of a molecular scale, the capacity for ion-exchange, a strong surface acidity and a unique

124 with transition metal oxide species, such as M o, V, or Ti-oxides, are of special interest due to their high and unique catalytic and photocatalytic properties [1,2]. Thus, it is very important to obtain detailed information on the effect of the zeolite framework structure on the chemical function of these metal oxide species as well as on the relationship between the local structures of these oxide species and their photocatalytic reactivities. The present study deals with the characterization of the active sites of various hydrothermally synthesized zeolite materials which include the Mo, V, or Ti-oxide species within their frameworks and cavities, and their photocatalytic reactivities including the detection of the intermediate species. Variousmolecular spectroscopic methods such as insitu photoluminescence, ESR, XAFS (XANES and FT-EXAFS), were employed along with analyses of the reaction products to clarify the reaction mechanisms at the molecular level. 2. EXPERIMENTAL The M o-MCM-41 mesoporous molecular sieves (0.5, 1.0, 2.0, 4.0 M o wt%) were synthesized using tetraethylorthosilicate (TEOS) and (NH4)6Mo7024"4H20 as the starting materials and cetyl trimethylammonium bromide (CTMABr) as the template, in accordance with previous literature [3]. Vanadium silicalites (VS-1 and VS-2; 0.2 wt% as V) were prepared by hydrothermal synthesis using tetraethylorthosilicate (TEOS), VOSO4 and VCI3 as the starting materials, and tetrapropylammonium hydroxide (TPAOH), and tetrabutylammonium hydroxide (TBAOH) as a structure directing agent, respectively, under conditions reported in previous literature [4,5]. The V-HMS mesoporous molecular sieve (0.2 wt% as V) was synthesized using tetraethylorthosilicate (TEOS) and VOSO4 and dodecylamine (DDA) as the structure directing agent under conditions reported in previous literature [3]. The V/SiO2 catalyst (0.2 wt% as V) was prepared by an impregnation method of SiO2 with an aqueous solution of NH4VO3. After the products were recovered by filtration, washed with distilled water several times and dried at 373 K for 12 h, calcination of the samples were carried out under a dry flow of air at 773 K for 8 h. TS-1 and TS-2 (Si/Ti -- 85), Ti-MCM-41 (Si/Ti - 100) and Ti-MCM-48 (Sifri -- 80) were hydrothermally synthesized according to procedures previously reported [6,7].-. Ti/FSM-16 and Ti/Vycor glass were prepared by a chemical vapor deposition method (CVD) of the Tioxides onto FSM-16 or Vycor glass, respectively, through a facile reaction of TiCh with the surface OH groups of these supports in the gas phase at 453-473 K, followed by treatment with water vapor to replace the chlorine atoms with the OH groups [8,9]. A TiO2 powdered catalyst, JRC-TIO-4 (anatase 92 %, rutile 8 %), supplied by the Catalysis Society of Japan, was used. Prior to spectroscopic measurements and photocatalytic reactions, the catalysts were degassed at 773 K for 2 h and calcined in 02 (> 20 Torr) at 773 K for 2 h, then degassed at 473 K for 2 h. The photoluminescence and lifetimes were measured at 77 K with a Shimadzu RF-501 spectrofluorophotometer and an apparatus for lifetime measurements, respectively. The ESR spectra were recorded with a JEOL-2X spectrometer (X band) at 77 K. XAFS (XANES and EXAFS) spectra were obtained at the BL-10B facility of the High Energy Acceleration Research Organization (KEK) in Tsukuba. The XAFS spectra of the

125 dehydrated samples were recorded at the M o K-edge, Ti, and V K-edge absorption in the transmittance and fluorescence mode at 293 K, respectively. The EXAFS data were examined by an analysis program by Rigaku EXAFS (REX). The photocatalytic reactions of NO in the absence and presence of the CO molecules were carried out at 298 K with a high pressure mercury lamp through an UV cut filter (/l > 270 nm). The products were analyzed by online gaschromatography. 3. RESULTS AND DISCUSSION

3.1. Molybdenum Oxide Catalysts Results of the XRD patterns and the BET surface area of the Mo-MCM-41 catalysts indicated that they have a hexagonal lattice having mesopores larger than 2 0 A and that they possess a high BET surface area (-- 1000 m2/g) as compared with amorphous silica (300 m2/g), so that they can be considered effective photocatalysts [3]. From analyses of the XAFS (XANES and EXAFS) spectra, it was found that M oM CM-41 in the lower loadings of the M o-oxides (1.0 M o wt%) include highly dispersed tetrahedrally coordinated M o-oxide species, having two shorter M o-O bonds and two longer ones, while the M o-MCM-41 in higher loading amounts of Mo-oxides (4.0 M o wt%), tetrahedrally coordinated M o-oxides (M oO42")n with an additional M o-O-M o bond could be observed [ 10]. M o-M CM-41 (1.0 M o wt%) exhibits a photoluminescence spectrum at around 400-600 nm upon excitation at around 295 nm (defined as X), which coincides with the photoluminescence spectrum of the tetrahedrally coordinated M o-oxides highly dispersed on SiO2, as shown in Fig, 1 [11]. The excitation and emission spectra are attributed to the following charge transfer processes on the M o-O moieties of the tetrahedral molybdate ions (MOO42), involving an electron transfer from the 0 2- to M o 6+ ions and a reverse radiative decay from the charge transfer excited triplet state [2,11 ]. hv

[ M 0 6+-

hv' [ M o s+ - O" ]

O 2" ]

absorption

W [ M 0 6+ photoluminescence

-- 0 2- ]

The width and the wavelength at the maximum intensity of the emission band do not change upon varyingthe excitation wavelength, indicating that there is only one emitting site with a photoluminescence lifetime of 2.25 ms at 77 K. These results indicate that the M ooxides showing absorption in the region of 295 nm form a tetrahedral coordination in a highly dispersed state. On the other hand, as shown in Fig, 2, there are at least two luminescent species (the absorption spectrum can be deconvoluted into two components having wavelength regions of X and Y in Fig. 3 at 295 and 310 ran, respectively) on Mo-MCM-41 (4.0 Mo wt%) [12]. The increase in M o content, from 1.0 to 4.0 M o wt%, leads to the formation of not only the emitted X site with a photoluminescence lifetime of 2.25 ms but also another emitting site (in the region of Y) probably induced by M o-M o interactions via the oxygen ions (M o-O-M o), which cause a more efficient radiationless energy leading to a decrease in the

126 photoluminescence lifetime (0.91 ms). Taking into account the XAFS data, only the isolated tetrahedrally coordinated M o-oxides are formed in lower M o loadings, while two types of tetrahedrally coordinated M o-oxides at highly dispersed levels and (M 0042-) n are formed in higher Mo loadings, as shown in Fig. 3.

A a't

(a) )

(A)

5

(el

.z,

(e)

J 9b(Y)

(/) E:

.

(b)

._c m

(x

.>

~ff.

)

Ar I, 200

.~~

300

400

500

Wavelength / nm

Fig. 1. Effect of the addition of NO on the photoluminescence spectrum and the excitation spectrum of Mo-MCM-41 with loading amount of 1.0 Mo wt%. Pressure of added NO : (A, a) 0; (b) 0.07; (C, c) 0.4 Torr; (d) excess; (e) degassed after (d).

(a)

Sl

H

\Z ";" \o

2,1,.,. 300

400

600

Fig. 2. Effect of the addition of NO on the photoluminescence spectrum and the excitation spectrum of Mo-MCM-41 with a Si/Mo ratio of 40. Pressure of added NO : (A, a) 0; (b) 0.6; (C, c) 4 Torr; (d) excess; (e) degassed after (d). Spectrum (A) can be deconvoluted into (X) and (Y).

O

.O

Q

1.74A~kk / 3.1~9A~ // /

500

Wavelength / nm

(b)

,.r~A

~, .//Mo

200

600

(c)

(c)

o

/H

d9o/

Fig. 3. Proposed local structures of the isolated (a) as well as oligomeric Mo-oxide sites (b) in the Mo-MCM-41 catalyst.

3.1.1. Photocatalytic Decomposition Reaction of NO by the Coexistence of Additive Gasses on the Mo-MCM-41 Catalysts and their Photocatalytic Reactivity The photocatalytic decomposition reactions of NO in the absence and presence of various kind of additive gases such as CO, propane, ethane, methane, and propylene were performed on M o-MCM-41 under UV-irradiation (X > 270 nm). No products could be detected under dark conditions nor did the silicious M CM-41 or bulk M 003 exhibit any photocatalytic reactivities. However, UV-irradiation of Mo-MCM-41 in the presence of NO led to the evolution of N2 as well as N20 and NO2. It was found that the efficiency of

127 the photocatalytic decomposition reactions of NO strongly depended on the kind of additives used. The order of the reactivity for the photocatalytic decomposition reactions is as follows: CO > propane > ethane > propylene -- methane. In line with these results, further investigations showed that the photocatalytic decomposition reactions of NO exhibited high efficiency by the coexistence of propane and CO. The photocatalytic decomposition of NO into N2 and CO2 on M o-M CM-41 was found to proceed effectively and efficiently by the coexistence of CO. As shown in Fig, 4, UVirradiation (A > 270 nm) of M oMCM-41 in the presence of a

Fig, 4. Reaction time profiles of the decomposition reaction of NO by the CO on M o-M CM-41 (1.0 M o wt%). (A), N2 (11), N20 ( O ) ; conversion

photocatalytic coexistence of Yields of CO2 of NO (C)).

Amount of added NO or CO: 180 /z mol-g-catl

mixture of NO and CO led to the formation of N2 and CO2 with a good linearity against the UV-irradiation time as well as a good stoichiometry, while the turnover frequency exceeded unity after irradiation for 2h. These results clearly indicate that the reaction proceeds photocatalytically. Also, atter UV-irradiation for 3 h, NO conversion and selectivity for the formation of N2 reached close to 100 %, leading to the formation of small amounts of N20 during this reaction in the gas phase [ 13,14]. UV-irradiation of Mo-MCM-41 in the presence of CO alone and its subsequent evacuation at 293 K led to an efficient quenching of the photoluminescence, which suggests ..

that the charge transfer excited triplet state of the [M 05+ - O-]* complex reacts with CO, leading to the formation of M o4+ ions as well as CO2, which exhibits no ESR signals due to the M 05+ ions [ 13-16]. Exposure of the NO molecules into the photo-formed M o4+ ions led to the formation of N20 under dark conditions. In fact, after subsequent evacuation, the photoluminescence intensity recovered, but not to its original photoluminescence intensity due to the formation of carbonyl species such as [M 04+ - CO] which decompose only upon heating at temperatures above 373 K [ 17]. In fact, the exposure of NO and N20 onto M o4+ ions under dark conditions led to the formation of N20 and N2, respectively. From these results, the photocatalytic decomposition reaction mechanism of NO by the coexistence of the CO reaction can be proposed, as shown in Scheme 1. After the subsequent evacuation of the catalyst, the photoluminescence intensity recovered accompanied by the oxidation of Mo 4+ to Mo 6+ ions. In-situ photoluminescence and ESR measurements demonstrated that this reaction proceeds in a redox cycle between alternating M 06+ and M o4+ ions, i.e., it was

128 found that the photo-formed M o4+ ions, through a reaction of the charge transfer excited triplet state with CO, are oxidized to the original M 06+ ions in the presence of NO or N20, leading to the formation of N2. (MOs+- O')*

hl ~I/ h V

cited triplet state of t h e ~ S xtetrahedral!y coordinated Mtor_oxides )

(M06+= OZ-) ff etrahedrallycoordinated Mo-oxides)

~~----

N2 [ t - - ' t

ated

CO

~,., L,u ~ C O 2

(M04+)

CO2

(M~4+) NO

~ ~ . .

(M06+," ~ ' x

NO

Scheme 1. Catalytic cycles for the photocatalytic decomposition of NO in the coexistence of CO.

3.1.2. Relationship between the Local Structures of Mo-oxides and their Photocatalytic Reactivities for the Decomposition of NO by the Coexistence of CO Photoluminescence and XAFS investigations of M oMCM-41 were performed and the results revealed that the absorption in the X and Y regions are attributed to tetrahedrally coordinated Mooxides at a highly dispersed level and (M 0042-) n, respectively. Figure 5 shows the parallel relationship between the yields of N2 formation for the decomposition of NO on MoMCM-41 (0.5-4.0 M o wt%) by the coexistence of CO and the relative intensity of the absorption spectra observed in the total region (X and Y) of the catalyst. The intensities of the

Fig, 5. Relationships between the yields of N2 formation for the photocatalytic decomposition reactions of NO by the coexistence of CO, and the relative intensity of the absorption in the total region of (X and Y) of M o-M CM-41 (0.5, 1.0, 2.0, and 4.0 M o wt%). Added NO or CO: 180 tt mol-e-cat. -I

129 absorption spectra of two types of tetrahedral M o-oxides in the total region of X and Y were found to have a good relationship with the yields of N2 for the photocatalytic decomposition of NO in the presence of CO [13]. These results indicate that in the presence of CO, two types of tetrahedral M o-oxides at a highly dispersed level as well as (M 0042) n work as the active sites. 3.2. Titanium Oxide Catalysts

The development of efficient photocatalytic systems which are able to decompose NO directly into N2 and O2 or to reduce CO2 with H20 into chemically valuable compounds such as CH3OH or CH4 are among the most described yet and challenging goals in the research of enviromentally-friendly catalysts. From this point of View, much attention has been focused on the useful application ofTi-oxide photocatalysts, mainly as TiO2 semiconductors, TiO2 thin films, and isolated tetrahedrally coordinated Ti-oxides [1,2]. Recently, we have reported that highly dispersed tetrahedrally coordinated Ti-oxides, when compared with bulk TiO2 powder, exhibit high and unique photocatalytic reactivity for the NO decomposition reaction as well as the reduction of CO2 with H20 [1,8,9]. It can be seen that understanding the relationship between the local structure of the Ti-oxides and their photocatalytic reactivity, especially their selectivity among various types of Ti-oxide catalysts is of special importance. In-situ characterizations of Ti-oxides included within various types of zeolites or anchored on support surfaces by means of UV-Vis, ESR, photoluminescence and XAFS (XANES and EXAFS) investigations provided important insights into their local structure and their photocatalytic reactivity for the decomposition of NO into N2 and 02 as well 100 , ~ as the reduction of CO2 with H20 into .~ Ileal,." CH3OH and CH4. It was found that Ti- c 8 0 " o12~ o oxides prepared within zeolites or on ~ oasupport surfaces exhibit quite different and ~ 60 o.~"rl ~ o 2 high photocatalytic reactivity as compared o oa-" ~ /Oa" 0 2to bulk powdered TiO2 and also that the high z 6 - ~ [i reactivity of the charge transfer excited o 4 0 " II 02triplet state of the tetrahedrally coordinated ~iTi-oxides, (Ti 3+ - O-)*, plays a significant _~ 20 role in the unique and high photocatalytic 0~ reactivity of these catalysts. I t I I XAFS (XANES and EXAFS) 03.5 4 4.5 5 5.5 6 6.5 investigations of these Ti-oxide catalysts at Coordination Number the T i K-edge were carried out and the results revealed the Ti-oxides to have a Fig, 6. Relationship between the coordination number of the Ti-oxides and the tetrahedral coordination within the Ti-oxide catalysts, while the Ti-oxides have an selectivity for N2 formation in the octahedral coordination in the case of the photocatalytic decomposition of NO into N2 and 02 on various titanium oxide catalysts. bulk TiO2 photocatalyst. Figure 6 shows

130 the relationship between the coordination number of the Ti-oxides and the selectivity for N 2 formation in the photocatalytic decomposition reaction of NO on various Ti-oxide photocatalysts. The clear dependence of the N2 selectivity on the coordination number of the Ti-oxides can be observed, i. e., the lower the coordination number of Ti-oxides, the higher the N2 selectivity [1]. From these results, it can be proposed that a highly efficient and selective photocatalytic decomposition of NO into N2 and 02 can be achieved using Ticontaining zeolites as a photocatalyst which involves highly dispersed tetrahedrally coordinated T i-oxides as the active species. The reactivity of such a charge transfer excited state was also found to strongly depend on the differences in the molecular environment of the T i-oxides such as the rigidity or flexibility of the zeolite framework and the local structures of the TiO 4 unit, i. e., Ti(OSi)4, Ti(OH)(OSi)3 or Ti(OH)2(OSi)2 [ 1,18,19]. 3.3. Vanadium Zeolite Catalysts Zeolites having V-oxides in their frameworks have been the focus of much attention for their interesting and distinctive physico-chemical properties as well as photocatalytic reactivities. So far, several types of vanadium silicalite catalysts in which vanadium ions are incorporated into the zeolite framework have been developed, however, the true chemical nature and reactivities of these vanadium silicalites are yet little known.. The results of XAFS (XANES and EXAFS), ESR, photoluminescence and FT-IR measurements of such Vsilicalites (VS-1 and VS-2), V-HMS, and V/SiO2 have shown that they include highly

dispersed tetrahedrally coordinated V-oxides having one oxygen in the shorter V-O distance and three oxygen atoms in the longer V-O distance within the zeolitic framework or on the silica surface. These V-oxide catalysts exhibited a phosphorescence spectrum attributed to the radiative decay from the charge transfer excited triplet state [ 1,2,20]. Table 1 shows a comparison of the chemical properties of the VO4 unit of the various types of V-oxide catalysts. The values of the vibrational transition energy between the (0 ---~ Table 1. Comparison of the various physical and chemical parameters of the Voxide species formed within the zeolite frameworks and SiO 2 surface. Photocatalysts

VS-I

VS-2

WSiO 2

V-HMS ,

Coordination

tetrahedral

tetrahedral

1.68

1.66

1.63

1.62

V-O bond length, (A)

1.78

1.77

1.77

1.78

V=O vibrational energy, (cm-1)

960

980

1010

1035

Lifetime of the excited state, (ms)

5.8

6.9

7.6

V=O bond length, (A)

tetrahedral

tetrahedral

,.

O=V-O bond angle, ( 4~)

4~1

___

4~2


Pt 0 + 2H + . This9 indicates that after the calcination P(+ ions are dominant species. ~H chemical shift depends on the concentrations of Pt and the acidic hydroxyl groups and also on the Pt state. The stronger acidity is originated in the following order of Pt 2§ > H § > K §

II-P-08 - Synthesis and characterization of mesopore Y zeolite B.

Ma

a,b, W.F. Sun c, Z.L. Sun b and L.R. Chen a

aLanzhou Institute of Chemical Physics, The Chinese Academy of Sciences, Lanzhou, P. R. China," bFushun Petroleum Institute, Fushun, P R China CFushun Research Institute of Petroleum and Petrochemicals, Fushun, P R China In this presentation, the HY zeolite with a lot of secondary pores (the diameters of the secondary pores are larger than 2 nm), unblocked channels and low acid site density has been prepared by steaming and acid leaching treatment of HY zeolite. The steaming and acid leaching treatment conditions were examined in details, and the optimal treatment conditions were determined. This kind of HY zeolite, so called mesopore HY zeolite, showed higher activity than HY zeolite in hydrocracking larger molecules 9

209

1 l-P-09 - Controlling the pore size of HI~ zeolite by improved chemical vapor deposition of (CH3)aSi-O-Si(CHa)a Y. Chun a*, X. Ye b, Q.H. Xu a and A.-Z. Yan a

Department of Chemistry, Nanjing University, Nanjing 210093, China,"[email protected] bDepartment of French, Nanjing University, Nanjing 210093, China The pore size of large-pore zeolite HB is controlled by an improved chemical vapor deposition (CVD). In this method, ammonia or tripropylamine was used to protect the acidic sites in zeolite before deposition of (CH3)3Si-O-Si(CH3)3, differently from the conventional CVD. The pore volume of zeolite HI3 was reduced and the pore size was narrowed upon this modification. The results from IR spectra and catalytic decomposition of isopropanol demonstrated that the modified samples showed stronger acidity than that prepared from conventional CVD. In the transformation of trimethylbenzenes (TMB), conversion of 1,3,5TMB was suppressed while conversion of 1,2,3-TMB was almost unaffected on the improved CVD samples; the selectivity of 1,2,4-TMB on these samples was increased in the alkylation reaction of m-xylene with methanol.

I I - P - 1 0 - I n f l u e n c e of pH of the solution on r e a l u m i n a t i o n of B E A zeolite Y. Oumi (a), R. Mizuno (a), K. Azuma (a), S. Sumiya (a), S. Nawata (b), T. Fukushima (b), T. Uozumi (a) and T. Sano (b)

a School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, [email protected], Japan. b Tosoh Corporation, Shin-nanyo, Yamaguchi 746-8501, Japan. The influence of pH value in the solution on the realumination process of BEA zeolite was investigated by mean of nitrogen adsorption, XRD, 27A1 MAS NMR and FT-IR. It was found that non-framework aluminum species (octahedrally coordinated aluminums) in the solution are easily reinserted into the framework of dealuminated BEA zeolite by controlling the pH value o( the solution below 7. The cumene cracking activity of the realuminated BEA zeolite at pH 5.1 was comparable to that of the parent BEA zeolite. The influence of aluminum species in the solution on the realumination process was also investigated using various aluminum compounds.

I I - P - I I - Formation of carbon-intercalated molybdenum sulfides J.-S. Chen,* Y. Wang, Y. Guo, Y. Zou and W. Xu

Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin University. [email protected], Changchun, P R. China Molybdenum sulfide compounds (MoS2-C) with intercalated carbonaceous matter have been obtained by pyrolysis of a surfactant-containing mesolamellar molybdenum sulfide in a nitrogen flow at various temperatures. The samples contain about 22 wt% of carbon, and the interlayer distance for the MoS2-C compounds is about 9.8 A. The solid obtained by treatment at 973 K exhibits considerable N2 adsorption capacity. The electrical conductivity for the MoS2-C materials is higher than that of the pristine MoS2 at low measurement temperatures, and it strongly depends on the pyrolysis temperature. It is believed that the carbon intercalated between the MoSa sheets plays a role in the conductivity enhancement.

210

1 I - P - 1 2 - Characterization of partly-detemplated GaPO4-LTA S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen*

Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, [email protected], edu. cn, Changchun, P. R. China Gallophosphate GaPO4-LTA crystals were heated under vacuum and in a nitrogen atmosphere, respectively. It has been found that the resulting materials are partly-detemplated and retain the LTA framework structure even in moist atmosphere. The thermally-treated GaPO4-LTA compounds exhibit considerable adsorption capacities for water and nitrogen but the adsorption behavior depends on the pyrolysis conditions. In contrast to the channels of AFI in which the generation of carbon nanotubes has been realized, the a-cages of GaPO4LTA have a space large enough for the formation of fullerene-like materials that might exist in the carbonaceous matter of the partly-detemplated GaPO4-LTA compound.

l l - P - 1 3 - Another study on the microwave heating of zeolite without special loading materials J. Dong (a), L. Xie(a), X. Jing(a), H. Xu (a), F. Wu (b) and J. Hao (c)

a Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi, P.R.China* email: jxdong @ public ty.sx.cn; b Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P.R.China; c Department of Information Engineering, Taiyuan University of Technology, Taiyuan 030024, PR. China The heating and phase-transformation of zeolites caused by microwave irradiation at 2450MHz without special loading materials are examined. It is found that zeolite X was heated to 1473K about 90 seconds at power output of 400W. It is verified that the center of microwave absorption is not water or surface hydroxyl groups, not silica in zeolites, but electron bearing AIO4 tetraedra. The ability of zeolites to absorb microwave energy depends on zeolitic framework structure, exchangeable cations, Si/AI molar ratio, as well as adsorbed compounds in zeolite.

II-P-14 - Microwave plasma treatment as an effective technique for activation of zeolite catalysts I.I. Lishchiner (a), O.V. Malova (a) and E.G. Krasheninnikov (b)

(a) Institute of Organic Chemistry RAS, [email protected] (b) Russian Research Center "Kurchatov Institute" Moscow, Russia An afterglow microwave plasma with stabilized pulse power was applied to the activation of zeolite catalysts for isobutane alkylation with butenes. It was found that the pretreatment of zeolite catalysts in a microwave plasma discharge affected their properties. The catalysts exhibited higher activity, stability in operation, and selectivity (the fraction of trimethylpentanes in the alkylate increased). The properties of catalysts after plasma activation depend on the treatment conditions such as plasma "temperature" and nonequilibrium character and depend only slightly on the initial activity of catalysts, which is primarily controlled by the catalyst preparation conditions.

211

1 I - P - 1 5 - Synthesis and characterization of microporous titanium-silicate materials S. Mintova, B. Stein, J.M. Reder and T. Bein*

Department of Chemistry, University of Munich, Butenandtstr. 11-13 (E), 813 77 Munich, Germany, svetlana, mintova@cup, uni-muenchen, de The synthetic counterparts of the minerals zorite and pharmacosiderite were hydrothermally synthesized in SiQ-TiOz-MzO-(TMA)20-water systems using atypical precursor gel compositions which result in different crystal morphologies. Nanocrystalline pharmacosiderite with individual particles of o-). N-methylation products (NMA+NNDMA) were predominant with a selectivity over 97 mol% at 573 K.

282

25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular sieve AIMCM-41 in the Friedel-Crafts reaction of bulky aromatic compounds H. Hamdan (a), A.B. Kim (b) and M.N. Mohd Muhid (b)

albnu Sina Institute for Fundamental Science, [email protected] bFaculty of Science, Universiti Teknologi Malaysia, UTM 81310, Johor, Malaysia Secondary aluminated MCM-41 (A1MCM-4 l(sec)) with Si/A1 ratio of 1.75 was synthesized. Characterization indicates that secondary alumination incorporates aluminium into the framework without affecting the long range order of the mesopores and structural stability of the framework. Friedel-Crafts alkylation of 2,4-di-t-butylphenol with cinnamyl alcohol catalyzed by the A1MCM-41 (sec) catalyst gave a high conversion. 29Si MAS NMR shows a different distribution of aluminium in the framework of MCM-41 by secondary synthesis as compared to direct synthesis. A1MCM-41 (sec) possesses Lewis and Br6nsted acidity and is a more efficient catalyst for reaction of large compounds.

25-P-13 - Naphthalene alkylation with methanol employing solid catalysts J. Aguilar-P, A. Corma a, J.A. de los Reyes b, L. Norefia, G. Mufioz, J.M. Sanchez, A. Torales and I. Hemdndez.

Area de Qu/mica Aplicada, UAM-A. Av. San pablo 180, CP 02200, Mdxico, D.F. a Instituto de Tecnologia Quimica, UP V-CSIC, Av. de los Naranjos s/n 46022, Val. Spain. b UAM-L Av. Michoacan y la Purisima, CP 09340, Mdxico, D.F. The relation between the structure of the catalyst and the reaction activity and selectivity was studied with MCM-22, MCM-41, HY, Beta and BZR5 catalysts. High selectivity in 13methylnaphthalene (2-MN) was obtained using MCM-41 catalyst. For the MCM-22 catalyst, the presence of 10 member ring (MR) channels and windows present severe constraint for the diffusion of naphthalene into the channels, therefore, the reaction possibly takes place at the external surface of this material. The order of activity is as follows: MCM-22 > Beta > HY > MCM-41 >BZR5.

25-P-14- Aikylation of biphenyl and naphthalene with propene. Is zeolite beta a shape-selective catalyst? D.M. Roberge and W.F. H61derich

Department of Chemical Technology and Heterogeneous Catalysis, R WTH-Aachen, Worringerweg 1, D-52074 Aachen, Germany, [email protected]. An acid treated zeolite beta with a 6 M HNO3 acid solution is a shape-selective catalyst for the alkylation of biphenyl with propene. This is however not the case for the alkylation of naphthalene. The reaction is highly mass transfer limited and the selectivity mechanism is attributed to a product selectivity. The major effect of the acid treatment is to deactivate the external surface area so that the intrinsic micropore properties can come out. Contrary to zeolite mordenite, the acid treatment does not reduce deactivation and the formation of highly aromatic coke remains important at high temperatures.

283

25-P-15- Aikylation of benzene by propane with participation of space divided centres S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov

Institute of Petrochemical Processes, Academy of Sciences of Azerbaijan 30 N.Rafiyev st., Baku-370025, Azerbaijan Republic Fax." (9412) (90-35-20); E-mail. [email protected],[email protected] The benzene alkylation by propane has been investigated using a zeolite-containing catalyst. The isopropylbenzene formation is shown to begin at 180-350~ over HY and Pt, Re/A1203 admixed catalysts. The temperature increase leads to C3H6(250~ and other alkylbenzenes (300~ formation. The by-products may be reduced by the selective poisoning of Br6nsted acidic centres by ammonium. From the considerations on the reaction, the probable mechanism of benzene dehydroalkylation by propane has been proposed.

25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts supported on mesoporous materials M.-W. Kim a, W.-G. Kim a, J.-H. Kim a, Y. Sugi b and G. Seo a

~Department of Chemical Technology & The Research Institute for Catalysis, Chonam National University, Gwang/u 500- 75 7, Korea bDepartment of Chemical, Faculty of Engineering, Gifu University, Gifu 501-1193, Japan The isopropylation of 2-isopropylnaphthalene was studied over heteropoly acid catalyst supported on mesoporous material. The physico-chemical state of loaded heteropoly acid was investigated using XRD, nitrogen adsorption measurement and FT-IR techniques. Heteropoly acid was highly dispersed on the wall of mesoporous material, and retained its Bronsted acidity. The conversion and the selectivity for [3, 13 -diisopropylnaphthalene were very high over the mesoporous material with a large loading amount of heteropoly acid. The treatment of heteropoly acid was helpful for the improvement of the acidity of mesoporous material.

25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta C.R. Patra, S. Kartikeyan and R. Kumar

Catalysis Division, National Chemical Laboratory, Pune 411 008, INDIA raj [email protected] 1.res. i n) The isopropylation of xylenes to form corresponding dimethyl cumene(s) was carried out with isopropanol over large pore high silica zeolite H-beta as catalyst under continuous vapor phase fixed bed down flow glass reactor system at atmospheric pressure and moderate temperatures (413K to 453K). Zeolite H-Beta exhibited quite high activity, selectivity and stability. The effect of reaction temperature, space velocity, substrate to alkylating agent molar ratio and time-on-stream on conversion and selectivity was studied. As high as 90-99 % selectivity for dimethylcumene(s) was obtained in relatively lower reaction temperature range of 413-433 K at quite high xylene conversion (80-90% of theoretical value).

284

08- Syntheses with Non-Ionic surfactants (Wednesday) - The double-step synthesis of MSU-X silica: decoupling the assembly mechanism 08-P-05

E. Prouzet*, C. Boissi&e, N. Hovnanian and A. Larbot. Institut Europden des Membranes, L.M.P.M. (CNRS UMR 5635) Universitd Montpellier II, CC 047, F-34095, Montpellier, cedex 5, FRANCE. e-mail : [email protected] In a new double-step synthesis of MSU-X type silicas, which was reported previously, a first step allows the preparation of a colorless stable and homogeneous aqueous solution where both nonionic surfactants and silica oligomers are mixed. Dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and 29Si NMR analyzes revealed that this first step allows the assembly of surfactants and silica oligomers in specific micellar hybrid objects that are described.

0 8 - P - 0 6 - S t e a m - stable aluminosilicate MSU-S mesostructures assembled

from zeolite seeds

Yu Liu, W. Zhang and T.J. Pinnavaia Department of Chemistry, Michigan State University, [email protected] The hydrothermal stability and acidity of aluminosilicate mesostructures can be improved substantially through the surfactant - directed assembly of protozeolitic aluminosilicate nanoclusters that normally nucleate (seed) the formation of microporous zeolites. Our results indicate that zeolite type Y, Beta, and ZSM-5 seeds are particularly effective at forming steam stable aluminosilicate mesostructures, which we generally denoted as MSU-S.

0 8 - P - 0 7 - A Study on the mesoporous silica structures templated by triblock

copolymers C.-P. Kao(a), H.-P. Lin(b), M.-C. Chao(a), H.-S. Sheu(c) and C.-Y. Mou(a)*

a National Taiwan University, Taipei, [email protected], Taiwan b Institute of Atomic and Molecular Sciences Academia Sinica, Taipei, Taiwan c Synchrotron Radiation Research Center, Hsinchu, Taiwan The well-ordered mesostructures SBA-15 or SBA-16 could fast grow from the chemical composites of triblock copolymers (EOnPOmEOn)-TEOS-HC1-H20. At the desired TEOS/EOz0PO70EO20 ratio, an organic surfactant-silica macrosphere of about 1 cm was successfully obtained, and the organic-inorganic mesostructural macrospheres have the particularly elastic property. Post-hydrothermal treatments at high temperature promoted the increase of the unit cell and pores.

285

08-P-08 - Study of methyl modified M S U - X silicas Y. Gonga, Z. Lia, S. Wanga, D. WUa, Y.-H. Suna, F. Dengb, Q. Luob and Y. Yueb a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences(CAS), Taiyuan China bState Key Laboratory of Magnetic Resonance and Atomic Molecular Physics, Wuhan Institute of Physics and Mathematics, CAS, China Methyl-modified MSU-1 mesostructures were prepared by one-pot strategy. The microstructure and the interfacial characteristic were measured with N2 sorption, IR, 29SiNMR, SEM, TEM, TGA and SAXS. The results showed that methyl groups have been incorporated into MSU-X silica framework and the surface and texture properties of the resultant materials varied with the amount of incorporated methyl groups.

08-P-09 - Study of mesoporous materials with ultra high surface area prepared from alternate surfactants and silicate sources J.F. P4rez-Ar~valo a'b, J.M. Dominguez c, E. Terr6s c, A. Rojas-Hem~indez b and M. Miki d a UNAM,, FES-Cuautitl6n, b UAM-I, c1MP, aCIMAE [email protected] A comparison study on the synthesis of mesoporous materials from Triton X-100/Nametasilicate and CTAB/TEOS was performed and their textural and structural parameters were characterized by XRD, N2 adorption and TEM. The CTAB/TEOS solids presented high surface mesopore areas, exceeding 1100 m2/g, while the Triton X-100/Na-metasilicate presented areas from 1200 up to 1467 m2/g. The analysis of the textural data indicated that upon calcination pore sintering occurs in the Triton/Na-metasilicate solids, while it does not occurs in the CTAB/TEOS system. This is probably due to the different packing effective factor of the surfactant molecules.

08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials from gels containing non-ionic surfactants I. Diaz, F. Mohino, E. Sastre and J. P6rez-Pariente Instituto de Cat6lisis y Petroleoquimica, C.S.1.C., esastre@icp, csic. es, Madrid, Spain A variety of mesoporous silicates containing mercaptopropyl groups have been prepared by direct synthesis from gels containing non-ionic surfactants. By adjusting properly several synthesis parameters, thiol-containing SBA-15 have been obtained from gels containing Pluronic 123, whereas a stable material probably related with SBA-12 has been synthesized from Brij 76. These materials possess large surface areas and pore sizes of 3.2 and 1.8 nm, respectively and have been structural characterized by transmission electron microscopy. The oxidation of the thiol groups with hydrogen peroxide leads to sulfonic acid groups which have been shown to catalyze the esterification of glycerol with oleic acid. Factors affecting the catalytic performance of these materials are discussed.

286

08-P-I1 - Secondary hydrolysis process to synthesize highly ordered mesoporous silica from nonionic surfactant with long hydrophilic chain J. Fan, C. Yu and D. Zhao*

Department of Chemistry, Fudan University, Shanghai 200433, P. R. China dyzhao@)Cudan,edu. cn In this paper, we have demonstrated a simple secondary hydrolysis process to synthesize a highly ordered hexagonal mesoporous silica structure by using nonionic oligomeric surfactant with long hydrophilic chain. This process involves an adsorption step of extra silica source and secondary hydrolysis process and can result in large improvement on the ordering and hydrothermal stability for the mesoporous silica materials.

08-P-12 - Mesostructure design using mixture of nonionic amphiphilic block copolymers 9

a

J.M. K l m , S.-E. Park a and G.D. Stucky b

a Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), P.O. Box 107, Yusong, Taejon 305-600, Korea; separk@pado, krict, re. kr b Department of Chemistry, University of California, Santa Barbara, CA 93106, USA Formation of mesoporous silica materials has been studied using mixtures of amphiphilic diblock copolymers (CnH2,+I(OCH2CH2)xOH, C,EOx, n = 12 - 18 and x = 2 - 100) as the structure directing agents and sodium silicate as the silica source. Results obtained from X-ray diffraction patterns and transmission electron microscopy indicate that silica/polymer mesostructures are transformed from lamella to 2-d hexagonal (P6mm), 3-d hexagonal (P6y'mmc), cubic Pm3m and cubic Im3m, as the size (x) of hydrophilic head group increases. Optimum ratios between the hydrophilic EO groups and hydrophobic tail groups are investigated in order to obtain highly ordered mesoporous silica materials.

08-P-13 - Stability of mesoporous material SBA-15 and its benefit in catalytic performance C. Nie, L. Huang, D. Zhao and Q. Li*

Dep. Chem., Fudan University, Shanghai 200433, P. R. China qzli@)Cudan.edu.cn The stability of mesoporous material SBA-15 and A1-SBA-15 was investigated under steaming treatment (100 % H20) at 800 ~ for different time. A1-SBA-15 catalyst has been prepared via post-synthesis procedure. The results show that the mesostructure of SBA-15 and A1-SBA-15 can be retained at 800 ~ steaming for 8 h, while MCM-41 totally loses its mesostructure under the same condition just for 2 h. Moreover, A1-SBA-15 still has cracking activity of n-hexadecane and Pt/A1-SBA-15 has hydroisomerization activity of n-dodecane to some extent even after steaming treatment at 800 ~ for 8 h. Meanwhile, A1-MCM-41and Pt/A1-MCM-41 catalysts totally lose their activity under the same treatment condition just for 2h.

287

08-P-14 - Comparative study of the wall properties in highlyordered silicate and aluminosilicate mesostructured materials of the MCM-41 and SBA-15 types L.A. Solovyov (a), V.B. Fenelonov (b), A.Y. Derevyankin (b), A.N. Shmakov (b), E. Haddad (c), A. Gedeon (c), S.D. Kirik (a) and V.N. Romannikov (b). a Institute of Chemistry and Chemical Engineering, [email protected], infotel.ru. b Boreskov Institute of Catalysis: [email protected] c Universit6 P. et M. Curie [email protected]. X-ray diffraction structural modeling based on a continuous electron density representation and textural analyses by the combined XRD-adsorption method were applied for to quantify distinctions in the wall structure of the MCM-41 and SBA-15 types of mesostructured materials.

288

09-Crystal Structure Determination (Wednesday) 09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated fully Cd(II)-exchanged zeolite X E.Y. Choi a, S.H. Lee a, Y.W. Han b, Y. Kim a and K. Seff c

aDepartment of Chemistry, Pusan National University, Pusan, Korea, [email protected] bDepartment of Science Education, Pusan National University of Education, Pusan, Korea CDepartment of Chemistry, Universityof Hawaii, 2545 The Mall, Honolulu, Hawaii 96822, U. S. A. A single crystal of fully dehydrated Cd2+-exchanged zeolite X, Cd46SiI00A1920384, was exposed at o

320 C to 0.005 Torr of Cd vapor for 9 d. The resultant crystal, Cd68SiI00A1920384 (a = 24.953(6) A), was studied by single-crystal XRD techniques in the cubic space group Fd-3 m at 21(1) ~ In this structure, Cd species are found at seven sites. Twenty-eight Cd 2+ are found at sites I', II', and II with occupancies of eight, six, and fourteen. Thirty-six Cd + are found at sites I, I', and II with occupancies of six, eighteen, and twelve. The eight Cd 2+ at I' associate with four Cd ~ atoms (II') to form four bent Cd2+-Cd~ 2+ clusters per unit cell in the sodalite cavities.

09-P-07 - The structure of a copper molybdate and its relation to other natural and synthetic porous materials based on transition metal polyhedra L.A. Palacio (a), A. Echavarria (a), A. Simon (b) and C. Saldarriaga (a)*

(a)Department of Chemical Engineering, University of Antioquia A.A. 1226, Medellin, Colombia ([email protected]) (b)Laboratoire de Materiaux Mineraux, UPRES-A-7016, C.N.R.S., 3 rue Alfred Werner 68093 Mulhouse Cedex, France A new non-stoichiometric copper molybdate of ideal composition (NH4OH)3/2(CuMoO4)2 was synthesized hydro thermally and its crystal structure was solved from powder data. The material shows the hexagonal parameters a=6.0775(3) and c=21.601(1) A in the space group R-3m. The green powder exhibits the same building units observed in the mineral Volborthite and the layered structure of other materials based on transition metal polyhedra.

0 9 - P - 0 8 - A 3-D Open-framework nickel aluminophosphate [NiAIP2Os][C2N2H9]" assembly of I-D AIP2Os a" chains through [NiOsN] octahedra B. Wei a, J. Yu a, G. Zhu a, F. Gao a, Y. Li a, R. Wang a, B. Gao a, Xian. Xua,S. Qiu a* and O. Terasaki b

aKey Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023, P. R. China,e-mail." [email protected]; bCREST; Department of Physics, Tohoku University, Sendai 980-8578, Japan A 3-D Open-framework [NiA1P208][C2NzH9] (NiAPO-1) was synthesized successfully in a solvothermal system. Its structure was solved by CCD single crystal X-ray diffractometer, with Monoclinic, space group P21/c (No. 14), a=8.542(2) A, b=15.564(3) A, c=7.627(1) A, and [3=110.60(1) ~ V=949.1(3)A 3, Z=4, assemblied by 1-D A1P2083- and 1-D [Ni-O-Ni] chains. It was characterized by powder X-ray diffraction, thermogravimetric/differential thermal analysis, ICP, element analysis, 27A1, 31p MAS NMR and magnetic measurement.

289

09-P-09- Structural modifications induced by high pressure in scolecite and heulandite: in-situ synchrotron X-ray powder diffraction study G. Vezzalini a, S. Quartieri b, A. Sani c and D. Levy d

~Dipartimento di Scienze della Terra, Universitg~ di Modena, Italy, giovanna@unimo, it bDipartimento di Scienze della Terra, Universit~t di Messina, Italy ~INFMand European Synchrotron Radiation Facility, Grenoble Cedex, France dDipartimento di Scienze Mineralogiche e Petrologiche, Universitdt di Torino, Italy We present an in-situ synchrotron X-ray powder diffraction study on the compressibility and the pressure-induced structural modifications in scolecite and heulandite. The cell parameter refinements were carried out up to 7.5 GPa and 6 GPa for scolecite and heulandite, respectively. The HP-induced deformations of both zeolites can be interpreted on the basis of the mechanisms observed during the dehydration processes of the two minerals. Heulandite amorphization process is reversible and occurs at a lower pressure.

09-P-10- Preparation, characterization, and crystal structures of fully indium-exchanged zeolite X N.H. Heo, a S.W. Jung, a S.W. Park, a J.S. Noh, a W.T. Lim, b M. Park a and K. Seff c

aDqpartment of Industrial _Chemistry, Kyungpook National University, Taegu 702-701, t~htieo~kvungpook, ac. kr, Korea ~ Accelerator Laboratory Pohang Institute of Industrial Science & Technology, P. O. Box 12S. Pohang 790-600, wtlimJ'~g)ostec~h.ac.kr, K6rea CDepartment of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822-2275, [email protected], U. S. A. o

In-X has been prepared by solvent-free redox ion-exchange of T1-X with In metal at 350 C. EPXMA showed the product to be an indium aluminosilicate (ca. 47 wt% In) free of T1. Single crystal X-ray diffraction and XPS experiments showed that In-X contained indiums in various oxidation states. In+ and In2+ ions are found at a variety of 3-fold axis and supercage sites, and In5n+ clusters are seen at the centers of some sodalite cavities. Exposure to the atmosphere, washing with H20, and redehydration caused only a small change in + 7+ composition, from (In+)v8(In57+)2-X to (In)74 5(In5 )2 5-X, with a change of space group from Fd3 to Fd3m.

09-P-11 - Structural investigation by powder X-ray diffraction and solid state nuclear magnetic resonance of AIPO4-SOD M. Roux a, C. Marichal a, J.L. Paillaud a, L. Vidal a, C. Femandez b, C. Baerlocher c and J.M. Chezeau a

a Laboratoire de Matdriaux Min6raux, ENSCMu,, [email protected], France. b Laboratoire de Catalyse et Spectrochimie, ISMRA, 14050 Caen, France. c Laboratoriumfiir Kristallographie, ETH, CH-8092 Z~rich, Switzerland The crystalline structure of A1PO4-SOD, an aluminophosphate, was investigated by high resolution powder X-ray diffraction and various solid state nuclear magnetic resonance (NMR) techniques. In particular, 31p homonuclear correlation and 27A1/31P 3QHETCOR NMR experiments allowed the complete assignment of 3~p and 27A1 resonances to the corresponding crystallographic sites. All results from the different NMR techniques are compared with the refined structure resulting from a Rietveld analysis on powder synchrotron data.

290

09-P-12 - Layered germanates with 9-membered rings X. Zou, T. Conradsson and M.S. Dadachov

Structural Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden Two germanates, (NH4)4[(GeO2)3(GeOI.sF3)2]'0.67H20 and (C2N2HI0)2[(GeO2)3(BO2.5)2], were prepared by hydrothermal synthesis. The framework layers are formed by 3- and 9membered rings in both compounds and the structure topology within the layers is very similar. The 3-membered rings in both compounds are built by three GeO4 tetrahedra. These 3-rings are connected by pairs of GeO3F3 octahedra in (NH4)4[(GeO2)3(GeO1.sF3)2]'0.67H20 and by pairs of BOa tetrahedra in (C2N2Hlo)2[(GeO2)3(BO2.5)2] in such a way that 9-membered rings are formed. The framework layers are interrupted by ammonium cations and water molecules in the former compound and protonated ethylenediamine in the latter compound. The 2D frameworks of the germanate and the borogermanate are compared with other related structures.

0 9 - P - 1 3 - Dehydration dynamics of mordenite by in-situ time resolved

synchrotron powder diffraction study: a comparison with electrostatic site energy calculations. A. Martucci, M. Sacerdoti and G. Cruciani

Dipartimento di Scienze della Terra, Sezione di Mineralogia, Universith di Ferrara, Corso Ercole I d'Este, 32, 1-44100 Ferrara, Italy; e-mail: [email protected] The structural transformation of a natural mordenite by in-situ heating to 830~ was studied, using Rietveld structure analysis. At 830~ mordenite maintains the space group Cmcm and behaves as a non-collapsible framework, featuring only a slight cell volume contraction (-1.9%) related to the water release. The removal of water molecules was accompanied by a migration of the cation sites near the framework oxygens. The extra-framework cation positions in dehydrated mordenite were also simulated by electrostatic energy calculations.

09-P-14 - Study of water vapor adsorption in the organically-lined channels of AIMepO-[3 using X-ray powder diffraction K. Maeda (a,b), L.B. McCusker (a) and C. Baerlocher (a)

Laboratory of Crystallography, ETH-Zurich, Zurich, Switzerland bNational Institute of Advanced Industrial Science and Technology (National Institute of Materials and Chemical Research), Tsukuba, [email protected], Japan The structural changes in the framework of the aluminomethylphosphonate A1MepO-13 upon water vapor sorption and the location of the sorbed water molecules have been investigated using X-ray powder diffraction techniques. Only small differences between the framework structures of the degassed and the water-sorbed sample were found. However, the latter did contain additional water positions in the channels. The differences between the water sorption behavior of the two polymorphs of A1MepO (-cz and-13) are discussed.

291

20 - Zeolite Membranes and Films (Wednesday) 2 0 - p - 0 6 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type zeolite membranes as reactors X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu

Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, 158 Zhongshan Road, Dalian 116012, [email protected], China. Factors on dehydrogenation of ethylbenzene to styrene in ZSM-5 type zeolite membrane reactors were studied. About 18% conversion of ethylbenzene increase in the Fe-ZSM-5 membrane reactor can be obtained over the fixed-bed reactor. This result is better than that obtained in the other membrane reactors. The bigger is the permeability and permselectivity of ZSM-5 membranes, the higher is the conversion of ethylbenzene. The order of membrane stability for ethylbenzene dehydrogenation is silicalite-1 > Fe-ZSM-5 > Fe/ZSM-5 > ZSM-5.

2 0 - P - 0 7 - Preparation of high-permeance ZSM-5 tubular membranes by varying-temperature synthesis Y.-S Li, Xio. Zhang, J.-G. Wang and S. Guo

Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, Dalian, 116012, China, [email protected] In this work, high-permeances ZSM-5 zeolite membranes were synthesized on porous a-alumina tubes by a varying-temperature in-situ hydrothermal treatment using n-butylamine(NBA) as a template. The membranes were characterized by XRD, SEM and single-gas permeation measurements. The highest H2 permeance is up to 2.3x 106mol/m2.s.Pa, the highest ideal selectivities are 201 for H2/n-C4Hl0, 13 for n-C4Hlo/i-C4Hlo, at 293 K. Few non-zeolite pores formed in the membrane when the sol was renewed during the varying-temperature process, so that the membrane had high ideal selectivity of n-C4Hlo/i-C4Hlo above 473 K. The separation properties of the membranes were largely determined by synthesis procedure.

20-P-08 - Synthesis of FAU type films on steel supports using a seeding method Z. Wang, J. Hedlund and J. Sterte

Division of Chemical Technology, Lulegt University of Technology, [email protected], Sweden FAU type films were synthesized on polished steel supports using a seeding method. The feasibility of the method was demonstrated for a wide variety of steel types. After 12 h of synthesis the film was continuous with a thickness of about 2 gm. A prolonged synthesis time in one single step resulted in significant attachment of sediments on the film surface for some preparations. Several identical 12 h synthesis steps were therefore used to increase the thickness of the films by approximately 2 ~tm with each additional synthesis step. Morphology and film thickness was independent of steel type. All films were continuous and crack free prior to calcination.

292

20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials O. Ohrman, U. Nordgren, J. Hedlund, D. Creaser and J. Sterte

Luledt University of Technology, Sweden. Email."[email protected] Homogeneous coatings of zeolite ZSM-5 were prepared by the seed film method on porous ceramic foams and on alumina spheres. The zeolite was predominately present in the form of a film on the support surface rather than as aggregated crystals on the surface. The results from gas adsorption and SEM analysis indicated that the entire surface of the foams was successfully covered with a 450 nm film. A 500 nm film was formed on the external surface and also in pores close to the external surface of the spheres. Zeolite was not formed on the internal surface of the alumina spheres. Aluminum leaching from the foams was observed but did not seem to have any detrimental effects on the substrates.

20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in zeolite A membranes M. Lassinantti, J. Hedlund and J. Sterte

Division of Chemical Technology, Lule~t University of Technology, [email protected], Sweden Na-A films were synthesized on porous substrates using a seeding technique. Effects of synthesis temperature, synthesis duration and gel composition on the morphology of the films were evaluated. Higher synthesis temperature resulted in relatively more growth of zeolite into the porous support compared to the film growth on top of the support. By using a multistep synthesis procedure at low temperature, thicker films with less growth into the support could be prepared.

20-P-II Pure-silica zeolite Iow-k dielectric thin films by spin-on process Zhengbao Wang, H. Wang, A. Mitra, L. Huang and Y. Yan*

Department of Chemical and Environmental Engineering, University of California, Riverside, CA 92521, USA; yushan,[email protected]. Spin-on silicalite thin films were prepared from silicalite nanocrystals. Spin-on silicalite films with high porosity have a dielectric constant (k) of 1.8-2.2. A secondary growth of nanocrystals was carried out on spin-on films under microwave treatment. It was found that a secondary growth of nanocrystals by microwave treatment could increase the mechanical strength and control the inter-particle pore size and porosity of spin-on silicalite films. Microwave-treated spin-on films have a k value of 2.2-2.4. The effect of moisture on k value was also studied. The silylation of silicalite films with chlorotrimethylsilane was conducted to eliminate the effect of moisture on the dielectric constant. It was revealed that stable k values were obtained after silylation.

293

20-P-12 - Preparation of silicalite-I and beta zeolite/ceramic composite membranes and removal of trace phenol and benzene from water through them Xiansen Li and S. Xiang* Department of Chemistry, Nankai University, Tianjin, [email protected], P. R. China The in-situ syntheses of silicalite-1 and beta zeolite membranes on the ceramic filter substrates were performed. The physico-chemical properties of the zeolite composite membranes were characterized by XRD, SEM and UV. The removal of phenol and benzene from water through the zeolite composite membranes was studied. It was found that silicalite1 and beta membranes possessed good separation ability for PhOH/H20 and C6H6/H20 and that beta membrane was better than that of silicalite-1 for PhOH/HzO. The average rejection rates of beta and silicalite-1 membranes for PhOH/H20 were 69.9% and 51.5% respectively. The separation capacity of silicalite-1 zeolite membrane for PhOH/H20 and C6H6/H20 increased after twice synthesis and steam treatment

20-P-13 - Factors affecting film thickness in the preparation of supported ZSM-5 zeolite E.I. Basaldella, A. Kikot, J.F. Bengoa and J.C. Tara Centro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad Nacional de La Plata, CONICET, CIC, 47 N~ (1900) La Plata, Argentina. The growth of hydrogel based ZSM-5 zeolite films on cordierite monoliths was studied varying some specific synthesis parameters. More diluted gels decrease the simultaneous production of loose crystals without altering the characteristics of the film formed, while a temperature decrease leads to similarly thick films, though made up of smaller crystals. As films of about the size of a crystal were obtained by increasing acid addition, it would be possible to control film thickness by changing the acidity of the medium. Besides, stirring proved to be essential to obtain uniform coating.

20-P-14 - Growing zeolite films onto gold surfaces E.I. Basaldella a, A. Kikota, J.O. Zerbino b and J.C. Taraa aCentro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad Nacional de La Plata, CONICET, CIC, 47 N~ (1900)La Plata-Argentina. blnstituto de Investigaciones Fisicoquimicas Te6ricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CIC, C. C. 16, Suc. 4, (1900) La Plata- Argentina Silicalite layers were hydrothermally synthesized on gold surfaces by the in-situ crystallization method, using hydrazine and oxigenated water as additives. In this way, it is possible to alter the gold-zeolite electrostatic interaction by changing the electric charge of the metal surface. The effects on the layer growth process related with this change are discussed. Besides, it is proved that metal roughness improves the zeolite layer adherence.

294

20-P-15 - Diffusivities of zeolite coatings M. Tather, ~;.B. Tantekin-Ersolmaz and A. Erdem-$enatalar

Department of Chemical Engineering, Istanbul Technical University, Maslak, 80626 Istanbul, (aerdem@itu. edu. tr), Turkey A method was proposed for the determination of the diffusivities of zeolite coatings. The simulation of the operation of a thermogravimetric analyzer by modeling studies together with experimental TGA measurements allows the estimation of the diffusion coefficient whenever relatively thick zeolite coatings, for which mass transfer resistances exist, are available. The diffusion coefficient of the zeolite 4A-water pair obtained by using the method developed was quite close to the value measured by using the PFG NMR method. This deduction could be made by taking into account the results obtained for a consolidated 4A powder sample and a coating prepared by repeated syntheses. Relatively higher apparent diffusivities were obtained for the relatively thicker zeolite 4A coatings prepared by using the direct heating method, which leads to the formation of coatings with more open structures.

20-P-16 - Crystal growth mechanism of LTA and FAU and densification process of zeolite film by seed growth I. Kumakiri a* , Y. Sasaki,b W. Shimidzu,b T. Yamagushi a and S.-I. Nakao a

aDepartment of Chemical @stem Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan, bResearch and Development Laboratory, Japan Fine Ceramics Centre, 2-4-1, Mutsuno, Atsuta-ku, Nagoya, 456-8587, Japan Zeolite NaA and FAU crystals were grown under the same hydrothermal condition using the same composition of clear solution. The only difference was the type of seed crystal used. This result suggested that the crystal growth did not occur by the attachment of nano-crystals. Zeolite films/membranes were prepared by the growth of seeded crystals. Based on the SEM and TEM observations and single gas permeation measurements, densification model of film/membrane is presented.

20-P-I 7 - In-situ synthesis of ZSM-5 on aluminum surfaces F. Scheffier and W. Schwieger

Institute of Industrial Chemistry I, University of Erlangen-Nuremberg Egerlandstr. 3, D-91058 Erlangen, Germany In this study the hydrothermal formation of ZSM-5 zeolitic coatings o n the surface of different pretreated flat aluminum sheets has been investigated. The specific feature of the reported preparation method is the fact that the aluminum sheet acts as a support as well as an aluminum source as well to achieve a good connection between the support and zeolite layer. The reaction was carried out under various synthesis conditions. The obtained products were characterized by XRD, SEM and chemical analysis.

295

20-P-18 - Conceptual process design of an all zeolite membrane reactor for the hydroisomerization of CJC6 E.E. McLeary a*, R.D. Sanderson a, C. Luteijn ~, E.J.W. Buijsse b, L. Gora b, T. Maschmeyer b and J.C. Jansen a'b

~Institute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology, Delft, The Netherlands," CLaboratory of Process Systems Engineering, Delft University of Technology, Delft, The Netherlands Membrane reactors provide opportunities for overcoming thermodynamic limits on the maximum attainable conversion of reversible reactions. A simple membrane reactor model has been employed to investigate the performance of C5/C6 hydroisomerization process on zeolites and compare it to a state-of-the-art total isomerization (TIP) process. A RON of 88.0 was obtained, slightly higher and promising compared to the TIP process with RON of 86.

296

21 - Nanocomposite Fundamentals and Applications (Wednesday) 21-P-06- Fabrication of hollow fibers and spheres composed of zeolites by layer-by-layer adsorption method Y. Tang (a), Y.-J. Wang (a), X.-D. Wang (a), W.-L. Yang (b)and Z. Gao (a)

a Department of Chemistry, Fudan University, Shanghai 200433, China, yitang@)Cudan.edu.cn b Department of Macromolecular Science, Fudan University, Shanghai 200433, China Hollow fibers and spheres of zeolite (labeled as HFZ and HSZ, respectively) were successfully fabricated using carbon fibers and polystyrene (PS) spheres as templates respectively, through layer-by-layer technique, coupled with removal of the templates by calcination. The optimum performance conditions to obtain these kinds of materials were systematically studied. The wall thickness and composition of these novel materials can be readily tailored by varying the number of nanozeolite/PDDA (poly(diallyldimethyl ammonium chloride)) deposition cycles and zeolite type used, respectively. The properties of these novel materials were characterized by means of XRD, IR and SEM.

21-P-07- The zeolitisation of diatoms to create hierarchical pore structures S.M. Holmes(a), R.J. Plaisted(b), P. Crow(b), P. Foran(b), C.S. Cundy(b) and M.W. Anderson(b)

a Environmental Technology Centre, Chemical Engineering Dept. UMIST, Sackville Street, Manchester, M60 1QD, UK. e-mail." [email protected], fax: +44 161 2004399 b UMIST Centre for Microporous Materials, Sackville Street, Manchester, M60 1QD, UK. The synthesis of a hierarchical pore structure, combining the macroporous diatomaceous earth with microporous zeolites, is reported. Diatomaceous earth is an abundant and varied source of macroporous silica which has been 'zeolitisatised' to produce a bifunctional, hierarchical composite. A range of different zeolites have been synthesised to generate different pore architectures, hydrophobic/hydrophilic materials and ion-exchange/catalytic properties.

21-P-08 - Generating the narrowest single-walled carbon nanotubes in the channels of AIPO4-5 single crystals G.D. Li (a,b), Z.K. Tang (b), N. Wang (b), K.H. Wong (b) and J.-S. Chen* (a)

a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, [email protected], edu. cn, Changchun, P. R. China b Department of Physics, HKUST, Hong Kong, P. R. China The pyrolysis of tripropylamine trapped in the framework structure of A1PO4-5 (AFI) single crystal results in the formation of the narrowest single-walled carbon nanotubes. The diameter of the nanotubes, which are stable enough when located in the AFI channels, is 0.42+0.02 nm. As the nanotubes are strictly aligned in the one-dimensional channels, the AFI crystal containing the tubes shows distinct anisotropic property. The growing process of the nanotubes was monitored by polarized optical microscopy. It has been found that the optimal temperature range for the growth of the nanotubes in A1PO4-5 single crystals is 773-873 K.

297

2 1 - P - 0 9 - Zeolite- an effective nucleating agent of Na2HPO4"I2H20 J. Dong, X. Jing and Yu. Zhang

Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi, P. R. China, [email protected] The use of zeolites, including LTA, Y, LTL, VPI-7, MFI and MOR, as nucleating agents of phase-change-material Na2HPO4"12H20 was first reported. The results showed that all the selected zeolites could inhibit the supercooling of Na2HPO4"12H20 to some extent. Among them MOR displayed the best effect. When the amount is 5%, it can lower the supercooling to 2.03---1.02~ and this system showed good stability and reversibility. At the same time, the morphology of samples after many times of re-crystallization was studied with SEM. The photograph of the SEM and microprobe analysis results showed that these different zeolites could form mixed isomorphous crystals with NazHPO4" 12H20. The function of zeolite on the nucleation had no direct relation with its own crystal lattice and its cell parameters.

21-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite hosts Yi. Zhang, Xi. Wang and Xu. Wang

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116012, China, [email protected]. Zeolite-entrapped SnO2 nano-semiconductor was synthesized by microwave ion-exchange method and chemical vapor deposition (CVD). The materials were studied by XRD, UV-Vis, FS and l l9Sn MAS NMR. Sn(IV) can be effectively introduced into the channels of zeolite hosts by microwave ion-exchange method. The hydration of Sn(IV) with H20 can be lessened under microwave irradiation, which improves the incorporation of Sn(IV) ions into the channels of the zeolites. For the CVD method, zeolite NH4Y is superior to NaY and HY as the host for SnO2 nano-semiconductor. The chemisorption of SnCI4 on the zeolite is correlated to the surface hydroxyl. SnO2 entrapped in zeolite has obvious quantum size effect. The materials also have excellent gas sensing properties in detecting ethanol.

21-P-11 - Encapsulation different routes

of Mn(bipy)2 into the zeolite Y prepared

via

B. Fan, W. Cheng and R. Li*

Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P.R. China. E-mail. rfii@tyut, edu. cn A series of zeolite Y, post-treated with various acids, synthesized in the organic-aminecontaining system, exchanged with Mn 2§ and prepared by direct addition of Mn(II) chloride in the crystallized mixture of zeolite Y, are used as hosts for the encapsulation of Mn(bipy)2. XRD, SEM, DTA, FTIR, and DRS measurements show that by flexible ligand method Mn(bipy)2 can be effectively encapsulated in different hosts. The properties of the hosts strongly influence the thermal stability and catalytic performances of encapsulated Mn(bipy)2. Upon treatment of zeolite Y with acids and the use of Mn-containing Y and Y synthesized in the system containing large-molecule organic amine as hosts, the catalytic activity can be significantly increased.

298

21-P-12 - Preparation of zeolite Beta/polystyrene beads and the corresponding hollow spheres V. Valtchev and S. Sferdjella

Laboratoire de Mat~riaux Min~raux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universitd de Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France Zeolite shells on polystyrene beads were prepared by a combination of layer-by-layer (LbL) and hydrothermal synthesis techniques. The negatively charged polystyrene beads were surface modified in order to adsorb zeolite Beta nanocrystals. Such particles were then adsorbed on the surface of the beads and induced to grow into a continuous film of intergrown crystals of zeolite Beta. The effect of the preliminary treatment on the formation of the zeolite film was studied. Finally the polystyrene beads used as macro-templates were removed by calcination in air, yielding hollow spheres of zeolite Beta. The zeolite Beta/polystyrene composites and the corresponding hollow zeolite spheres were characterized by XRD, SEM, TG/DTA and BET surface area measurements.

21-P-13 - Synthesis, characterization and catalysis of manganese(II) complexes encapsulated in NaX and NaY zeolites J.M. Silva (a), R. Ferreira (b), C. Freire (b), B. de Castro (b)and J.L. Figueiredo (a)

a Faculdade de Engenharia da Univ. Porto, [email protected] b CEQUP, Faculdade de Ci~ncias da Universidade do Porto, Portugal. The encapsulation of manganese(II)salen complexes into the pores of synthetic zeolites (NaX and NaY) was evaluated by different techniques: ICP-AES, XPS and SEM, TG-DSC, N2 adsorption, FTIR, UV-Vis. The results are consistent with the location of Mn complexes inside the micropores; even at low loadings it was possible to confirm this evidence. Catalytic tests in olefin epoxidation proved the existence of catalytic activity and the stereoselectivity of the complex after encapsulation. These catalytic results indicate that Mn-salen-zeolites may be promising heterogeneous catalytic systems.

21-P-14 - Guest-host interactions in systems containing liquid crystals confined to molecular sieves S. Frunza(a), L. Frunza(a,b), A. Sch6nhals(c), H.-L. Zubowa(b), H. Kosslick(b) and R. Fricke(b)

~National Institute of Materials Physics, Bucharest, [email protected], Romania bInstitute of Applied Chemistry, Berlin-Adlershof Germany ~Bundesanstalt far Materialforschung und Prafung, Berlin-Dahlem, Germany 4-Pentyl-4'-cyanobiphenyl and 4-octyl-4'-cyanobiphenyl liquid crystals (LCs) confined in molecular sieves of MCM-41 and cloverite types are studied in a wide temperature range by dielectric spectroscopy, thermal analysis and in-situ FTIR spectroscopy. The phase transitions of the bulk LCs cannot be detected when confined in MCM-41 sieve. A relaxational process occurs due to the molecular motions in the layer at the pore walls; the temperature dependence of the characteristic frequency obeys a Vogel-Fulcher-Tamman law associated to a glassy state. In the cloverite cages, the LCs keep the phase transitions of the bulk but shifted. Interactions between Lewis and BrOnsted sites and the LC molecules are monitored by IR spectroscopy. DTA measurements put also in evidence strong guest-host interactions.

299

2 1 - P - 1 5 - Zeolite Beta ordered macroporous structures with improved mechanical strength and controlled mesoporosity V. Valtchev, S. Sferdjella and H. Kessler Laboratoire de Matdriaux Min&aux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universit~ de Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France Macroporous zeolite Beta structures were prepared by a self-assembly of monodisperse polystyrene spheres and zeolite nanocrystals followed by a hydrothermal treatment. The characteristic features of the self-assembled and hydrothermally treated macroporous structures were studied by XRD, FTIR, SEM, TG/DTA and nitrogen adsorption measurements. The hydrothermal treatment of the self-assembled composites led to intergrowth and closing of the mesopores between the nanocrystals building the walls of macropores. The mechanical properties of the macroporous zeolite structures were substantially improved by the secondary growth of the zeolite crystals.

21-P-16 - Synthesis of zeolites with organic lattice K. Yamamoto (a), Y. Takahashi (b) and T. Tatsumi (b) a The University of Tokyo, Tokyo, Japan. b Yokohama National University, Yokohama, [email protected], Japan. Organic-inorganic hybrid zeolites with organic lattice were successfully synthesized by using organically bridged silane as a silica source. 29Si and 13C MAS NMR spectra and IR spectra proved the presence of organic lattice (Si-CH2-Si) partially replacing siloxane bond (Si-O-Si), although some of Si-C bonds were cleaved. Their unit cell sizes were slightly larger than those of their completely inorganic counterparts presumably due to the longer bond length of Si-C than that of Si-O. When synthesized in the absence of organic template molecules, they showed microporosity like ordinary zeolites. This is the first example of the successful synthesis of zeolites having an organic group as lattice in a strict meaning.

2 I-P-17 - Crystallization mechanism of AIMepO-13 Y. Qi, G. Wang and Z. Liu Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China, [email protected] A microporous aluminum methylphosphonate, A1MepO-[3, was prepared by hydrothermal method. The crystallization process was studied using XRD, PC-NMR, IR and SEM. It was found that phase transformation occurred in the crystallization process. There is an intermediate phase (nominated Phase A) between the starting gel and A1MepO-13. A1MepO-13 is not stable in the crystallization condition, and apt to be converted to more stable products A1MepO-~ and amorphous phase. The scheme for the crystallization process is suggested as: staring material ~ Phase A --~ A1MepO-13 --+ A1MepO-~ + amorphous phase.

300

21-P-18- Crystal structure and magnetic properties of rubidium clusters in zeolite L T A T. Ikeda a and T. Kodaira b aNational Institute for Research in Inorganic Materials, 1-1, Tsukuba, 305-0044, Japan bNational Institute of Materials and Chemical Research, 1-1, Tsukuba, 305-8565, Japan The Rb metal-doped Rb-type LTA shows an interesting magnetic property whose magnetic susceptibility obeys the Curie-Weiss law with a negative Weiss temperature. Rb atoms can be loaded up to 5.4 atoms per Gt-cage. The crystal structure of the Rb loaded Rb-type LTA is determined using X-ray powder diffraction under ultrahigh vacuum conditions. By increasing the loaded density of the Rb cluster, arrangements of the Rb + ions in adjacent m-cages went from equivalent to nonequivalent and the local symmetry for framework was degraded from Oh to Yd. The structural arrangement is clearly revealed by electron density distribution using the maximum entropy method. The magnetic property, which can be interpreted by the Dzialoshinsky-Moriya (DM) interaction, is strongly related to the noncentrosymmetric arrangement of the Rb clusters.

301

26 - Catalysis for Oil Refining (Wednesday) 26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of m e t a l - a c i d balance and metal location L.B. Galperin, S.A. Bradley and T.M. Mezza UOP LLC, P.O. Box 5016, Des Plaines, Illinois, USA,"[email protected] Isomerization of n-decane in the presence of 1000 ppm H2S was studied on bifunctional PtMAPSO-3! catalysts. Sulfur suppresses the catalyst metal function, thereby changing the metal-acid balance which is required for high performance. Methods for controlling the catalyst metal-acid balance by changing the ratio between metal and acid functions are demonstrated. Catalysts with high isomerization selectivity in the presence of sulfur should have a strong metal function. Close proximity of metal and acid sites, as well as highly dispersed metal located on the binder, gives a catalyst with an isomerization selectivity of about 90%. This is similar to selectivity of the same catalyst in the absence of sulfur.

2 6 - P - 0 7 - Hydrodesulfurization of benzothiophene supported on mesoporous silica MCM-41

over noble metals

M. Sugioka(a), A. Seino(a),T. Aizawa(a), J.K.A. Dapaah(a), Y. Uemichi(a) and S. Namba(b) a Muroran Institute of Technology, Muroran, [email protected], Japan bTeikyo University of Science and Technology, Yamanashi, Japan It was found that the Pt/MCM-41 catalyst showed high and stable catalytic activity for the hydrodesulfurization of benzothiophene at 350 ~ and this activity was higher than that of commercial CoMo/A1203 catalyst. The Pt/MCM-41 catalyst has high sulfur-tolerant property towards hydrogen sulfide formed in hydrodesulfurization of benzothiophene. The silanol group (Si-OH) of MCM-41 and the spillover hydrogen formed on Pt particle in Pt/MCM-41 catalyst play important roles in the hydrodesulfurization of benzothiophene. Pt/MCM-41 might be a promising new hydrodesulfurization catalyst for bulky organic sulfur compounds in the petroleum feedstocks.

26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating catalysts K.S. Rawat, M.S. Rana and G. Murali Dhar* Indian Institute of Petroleum, Dehradun, INDIA - [email protected] USY zeolites of varying Si/A1 ratios were used as support for Mo, NiMo, CoMo and NiW catalysts. Both the effect of variation of Si/A1 ratio of the zeolite and Mo content on support at fixed Si/A1 ratio were studied. The catalysts were examined by XRD, oxygen chemisorption and TPR techniques. The hydrodesulfurization and hydrogenation reaction studies indicated that these catalysts are more active than y-A1203 supported catalysts and the increase in activities may be attributed to an increase in Mo dispersion and reducibility. It was found that oxygen uptake correlates well with the catalytic activity.

302

2 6 - P - 0 9 - Highly active, selective and stable ferrierite-based catalysts for the skeletal isomerization of n-C5-C7 C.P. Nicolaides a, J. Makkonen b and M. Tiitta b Chemical Process Engineering Research Institute, National Centre for Research and Technology - Hellas, Thermi- Thessaloniki - cnicolai@alexandros, cperi, certh, gr, Greece; 6Fortum Oil and Gas, Oil Research and Development, Porvoo - [email protected], Finland Various ferrierite zeolites prepared via different synthetic routes were tested as catalysts for the skeletal isomerization of n-Cs-C7 olefins. The ferrierite samples having a small particle size, low total aluminum content, but a high percentage of aluminum in framework positions, showed the highest activity and selectivity for the reaction and stable catalytic performance with time-on-stream.

26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or aromatics) on various zeolite catalysts A. Raichle, H. Scharl, Y. Traa and J. Weitkamp Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany, jens. weitkamp@po, uni-stuttgart, de Methylcyclohexane (which can be readily manufactured from toluene by conventional ring hydrogenation) is converted into a high-quality steamcracker feed over the acidic zeolites HY, H-Beta, H-ZSM-11, H-ZSM-5, H-ZSM-22 and H-ZSM-35, thereby opening a new route for the utilization of surplus aromatics. While the conversion decreases with increasing geometrical constraints, the selectivity to the desired C2+-n-alkanes (mainly ethane, propane and n-butane) shows the opposite behavior. This is attributed to a higher contribution of Haag-Dessau cracking on zeolites with narrow pores.

26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as model reactions to investigate the pore topology of NU-88 zeolite S. Lacombe, A. Patrigeon and E. Benazzi IFP, Rueil-Malmaison Cedex, France - [email protected]. The n-heptane hydroconversion is a useful and simple tool to get primary ideas on the pore topology of new zeolites, although a more precise investigation requires the use of more complex molecules. This model reaction was used to investigate the pore topology of NU-88 zeolite. By working on the rate of appearance of the products and on the composition of the isomers and cracked products, it could be proposed that NU-88 zeolite contains 10 MR channels with large intemal void spaces, which could be intersections of 10 MR channels or extra-cavities. The results were complemented with a methycyclohexane cracking test, where the importance of hydrogen transfer reactions confirms the presence of large cavities.

303

26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on AI-MCM-41. Effect of the support Si/A! molar ratio T. Klimova, M. Calder6n and J. Ramirez

Departamento de Ingenieria Quimica, Facultad de Quimica, Universidad Nacional Aut6noma de M~xico, Cd. Universitaria, M~xico D.F. [email protected], M~xico A series of Mo and NiMo catalysts supported on Al-containing MCM-41 was prepared and characterized. It was shown that the incorporation of A1 atoms into the siliceous MCM-41 framework causes a deterioration of the textural characteristics and some loss in the periodicity of the MCM-41 pore structure. However, the acidity of the Al-containing MCM41 is substantially higher. The dispersion of Mo and Ni oxidic species increases with the incorporation of aluminum in the MCM-41 support, that produces an increase in the total conversion of dibenzothiophene. It was found that this effect is due to the interaction of Mo and Ni oxidic species with aluminum atoms of the MCM-41 support.

2 6 - P - 1 3 - Hydrogenation and ring opening of mono- and diaromatics for Diesel upgrading on Pt/Beta catalysts M.A. Arribas, J.J. Mahiques and A. Martinez

Instituto de Tecnologia Quimica, UP V-CSIC, Valencia, amart@itq, upv. es, Spain The combined hydrogenation and ring-opening of tetralin and 1-methylnaphthalene has been carried out on bifunctional Pt/Beta catalysts. The influence of the acidic and textural properties of the zeolite on activity and selectivity has been studied by varying the zeolite crystal size and the Si/A1 ratio by means of acid and steaming treatments. Similar trends were found for both aromatic reactants. Selectivity to products with the same number of carbon atoms than the feed and yield to ring-opening products increased while decreasing the BrOnsted acidity of the zeolite and by decreasing the size of the crystallites. Better catalytic performance was obtained for the catalyst prepared from a Beta zeolite dealuminated by steaming thus having a higher mesoporosity and reduced acidity.

26-P-14 - Hydro denitrogenation activity of N i O supported on various mesoporous alumino silicates

MoO3

catalysts

K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar

Department of Chemistry, Anna University, Chennai, India. Mesoporous alumino silicate molecular sieves with MCM-41 type structure synthesized using various A1 sources (i.e.: aluminum sulphate, aluminum isopropoxide, pseudo boehomite and sodium aluminate) have been used as supports for N i - Mo catalysts. The HDN of o-toluidine and cyclohexylamine was studied in a fixed bed flow reactor at 450~ and PH2 = 1 atm. The activity per unit of weight of the M C M - 41 supported catalysts was evaluated and compared to that of supported catalysts prepared by sequential impregnation method. The XRD and DRS data have been used to explain the observed trend in catalytic activity towards HDN reaction

304

26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and large-pore zeolite" effect of the zeolite nature on the location of NiMo sulfide in relation with catalytic properties J. Leglise (a), D. Cornet (a), M. Ba~lala (a), C. Potvin (b) and J.-M. Manoli (b) a Catalyse et Spectrochimie, ISMRA, Caen - [email protected]. b Rdactivitd de Surface, Universitd P. & M. Curie, Paris- [email protected] Ni and Mo ions were deposited into HBEA and HY zeolites, then sulfided. The solids were characterized at all preparation stages by various methods, notably by MAS-NMR, FT-IR, and TEM-EDX. The catalytic bifunctional properties were determined in the hydroconversion of benzene (8 MPa H2, 1 h"l, 240-360~ With both zeolites, about half of the Ni-Mo is located in cavities and mesopores, but the internal NiMo is better sulfided with the nanocrystalline BEA zeolite. Catalyst NiMoS/BEA was much more active and slightly more selective for hydrogenation than NiMoS/Y.

26-P-16 - Effect of zeolite acidity characteristics on the deactivation behavior of bifunctional large-pore zeolite catalysts during cyclopentane hydroconversion S. Gopal and P.G. Smirniotis Department of Chemical Engineering, University of Cincinnati, Cincinnati, USA Panagiotis. Smirniotis@uc. edu Time stability of Pt loaded zeolite Y, beta, mordenite and ZSM-12 was investigated at several different Si/AI ratios using cyclopentane as a coke producing agent. Although zeolite pore structure determined coking resistance to a large extent, significant differences in catalytic performance were observed within a particular type of zeolite depending on the Si/A1 ratio. This could be explained based on acid site density as it not only decreased the coking severity but also controlled metal dispersion and metal acidity balance in the catalyst. In general zeolites with Si/AI ratios between 15 and 40 showed the best stabilities in this study.

26-P-17 - Characterization and catalytic activities of MCM-41 supported WS2 hydrotreating catalysts T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao Catalysis Division, Indian Institute of Petroleum, Dehradun,, INDIA WO3-MCM-41 catalysts were prepared with good dispersion of WO3. The oxygen chemisorption in the sulfided state indicated that WS2 is also well dispersed on MCM-41 surface. 02 chemisorption as a function of W loading indicated that maximum dispersion and maximum number of anion vacancies are obtained with 19wt% W with highest catalytic activities for HDS, HYD, HDO. The small crystallite size and its constancy as function of W loading coupled with low surface coverage by WS2 indicated that monolayer WS2 patches are formed on the selected regions of support surface. The correlation between 02 uptake and catalytic activity indicated that oxygen chemisorption is not specific to any of the functionalities of the overall dispersion of WS2. Co and Ni addition resulted in promotional effect for both HYD and HDS; it is suggested that the three catalytic functionalities originate from different set of sites on the WS2 and its promoted analogues.

305

26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over bifunctional mesoporous molecular sieves C. Bischof and M. Hartmann

Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, hartmann@rhrk, uni-kl,de n-Heptane and n-decane hydroconversion have been investigated on platinum-, palladiumand ruthenium-containing A1MCM-41 (nsi/nal = 23) mesoporous molecular sieves. High selectivities for branched isomers have been observed on 0.27 Pd/HAIMCM-41 at reaction temperatures ranging from 250 to 380~ The product distribution is comparable with the one found for ideal bifunctional catalysis. While on 0.27 Pd/HAIMCM-41 no cracking on the metal function (hydrogenolysis) was observed, the cracked product distribution found on 0.5 Pt/HA1MCM-41 indicates that hydrogenolysis also occurs. Over 0.26 Ru/HAIMCM-41, the high yields of methane, ethane and linear hydrocarbons reveal a high hydrogenolysis activity of the ruthenium metal supported on AIMCM-41.

26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on zeolite catalyst A. Holl6 (a*), J. Hancs6k (a) and D. Kall6 (b)

a University of Veszpr~m, Veszpr~m, [email protected], Hungary. b Chemical Research Center, Hung. Acad. of Sci., Budapest, [email protected], Hungary *Present address." Hungarian Oil and Gas Co., Sz6zhalombatta, [email protected], Hungary Isomerization of c-C6, n-C6 and their mixtures has been investigated on Pt/H-MOR. The effects of reaction conditions and feed composition on the yield of isomers, as well as on the composition of cracked and other products were examined. Rate equations and parameters involved were determined for the isomerization of pure alkanes and their mixtures. Isomerization rate equation can be derived assuming rate determining skeletal rearrangement, while in mixtures and at higher pressures the transport in micropores seems to control the transformation.

2 6 - P - 2 0 - Application of adsorption Dubinin-Radushkevich equation for study of n-pentane and m-xylene conversion catalysts microporous structure S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev

Institute of Petrochemical Processes, Azerbaijan Academy of Sciences 30, N.Rafiev st., 370025, Baku, Azerbaijan, E-mail." [email protected], [email protected] The adsorptive and catalytic properties of zeolites HY, HZSM-5 and HM (natural and synthetic) subjected to dealumination, ion exchange with rare-earth and transition elements have been studied.The changes in conversion and selectivity for m-xylene and n-pentane are shown to be connected with the changes of the zeolites microporous structure.These changes are in conformity with DR equation parameters. The DR equation could be applied to the simple test method elaboration of the starting and modified zeolites microporous structure through their adsorptive properties.

306

26-P-21 - Hydroisomerization of n-hexadecane catalysts: Two different AI incorporation methods

over

Pt/AI-MCM-41

K.-C. Park and S.-K. Ihm

Dept. of Chem. Eng., KAIST, Taejon, skihm@_mai!.kaist.ac.kr, Korea. The hydroisomerization of n-hexadecane was carried out over Pt/A1-MCM-41 catalysts at 350~ and 103 bar. A1-MCM-41 was prepared by two different methods; a direct sol-gel method (Pre) and a post-grafting method (Post). A1-MCM-41 was characterized by using XRD, nitrogen adsorption, 27A1 NMR and ammonia TPD. The higher the amount of acid sites was, the higher the reactivity and isomer yield were. Pt/A1-MCM-41-Post showed higher conversions and higher isomerization yield than Pt/A1-MCM-41-Pre. Reaction results did not agree with A1-NMR data but with ammonia TPD. This difference was attributed to the better accessibility of tetrahedral sites (Broensted acid sites) in AI-MCM41-Post than those in A1-MCM-41-Pre.

26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for hydrotreating catalysts N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova a and K. Jiratova a

Institute of Catalysis, Bulgarian Academy of Science, Sofia, Bulgaria - [email protected]; alnstitute of Chemical Process Fundamentals, Acad. Sci. czech Republic, Prague This work reports the preparation of new supports for Mo- and NiMo-hydrotreating catalysts. Zr-containing mesoporous silicas with Zr/Si ratio from 0 up to 0.04 were prepared using TEOS, ZrOC102 and dodecylamine as a template. The materials and those modified with 12 % wt. Mo from 12-phosphomolybdic acid (HPMo) and its nickel salt were characterised by IR, TPD of NH3, TPR and their activities were measured in thiophene HDS. Activities in HDS of thiophene of Mo-containing catalysts prepared with the mesoporous silicas were higher than those of the catalysts prepared with amorphous silica.

26-P-23 - New catalysts for isomerization of long-chain n-paraffins M.I. Levinbuk,1 L.M. Kustov,2 T.V. Vasina,2 O.V. Masloboishchikova,2 M.L. Pavlov,3 I.E. Gorbatkina 4 and V.A. Khavkin 4

1Moscow Oil and Gas University, 65 Leninsky prospect, 1117917 Moscow, Russia 2N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia 3Salavat Catalyst Factory, Salavat, 4 Moscow Research Institute of Oil Refining, Russia Novel Y-type zeolite-based catalysts for isomerization of long-chain paraffins (nCT-nCl6) and aromatics hydrogenation have been developed. They provide high selectivity to isomerate with minimal feed cracking. Isomerization of nC7 is accompanied by benzene hydrogenation into methylcyclopentane and cyclohexane. Each reaction occurs on different sites and proceeds without altering the other one. The effect of the ratio of iso to n paraffins in gasoline fraction (IBP-62~ and 100-130~ was studied. Altenative methods to use the new catalysts in oil processing have been considered.

307

2 8 - Confinement and Physical Chemistry for Catalysis (Wednesday) 28-P-06- Use of coke-selectivated H-ZSM-5 in xylene isomerization F. Bauer and A. Freyer

Institut fi~r Oberfli~chenmodifizierung, 5, Leipzig, Germany- fbauer@rz, uni-leipzig.de The deposition of carbonaceous residues is used as modifying technique for the selectivation of H-ZSM-5 during xylene isomerization. An enhanced selectivity and a reduction of xylene loss was achieved by a thermal treatment of coke-selectivated H-ZSM-5 with hydrogen and propane. In the presence of these reactive carrier gases internal coke may be effectively removed and the remaining external coke covers those acid sites located on the crystallite surface which are responsible for undesired transalkylation and secondary isomerization reactions. Compared with samples selectivated with the xylene feed under high severity conditions deposits of about 0.3 wt.-% modified pre-coke using methanol as coke precursor are sufficient to reduce the xylene loss to 1.1% while maintaining the desired activity for ethylbenzene conversion of about 55 %.

2 8 - P - 0 7 - Photocatalytic reactions on chromium containing mesoporous molecular sieves under visible light irradiation: Decomposition of NO and partial oxidation of propane H. Yamashita*, K. Yoshizawa, M. Ariyuki, S. Higashimoto, and M. Anpo*

Osaka Prefecture University, yamashita@chem, osakafu-u, ac,/p, Japan The photocatalytic reactivities of Cr-containing mesoporous molecular sieves (Cr-HMS) have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O. In the presence of NO, Cr-HMS exhibited photocatalytic reactivity for the decomposition of NO into N2, 02, and N20 not only under UV light irradiation but also visible light irradiation. Especially, under visible light irradiation, a higher selectivity for N2 formation was observed. In the presence of propane and 02, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein with a high selectivity, while a complete oxidation proceeded under UV irradiation mainly to produce CO2. The charge transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactivities.

28-P-08 - Enhancing the shape selectivity of nanocrystalline HZSM-5 zeolite via comprehensive modifications H..C. Guo, X.S. Wang and G.R. Wang

Institute of Industrial Catalysis & State Key Lab. of Fine Chemicals, Dalian Universityof Technolog)4, Dalian, P R. China- [email protected] Fine tuning of a nano-HZSM-5 (20-50 nm, S I O 2 / A 1 2 0 3 = 25) was achieved by systematic modifications. Evaluations were made through analyzing zeolitic overall acid strength, external surface acid sites and microporous geometric constraints and the shape-selectivity in ethylbenzene ethylation. It is concluded that nano-ZSM-5 can be trimmed into highly shapeselective catalyst by exploiting the synergic effect of zeolitic overall acid strength suppression, microporous geometric constraints regulation and external acid sites passivation.

308

28-P-09 - Nature of shape-selective catalysis in the ethylation and the isopropylation of biphenyl over H - m o r d e n i t e s Y. Sugi a*, S. Tawada a, T. Sugimura a, Y. Imada a, Y. Kubota a, T. Hanaoka b and T. Matsuzaki b a Department of Chemistry, Gifu University, [email protected], Japan b National Institutes of Materials and Chemical Research, Tsukuba 305-8565, Japan 4-Isopropylbiphenyl (4-IPBP) was consumed much faster than 3-IPBP in their competitive isopropylation. Selectivity for 4,4'-diisopropylbiphenyl (4,4'-DIPB) in bulk products decreased with the increase of 3-IPBP, however, the selectivity in encapsulated products kept constant. 4-Ethylbiphenyl (4-EBP) disappeared much faster than 3-EBP in their competitive ethylation. Selectivity for 4,4'-diethylboiphenyl (4,4'-DEBP) was less than 2 %, whereas total selectivity for DEBPs with 4-ethyl group was higher than 65 % in both products: DEBPs were predominantly produced from 4-EBP. HM-pores were too loose to form 4,4'-DEBP.

28-P-10 - A d s o r p t i o n of selected amino acids from a q u e o u s solutions on m e s o p o r o u s molecular sieves S. Ernst, M. Hartmann and S. Munsch Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, sernst@rhrk, uni-kl, de The adsorption of various amino acids from aqueous solutions using MCM-41-type mesoporous molecular sieves is discussed on the basis of their adsorption isotherms. The amounts adsorbed strongly depend on the pH and the nature of the individual amino acid: Amino acids with acidic side chains are hardly adsorbed, whereas basic amino acids show very high affinities to the mesoporous adsorbent. The uptake of amino acids with non-polar side chains increases with the chain length. The adsorption complex is proposed to consist of the cationic form of the amino acid attached to the negatively charged silica surface.

28-P-11 - Influence of O H groups of Beta zeolites on the synthesis of M T B E F. Collignon a and G. Poncelet Universit~ Catholique de Louvain, Unit~ de Catalyse et Chimie des Mat~riaux Divis~s, Place Croix du Sud 2/17, B-1348 Louvain-la-Neuve, Belgium. a Katholieke Universiteit Leuven, Centrum voor Oppervlaktechemie en Katalyse, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium, [email protected] Vapor phase synthesis of MTBE over zeolite Beta is very efficient. For example, Beta zeolite is three times more active than Amberlyst-15 for MTBE vapor phase synthesis at 50~ The better catalytic performance of H-Beta was verified in liquid phase. The external surface area, the amount of bridging A1OHSi, and silanol groups are important zeolite parameters for the ether synthesis. The reaction occurs on bridging A1OHSi acid sites. The highest yields are reached for low SiOH/A1OHSi ratios where methanol clusters bonded to silanol groups allow accessibility of isobutene to the active AIOHSi groups.

309

28-P-12 - About a possibilities of effectiveness increasing of porous catalyst granules with controlled activity profile v . v . Andreev Dept. of Control and Informatics in Technical Systems, Chuvash State University, Moskovskii pr. 15, 428015 Cheboksary, Russia; [email protected] The possibilities of effectiveness increasing of the porous catalyst granules with controlled activity profile are considered. Optimal control by the chemical reaction proceeding on such catalyst granules under artificially created non-steady-state conditions allows to make their productivity higher, than under steady-state conditions. On the base of analysis of critical phenomena of multiplicity states form it is possible to reach of the more high productivity of porous catalyst granule with controlled activity profile in case of a catalytic reaction proceeding under non-steady-state conditions.

2 8 - P - 1 3 - Effects of channel structures of wide pore zeolites on m-cresol transformation F. L6pez a, L. Gonzdlez a, J.C. Herndndez a, A. Uzcdtegui a, F.E. Imbert a and G. Giannetto b a Laboratorio de Cin6tica y Cat6lisis, Grupo de Materiales Microporosos en Cat6lisis, Departamento de Quimica, Facultad de Ciencias, Universidad ale Los Andes, La Hechicera b M6rida 5101A. Venezuela. Fax." +58 74 401286, e-mail. [email protected] ; Facultad de Ingenieria, Universidad Central de Venezuela, Los Chaguaramos, Caracas Venezuela. The m-cresol transformation was carried out on wide pore zeolites (HFAU, HBEA, HMOR and HOFF). The activity follows the sequence HFAU > HBEA>> HMOR > HOFF. The order of the acid strength determined by TPD-NH3 was HMOR>HOFF>HBEA>HFAU. On the HBEA. HMOR and HOFF the isomerization was the main reaction due to their pore system structure, that limits the formation of diphenylmethane intermediate of disproportionation, while on HFAU the disproportionation reaction was not impeded at low conversion. The p/o selectivity is mainly function of conversion.

28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid and gas phase esterification reactions. The influence of the hydrophobicity of the catalyst M.J. Verhoef", R.M. Koster b, E. Poels b, A. Bliek b, J.A. Peters a and H. van Bekkum a aTechnische Universiteit Delft, H. [email protected], The Netherlands blnstituut voor Technische Chemic, Universiteit van Amsterdam, The Netherlands Zeolitic materials with Si to AI r a t i o s - with accent on zeolite B e t a - were tested in esterification reactions. Hydrophilic materials proved to be inactive in the liquid phase esterification of apolar substrates. This may be ascribed to strong adsorption of water formed. More polar substrates are able to compete with water for the adsorption sites; thus, the influence of the hydrophobicity of the catalyst on its activity becomes less pronounced. Such influence is negligible on the activity of the catalysts in gas phase reactions. Here, the activity is mainly dependent on the amount and the strength of acid sites.

310 2 8 - P - 1 5 - The influence of pore geometry on the alkylation of phenol with

methanol over zeolites G. Moon, K.P. M611er, W. B6hringer and C.T. O'Connor

Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, Rondebosch, South Africa - gmoon@chemeng, uct.ac.za The alkylation of phenol with methanol, in the liquid phase, has been investigated using zeolites H-ZSM-5, H-beta, H-MCM-22, H-mordenite, H-USY as well as amorphous silica alumina. At the low temperature of 200~ anisole was the major product over all the catalyst investigated, second was cresols. H-Beta, H-USY, H-ZSM-5, H-mordenite and amorphous silica alumina showed similar cresol distributions. H-MCM-22, which has the smallest pore openings and the narrowest channel system among all zeolites studied, showed the highest preference for p-cresol.

28-P-16 - Diffusion analysis of c u m e n e cracking over Z S M 5 using a jetioop reactor P. Schwan and K.P. M~ller

Department of Chemical Engineering, University of Cape Town, South Africa. Cumene is cracked in a recycle reactor over commercial H-ZSM5 extrudates during a pulse experiment. The results are compared to those obtained from steady state measurements. A linear model for diffusion, adsorption and reaction rate is applied to reactants and products. In contrast to literature it is shown that if the Thiele modulus is greater than 5, the system becomes over parameterised. If additionally adsorption dynamics are negligible or not measurable, only one lumped parameter can be extracted, which is the apparent reaction constant found from steady state experiments. The pulse experiment of cumene is strongly diffusion limited showing no adsorption dynamics of cumene. However, benzene adsorbed strongly on the zeolite and could be used to extract transient model parameters.

311 2 9 - New Approaches to Catalyst Preparation (Wednesday) 2 9 - P - 0 5 - Catalytic properties of MFI zincosilicates s. Kowalac, E. Szymkowiak, I. Lehmann and G. Giordano*

Faculty of Chemistry, A. Mickiewicz University, Poznati, Poland. *Department of Chemical Engineering, University of Calabria, Rende, Italy. skowalak@main:amu.edu.pl A series of zincosilicates MFI was synthesized from the mixtures of even Zn/Si ratio and various silicon sources. The properties of the resulting samples differed considerably regarding their zinc content, the crystallite morphology and size and catalytic activity. The samples modified with various cations (Ca, Cu, Zn, AI, H) showed some activity for 2-propanol dehydration (no acetone was detected). The samples modified with AI cations showed the highest activity. It is likely that part of A1 could attain the framework positions or facilitate a generation of separated acidic OH groups. The lower activity of the H-forms could result from the presence of hydrogen bonds between adjacent hydroxyls.

2 9 - P - 0 6 - Acidity characterization of dealuminated H-ZSM-5 zeolites by

isopropanol dehydration C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis*

University of loannina, 45 110 Ioannina, [email protected], Greece A series of dealuminated ZSM-5 zeolites with various framework Si/A1 ratios were prepared by different methods (HC1, ammonium hexafluorosilicate, steaming). The number of acid sites that correspond to the high-temperature desorption peak of the ammonia-TPD spectra of all the dealuminated samples is in 1:1 mole analogy to the framework A1 (FA1), irrespective the degree and the type of dealumination method. The catalytic activity of the H-ZSM-5 zeolites for isopropanol dehydration is linearly related to the number of acid sites that correspond to the FAl-content (Brtinsted acidity). The Si-A1 amorphous phase that is formed in the hightemperature steamed samples affects activity and induces different product selectivity for propene and diisopropyl ether.

2 9 - P - 0 7 - A c i d i c Z r O 2 / S O 4 2 in mesoporous materials Y. Sun, L. Zhu, H. Lu, D. Jiang, and F.-S. Xiao*

Key Laboratory of Inorganic Synthesis and Preparative Chemistry & Department of Chemistry, Jilin University, Changchun 130023, China,[email protected] ZrO2/SO42 supported in mesoporous hexagonal materials such as MCM-41 were prepared by dispersion of ZrOC12.8HzO into the mesopores, followed by the hydrolysis and sulfation. They have been characterized by X-ray diffraction, nitrogen adsorption isotherms, infrared spectroscopy, and catalytic cracking of cumene and 1,3,5-triisopropylbenzene. The results show that ZrO2/SO4 2" was successfully loaded into the inner pores of MCM-41 and the as-synthesized catalyst showed favorable catalytic properties. The factors in the preparative process that affected the final activity were discussed.

312

29-P-08- HMS catalysts containing transition metals or transition metal complexes z. Fu, D. Yin ,W. Zhao, Y. Chen, D. Yin, J. Guo, C. Xiong and Luxi Zhang Institute of Fine Catalysis and Synthesis, Hunan Normal University, Changsha, 410081, P R China Copper, titanium, cobalt and iron substituted mesoporous silicas (Cu-, Ti-, Co-, and Fe-HMS) were synthesized with dodecylamine surfactant as templating reagent. Three assembled pathways were used to bond Ti tartrate complex over mesoporous silicas (HMS). The above described catalysts were characterized by XRD and FT-IR, their metal loadings were measured by chemical analysis method. In catalytic testing, Cu-HMS and especially Fe-HMS show the best catalytic activity for hydroxylation of phenol with H202 in the presence of water. Ti-HMS and especially Ti tartrate complex assembled HMS catalysts exhibit the best epoxidative activity for catalyzing epoxidation of styrene with tert-butyl hydroperoxide.

29-P-09 - Synthesis of hydrophobic mesoporous molecular sieves by surface modification K.-K. Kang and H.-K. Rhee* School of Chemical Engineering and Institute of Chemical Processes Seoul National University, Seoul 151-742, [email protected], Korea AlkyI-MCM-41 was prepared by surface modification technique. The modification was conducted by chemically bonding an alkyl substituent to the surface of pure silica MCM-41 via an organic reaction. In this work methyl and butyl groups were successfully introduced to MCM-41.

29-P-10 - Guanidine catalysts supported on silica and micelle templated silicas" new basic catalysts for organic chemistry D.J. Macquarrie DCM>TCE. The main oxidation products were CO, CO2, HC1 and C12. Some other chlorinated by-products were detected as well (vinyl chloride, methyl chloride and tetrachloroethylene). The destruction of chlorinated mixtures induced an inhibition of the oxidation of each CVOC. An important decrease in the formation of intermediates was noticed and HC1 selectivity was largely improved.

30-P-19 - Solid state MAS N M R studies of zeolites and alumina reacted with chlorofluorocarbons (CCI2F2, CHCIF2) I. Hannus (a), Z. K6nya (a), P. Lentz (b), J. B.Nagy (b) and I. Kiricsi (a)

a Department of Applied and Environmental Chemistry, University of Szeged, hannus@chem, u-szeged, hu, Hungary b Laboratoire de RMN, Facultds Universitaires Notre-Dame de la Paix, Belgium Multinuclear Magnetic Resonance of both the adsorbed and the solid phase allowed us to follow the reaction of various chlorofluorocarbons (CC12F2 and CHC1F2) on NaY, HZSM-5 zeolites and 7-A1203. The intermediates and the final products were identified by 13C and 19F NMR spectroscopy. At the same time the kinetics of the reactions could be determined at various temperatures. Over alumina dismutation reactions take place as primary steps caused by the Lewis acid sites. 29Si, 27A1 and 23Na NMR measurements were quite useful to identify the solid reaction products.

30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water from petroleum refineries A.K. Aboul-Gheit and S.M. Ahmed

Egyptian Petroleum Research Institute, Nasr City P.O. Box 9540, Cairo 11787, Egypt. E Mail [email protected] Photocatalytic degradation of petroleum representative hydrocarbons (o-xylene > decaline > n-hexadecane) was investigated using metal-phthalocyanines (Pcs) combined with Na-zeolites (1:1) as photocatalysts. This combination was found significantly synergistic, n-Hexane photodegradation was examined using : a) CuPc mixed with Na-mordenite, Na-Y, Na-Beta or Na-ZSM-5, b) CuPc mixed with Na-, H- and dealuminated-mordenite, and c) Pcs having different central oxidative metals: Ce, Co, Mn, Fe, Cr or Cu, mixed with Na-Beta zeolite. Crude oil photodegradation was also examined using the catalysts of item c). The illumination period for pure hydrocarbons testing was 15 minutes, whereas for crude oil was one week. Kinetics using Langmuir-Hinshelwood models was successful.

325

30-P-21 - Autoreduction of Cu 2+ species in Cu-ZSM-5 catalysts studied by diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry and elemental analysis G. Moretti a, G. Ferraris a and P. Galli b

a Centro CNR "SACSO", bDipartimento di Chimica, Universitdt "La Sapienza", [email protected], Roma- Italy The autoreduction process of Cu 2+ species in Cu-ZSM-5 catalysts, with Si/A1 = 80 and copper exchange levels 81 and 536 %, was studied by means of spectroscopic (in-situ diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy) and chemical methods (thermogravimetry in N2, elemental analysis, adsorption-desorption of N2 at 77 K and adsorption of N2 at 273 K). It appears that on the fresh catalysts (treated in air at 383 K) the majority of Cu 2+ species may be reduced to Cu +, under vacuum or in a flow of inert gas at high temperature, by means of the carbonaceous deposits left in the ZSM-5 matrix due to the incomplete burning of the organic template used in the zeolite synthesis.

30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the lean SCR of NOx by methane F. Bustamante (a), P. Avila (b) and C. Montes de Correa (a)

a Dept. of Chemical Engineering, Universidad de Antioquia, [email protected] b Instituto de Catdlisis y Petroleoquimica, CSIC 28049 Madrid. Espagta The lean NOx reduction by CH4 in the presence of 10-15% water vapor was studied on biand tri-metallic powder catalysts containing two or three of the following species: Co, Pd, Ce, and Pt on HMOR. A cooperative effect in the Pd-Co, Pd-Ce, Pd-Ce-Co and Pd-Pt-Ce systems was found for CH4-SCR under wet conditions. Pd-Ce/HMOR and Pd-Ce/Co-HMOR catalysts were more tolerant to the coexistence of H20 and SO2 in the gas feed than Pd/Co-HMOR. Co, Pd and Ce species were impregnated on ceramic monoliths washcoated with mordenite. The results of NOx reduction were different for the monolithic and powdered catalysts. However, a similar trend in the CH4-SCR activity of both catalyst types was observed.

30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation of toluene over CuY zeolites A.P. Antunes (a), J.M. Silva (b), M.F. Ribeiro (a), F.R. Ribeiro (a), P. Magnoux (c) and M. Guisnet (c)

a lnstituto Superior T~cnico, DEQ, Lisboa, Portugal, e-mail.'[email protected] b Instituto Superior Engenharia de Lisboa, DEQ, Lisboa, Portugal c Universit6 de Poitiers, UMR 6503, 40 Av. Recteur Pineau, 86022 Poitiers, France Transformation of toluene in low concentration (800 ppm) in air over CuY zeolites containing different copper contents and Si/A1 ratios was studied at temperatures between 150 and 500~ It was found that total oxidation is promoted on non dealuminated catalysts and depends on the copper content. The most active catalysts correspond to the catalysts with Cu contents that are close to the complete exchange of the zeolite. The presence of sodium cocations in CuY zeolites increases their combustion efficiency, by improving the dispersion of ionic copper species and preventing the formation of CuO clusters.

326

30-P-24 - Study on relationship between the local structures of Ti-HMS mesoporous molecular sieves and their photocatalytic reactivity for the decomposition of NO into N2 and 02 J. Zhang, a B. He, a M. Matsuoka, b H. Yamashita b and M. Anpob

a Institute of Fine Chemicals, East China University of Science and Technology, 7, China," [email protected]; b Dept. of Applied Chemistry, Graduate School of Engineering Osaka Prefecture University, 1-1, Gakuen-cho, Saka, Japan Titanium oxide species included within the framework of mesoporous zeolites (Ti-HMS) were studied using nitrogen adsorption/desorption. These mesoporous materials exhibited high and unique photocatalytic reactivity for the direct decomposition of NO into N2, N20 and 02 at 275K.

30-P-25 - Influence of synergistic effects on the selective catalytic reduction of NOx with CnHm over zeolites S.N. Orlik and V.L. Struzhko

L. V. Pisarzhevsky Institute of Physical Chemistry of NAS of Ukraine 03039, Pr.Nauki, 31, Kiev, Ukraine, fax: (044) 265 62 16; e-mail: [email protected] A synergistic effect leading to the increased catalyst activity and selectivity in selective catalytic reduction (SCR) of NO with methane or propane-butane mixtures was found when cobalt, calcium and lanthanum cations were introduced into the protic MFI-type zeolite. This non-additive increase of the zeolite activity is attributed to increased concentration of the BrOnsted acid sites and their defined location as result of interaction between those and cations (Co, Ca, La). Activation of the hydrocarbon reductant occurs at these centers. Doping the H-forms of zeolites (pentasils and mordenites) with alkaline earth metal and Mg cations considerably increased the activity of these catalysts and their stability to sulfur oxides.

30-P-26 - Catalytic properties of Fe-Co double synthesised with beta zeolite for toluene oxidation

layered

hydroxides

J. Carpentier, S. Siffert, J.F. Lamonier and A. Abouka'/s

Laboratoire de Catalyse et Environnement, E.A. 2598, Universit~ du Littoral- C6te d'Opale, MREID, 145, avenue M. Schumann, 59140 Dunkerque, France, [email protected]. Fe-Co layered double hydroxides with Co/Fe ratios of 2 and 3 were prepared with or without the presence of Beta zeolite and their catalytic potential was tested in toluene total oxidation. These calcined solids synthesised with [3-zeolite were less active and selective than those prepared without zeolite. However, a mechanical mixture of 1/3 Fe,Co-LDH (Co/Fe - 3) + 2/3 Na[3-zeolite presented higher catalytic performance which could be explain by a synergetic effect of the both Fe,Co-double oxide and [3-zeolite. The mechanism could undergo through a spillover of the adsorbed toluene from zeolite, which has a high toluene storage/release capacity, to the Fe,Co double Oxide, which is highly performant for this oxidation.

327

30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and i n - s i t u - D R I F T S studies F. Heinrich, E. L6ffler and W. Grtinert Lehrstuhl Technische Chemie, Ruhr-UniversitOt Bochum, P. O. Box 102148, D-44 780 Bochum, Germany An in-situ DRIFTS study of a Fe-ZSM-5 catalyst during the selective catalytic reduction of NO by isobutane is reported. The catalyst was prepared by vapour-phase exchange of HZSM-5 with FeC13. Catalytic data from in a micro-catalytic flow reactor have been in principle reproduced by using the DRIFTS cell as a flow reactor. Adsorbates, transient intermediates, and interactions of zeolite OH groups have been monitored at 873-523 K, with concomitant NO conversion measurement. It has been found that the spectra of deposits formed on H-ZSM-5 and Fe-ZSM-5 are identical at 523 K. In formation about the deposits obtained at 523 K was not representative for the temperature of peak NO conversion

3 0 - P - 2 8 - Selective catalytic reduction of NO by methane over A g N a Z S M - 5 catalysts in the excess of oxygen C. Shi a,b, M. Cheng a, Z. Qu a, X. Yangb and X. Bao a* a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, The Chinese Academy Sciences, Dalian 116023, P. R. China, [email protected] b Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, P. R. China AgNaZSM-5 catalysts were investigated for the selectively catalytic reduction of NO by methane in the excess of oxygen. It was clearly depicted that the conversion rate of NO to N2 had a linear dependence on the silver loading (4.32-~13.64%), which indicated that all silver species in the zeolite were active for the CH4-SCR reaction. The presence of excessive oxygen in the feed gas favored the CH4-SCR reaction. The temperature programmed desorption profiles in He and 2%CH4/He after the co-adsorption of NO and 02 revealed that surface nitrates were formed on silver catalyst, and could be effectively reduced by methane

30-P-29 - Z S M - 5 / R a n e y Fe composite used as D e N O x catalyst B. Zong, W. Wang, L. Lu and X.T. Shu Research Institute of Petroleum Processing, China Petrochemical Cooperation, Beijing, China Zeolite ZSM-5 was grown onto Raney Fe powder and wire gauze. ZSM-5/Raney Fe was used as catalyst for the selective reduction of NO with NH3 in the presence of 02, SO2 and H20. DeNOx activity of the composite catalysts were found to be increased after hydrothermal treatment. Migration of Fe from Raney Fe into zeolite ZSM-5 during the treatment contributes to the high performance of the ZSM-5/Raney Fe of DeNOx reaction. Using the technique of growth the zeolite in situ on Raney Fe, high hydrothermal stability and high mechanically strength catalytic packing of any required shape can be produced. The composite ZSM5/Raney Fe is promising catalyst for industrial DeNOx processing.

328

30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged zeolites B.I. Mosqueda-Jim6nez a'b, M. Brandmair a, A. Jentys a, K. Seshan b and J.A. Lercher a

a Technische Universit~it Mfinchen, Garching, [email protected], Germany b Faculty of Chemical Technology, University ofTwente, Enschede, The Netherlands The reduction of NO in the presence of excess oxygen with propane and propene over Niexchanged zeolites was studied. Incorporation of Ni led to the formation of Bronsted acid sites resulting from the hydrolysis of divalent Ni ions. Calcined catalysts showed a high selectivity to N2 formation, while after reduction of the Ni species significant concentrations of NO2 and N20 were formed. Higher NO conversions were obtained with propane compared to propene except for NiNaMOR catalysts with low nickel content. The concentration of acid sites did not play a major role in the NO reduction, high acid site concentrations, however, resulted in the formation of coke.

30-P-31- NOx Reactivity on microporous catalytic studies

MeAPOs. spectroscopic

and

A. Frache a, M. Cadoni a, S. Coluccia b, L. Marchese a*, B. Palella c, R. Pirone ~ and P. Ciambelli e

aDitz~'mento a~Scienzee tecr~logieAvamate, Universitgtdel Piemonte On'entaleA l e s s ~ Italy. ~chese(~;h wTito.it,"bDipartimentodi Chimica IFM, Universitgtdi Torino CDi~mento di l n g e ~ Chimic~ (fniversithdi Ntg~oli "FedericolI", N#~ol~ Italy. dlstitutook"Ricerchesulla Combus#one, CNR, Ncg~oli, Italy,"e o l ~ F l t O ~"I n g e ~ Chimicae Alimentare, Untversitgtdi Salerno, Italy. NOx reactivity on microporous aluminophosphates and silico-aluminophosphates containing Co and Cu ions in A1PO4-34, -5 and -11 type structures, is reported. CoAPO-34 is very efficient catalyst in the NO oxidation to NOz reaching the equilibrium conversion value at 350~ wfiereas is inactive in the NO reduction by CO, a reaction which, on the contrary, p ~ efficiently on Cu-based catalysts (specially in the 300-550~ range). N20 decomposition and NO oxidation to NO2 are also effective on Cu-containing catalysts, and followed the sequence of activity: Cu-SAPO-34 _>CuAPSO-34 > CuAPO-34 > CttAPO-5 ~ ChaAPO-11. NO adsorption on the most active catalysts was investigated by FTIR and this showed that Cu2+ and Cu+ mononitrosyl complexes were formed in much larger amount on the silicon-containingcatalysts.

30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon removal under cold-start engine condition H.K. Seo, J.W. Oh and S.J. Choung

School of Environmental and Applied Chemistry, KyungHee University, 449-701 Suwon, Korea, [email protected] Air pollution, mainly contributed by the emission from automobiles, has become the most serious urban environmental problems in many countries. In this study, so as to meet the SULEV regulation, the main idea has been focused on the utilization of HCA(Hydro-Carbon Adsorber) in order to adsorb the excess hydrocarbons emitted during the period of engine cold-start. As a main recipe of HCA materials, many types of zeolite as well as the combination of alumina, precious metals were used. In this study, physico-chemical factors of zeolite such as acidic properties and hydrophobic properties etc. has been characterized, and tried to find the optimum recipe of HCA materials. As results, among the acid properties of zeolites, the Si/A1 ratio is found to be the most important factor to get higher hydro-carbon adsorption capacity.

329

3 0 - P - 3 3 - In-situ synthesized Z S M - 5 on decomposition on the monolithic catalysts

cordierite

substrate

and

NO

N. Guan *a, X. Shan a, X. Zeng a, S. Liu a, S. Xiang a, U. Illgen b and M. Baerns b

aDepartment of Chemistry, Nankai University, Tianjin P.R. China; blnstitute of Applied Chemistry, Rudower Chaussee 5, Berlin-Adlershof Berlin, Germany For obtaining a monolithic catalyst with better mechanical and hydrothermal durability, ZSM5 zeolite with different Si/A1 ratios (60, 55, 40, 25, 15) have been synthesized in-situ on cordierite honeycomb substrate. SEM photos showed the different crystal size from sample to sample. Solid MAS NMR was used to determine Si/A1 ratios and the amount of zeolite on the substrate by the peak intensity 29Si. Investigation of NO decomposition (2000 ppm NO in He) on the Cu-exchanged ZSM-5/cordierite monolithic catalysts was performed at 723 K, GHSV=I 0,000/h. Results proved that the TOF of NO decomposition on monolithic catalysts is comparable with pure zeolite catalysts.

30-P-34 - Selective reduction of N O to N2 in the presence of oxygen T. Furusawa (a), K. Seshan (b), S.E. Maisuls (b), J.A. Lercher (c), L. Lefferts (b) and K. Aika (a)

alnterdisciplinary Graduate School of Science & Technology, Tokyo Institute of Technology, Japan [email protected].]p; bFaculty of Chemical Technology, University of Twente, The Netherlands," Clnstitutfiir Technische Chemic, Technische Universitgtt Mfmchen, Garching Germany Catalytic performance of Co-ZSM5 (Si/AI=I 1) prepared by SSIE (Solid State Ion Exchange) method was compared with that of Ag-ZSM5 prepared by LSIE method for the selective reduction of NO with propylene in the presence of oxygen. It was found that C3H6 acted as a reductant more effectively for production of N2 over Ag-ZSM5 than Co-ZSM5 and that a route for producing N2 exclusively existed over Ag-ZSM5 from the kinetic results.

30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean N O x - S C R with methane D. Sannino, M. Concetta Gaudino and P. Ciambelli

Dipartimento di Ingegneria Chimica e Alimentare, Universith di Salerno, 84084 Fisciano (SA), Italy. sannino@dica, unisa, it Lean NOx-SCR with CH4 has been investigated on Co-modified synthetic ferrierite prepared in different conditions of ion exchange (temperature, time, precursor zeolite composition). A maximum NOx conversion (50% at 100% CH4 conversion) was obtained at 500~ Activity and selectivity depend on the nature of Co species (from mononuclear to polynuclear cationic to oxidised phases) formed into ferrierite. The effect of side reactions such as uncatalysed and catalysed methane combustion on catalytic performance is discussed.

330 03- New Methods of Zeolite Synthesis (Thursday) 0 3 - P - 0 6 - Zeolitization of a spanish bentonite in seawater medium. Effect of

alkaline concentration and time R. Ruiz, C. Blanco, C. Pesquera and F. Gonzzilez

Dept. de Quimica. Univ Cantabria, [email protected], Santander (Spain). In this study a bentonite was modified to a zeolitic material by alkaline treatment in a seawater medium. The structural and textural characteristics of the clays modified in this medium were determined and compared with those of the natural clay and with those of the clays m.odified under the same conditions but in distilled water. The samples were characterized by XRD, IR, TG and SEM. The modifications observed in the composition of the resulting zeolitic products depend not only on the NaOH concentration and treatment time but also on the nature of the synthesis media. The zeolitic products synthesized in seawater showed higher crystallinity and less heterogeneity. The treatment can be designed according to the characteristics required for the process in which the zeolitic product will be applied. 03-P-07-

Silicalite-I spheres prepared from preformed resin-silicate

composites L. Tosheva and J. Sterte

Division of Chemical Technology, Luledt University of Technology, Luledt, Sweden, [email protected] Silicalite-1 spheres were prepared in two steps by treating resin-silicate composite particles with structure-directing template solutions. In a first step resin-silicate composites were obtained as a result of an ion exchange of silica species within macroporous anion exchange resin beads. In a second step the composite particles were hydrothermally treated in structuredirecting template solutions at 170~ for 24 h. Finally, the organic components were removed by combustion at 600~ A number of samples were prepared using TPAOH and TPABr solutions of different concentrations as well as different weight ratios between template solution and composites. 03-P-08 - The synthesis of offretite single crystals using pyrocatechoi as

complex agent F. Gao (a), G. Zhu (a, b), Xiaotian Li (a), S. Qiu (a*), B. Wei (a), C. Shao (a) and O. Terasaki(b)

a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry., Jilin University, Changchun, P. R. China, e-mail: [email protected] b CREST, Department of Physics, Tohoku University, Sendai, Japan. Offretite single crystals with perfect morphology have been succesfully synthesized using pyrocatechol as complex agent. Compared with other methods, zeolite offretite prepared in this system has much larger size and better morphology. The influence of pyrocatechol has been studied, and the XRD patterns and the SEM photographs of offretite single crystals have been shown. The role of pyrocatechol has been characterized by 27 A1 NMR and 29 Si NMR, which show that an aluminum-pyrocatechol complex is formed in the reaction gel.

331 03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran G.-Q. Guo (a, b), Y.-J. Sun (c) and Y.-C. Long (a*) a Department of Chemistry, Fudan University, Shanghai 200433, P. R. China, b Research Institute ofBeijng Yanshan Petrochemical Corporation, SINOPEC, Beijing 102500, P. R. China, [email protected] c Center of Analysis and Measurement, Fudan University, Shanghai 200433, P. R. China FER zeolite can be prepared by spontaneous crystallization under hydrothermal conditions from the reactant with molar composition of 0.5 THF (tetrahydrofuran)-o0.215NazO eSiOze0.05AlzO3e20H20. The influence of SIO2/A1203 molar ratio, alkalinity, amount of template and reaction temperature was explored as well.

03-P-10 - Utilization of dry-gel conversion method for the synthesis of gailosilicate zeolites beta, ZSM-5 and ZSM-12 R. Bandyopadhyay (a), Y. Kubota (a), S. Nakata (b) and Y. Sugi (a)* a Department of Chemistry, Faculty of Engineering, Gifu University, Gifu-501-1193, Japan Email" [email protected]; Fax. 81-58-293-2597 b Department of Materials-process Engineering and Applied Chemistry for Environment, Faculty of Engineering and Resource Science, Akita University, Akita O10-8502, Japan Synthesis of gallosilicate zeolites [Ga]-beta, [Ga]-ZSM-5 and [Ga]-ZSM-12 was performed by dry-gel conversion (DGC) method. The crystallization of the dry gel was performed in presence of small amount of water, without which the crystallization failed. The method was convenient and as effective as conventional hydrothermal method. The samples were pure and highly crystalline, and showed characteristic of typical gallosilicate zeolites.

03-P-I 1 - A novel method for the synthesis of cancrinite type zeolites C.F. Linares (a), S. Madriz (b), M.R. Goldwasser (b) and C. Urbina de Navarro (c) a Universidad de Carabobo. Dpto de Quimica, clinares@thor, uc. edu. re, Venezuela. b Universidad Central de Venezuela, Caracas, Venezuela c Centro de Microscopia Electr6nica, UCV, Caracas, Venezuela A novel method for the synthesis of cancrinite type zeolites was developed by modification of an X faujasite type zeolite. Synthesis parameters such as crystallization time (16 h), temperature (80~ and pressure (autogenous pressure) were highly reduced by this procedure compared to previous synthesis methods. A 100% conversion of the ZX to cancrinite was observed with crystallinity higher than 80%. No other phases different to that of the cancrinite were observed. The basic character of the cancrinite was ascertained by means of its catalytic activity in the Knoevenagel condensation reaction.

332

03-P-12 - High-throughput strategies for the hydrothermal synthesis of zeolites and related materials N. Stock (a), N. Hilbrandt (a), K. Choi (b) and T. Bein (a)

a Department Chemie, Ludwig-Maximilians-Universitgit Manchen, Butenandtstr. 5-13, 81377 Mfinchen, Germany b Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA We have developed an automated parallel synthesis methodology that permits the rapid and detailed investigation of hydrothermal systems. The general procedure is as follows: automatic dispensing of reagents into autoclave blocks followed by synthesis, product isolation and automated structure analysis with X-ray diffractometry. Here we describe the application of this technique to the exploration of the aluminophosphate synthesis field. The effects of template, template concentration, A1 sources as well as mixed template systems are investigated. Emphasis is put on the study of cooperative structure direction effects.

03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr.

Centerfor Advanced Microgravity Materials Processing, Chemical Engineering Department, Northeastern University, Boston, MA 02115, USA, [email protected]. A 2 4 factorial experiment (factors: the SIO2/A1203 (A), H2SO4/Na20 (B), and Hexamethyleneimine (HMI)/SiO2 (C) ratios of the synthesis mixture, and the synthesis time (D)) was carried out to study the crystallization behavior of MCM-22 grown statically without aging in a broad reaction composition range. The four-factor interaction was significant (i.e., none of the factors acted independently) in influencing the crystallization kinetics of MCM22. The two three-factor (A.B.C and A.B.D) interactions were significant (i.e., none of the factors acted independently) in influencing the average MCM-22 particle size. The feasibility of using the lower amounts of HMI, and more siliceous synthesis mixtures than before to statically grow highly crystalline MCM-22 was demonstrated.

03-P-14 - Influence of nano-particle properties of MFI zeolite

agglomeration

on the catalytic

S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata*

Department of Applied Chemistry, Waseda University,3-4-10kubo, Shinjuku, Tokyo, 1698555, Japan, *[email protected] Microstructures of spherical and coffin-shaped MFI zeolite and its influence on catalytic activity for cumene cracking were investigated. While spherical MFI was composed of nanoparticles, coffin-shaped one possessed a layered structure where "nano-particles" with ca. 30 nm in size were accumulated on the dense core. Both the thickness of nano-particles layer and mesopore volume linearly correlated with the activity for cumene cracking, suggesting that the mesopores in MFI particles formed during "nano-particles" agglomeration, and that the reaction rate of cumene cracking was significantly influenced by the diffusion of cumene molecule in the nano-particles agglomerating layer.

333

0 3 - P - 1 5 - Rapid and mass production of porous materials using a continuous microwave equipment D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park*

Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), Yusung, Taejon 305-600, Korea," [email protected] A continuous microwave equipment (CME) has been developed to achieve a rapid and mass production for ZSM-5 and NaY zeolite. A precursor mixture for synthesis of ZSM-5 was prepared by mixing aluminosilicate gel with a nanoseed solution obtained under microwave irradiation, and pumped into the CME. Duration time in the CME was 5 min to accomplish the crystallization of ZSM-5 under microwave irradiation. For NaY zeolite, the precursor gel without nanoseeds was introduced into the CME and crystallization time was within 30 min. XRD and SEM results indicate that the structural properties of ZSM-5 and NaY zeolite obtained are similar to those obtained using batch-type microwave instrument and by conventional hydrothermal synthesis.

0 3 - P - 1 6 - Hydrothermal synthesis of vanadium-containing microporous aluminophosphates via the design of experiments approach L. Frunza (a,b), P. Van Der Voort (c), E.F. Vansant (c), R.A. Schoonheydt (b) and B.M. Weckhuysen (b)

a National Institute of Materials Physics, Bucharest, [email protected], Romania b Centrum voor Oppervlaktechemie en Katalyse, K. U Leuven, Belgium c Department Scheikunde, U.I. Antwerpen, Belgium An experimental design has been applied to the hydrothermal synthesis of VAPO-11 molecular sieve (AEL structure) from a VOSO,.5H20"AI(iPrO)3"Pr2NH'H,O gel. Statistical models that relate the selected synthesis variables with the crystallinity are proposed. The optimal synthesis conditions for the two structures (single phase or physical mixture with the AFO (VAPO-41) structure) are inferred from the models and compared with the literature data on single phase synthesis. Highly crystalline single-phase VAPO-11 can be best prepared at 170~ from a synthesis gel with low vanadium content and high water content.

03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for use in a membrane reactor E.E. McLearya, A.W. Hoogestegera, R.D. Sanderson a and J.C. Jansen a'b

alnstitute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology, Delft, The Netherlands To meet the dual challenge of selectivity and permeability for membranes used in reactors, there has been a thrust to support thin layers of highly selective membrane material on a porous support with high permeability. In this report we present the synthesis of such a thin molecular sieve layer of Silicalite-1 on a c~-A1203 support through the sintering of colloidal zeolite crystals (---150 nm) deposited with the Langmuir-Blodgett technique on the support.

334

03-P-18 - Mixed alkali templating in the Si/A! = 3 and 10 systems" a combinatorial study G.J. Lewis a, D.E. Akporiaye b, D. Bem a, C. Bratu a, I.M. Dahl b, A. Karlsson b, R.C. Murray a, R.L. Patton a, M. Plassen b and R. Wendelbo b aUOP LLC, g/[email protected], Des Plaines, IL USA ; bSINTEF, Blindern, Oslo, Norway A combinatorial approach is used to investigate mixed alkali templating in the Si/A1 = 3 and 10 zeolitic systems. The experimental design includes 15 high-symmetry alkali combinations of Li +, Na +, K + and Cs +, decoupled variations in total hydroxide and total alkali, and four digestion conditions giving 960 reactions. Compositional fields for BEA, ANA, MER, LTL and pollucite (ANA-Cs), interactions between alkali cations in the templating process, and the use of Principle Components Analysis to streamline the analysis of large XRD data sets are presented.

03-P-19 -Factors affecting composition and morphology of mordenite F. Hamidil, M. Pamba 2, A. Bengueddach 3, F. Di Renzo4 and F. Fajula 4 ID6partement de Chimie, USTO, B.P. 1505 Elmenaouar, Oran, Algeria 2Lab. Physique de la Matibre Condens~e, Universit6 Montpellier 2, Montpellier, France 3Lab. Chimie des Mat6riaux, Universit6 0ran Es-Senia, Oran 4Lab. Mat6riaux Catalytiques et Catalyse en Chimie Organique, ENSCM, Montpellier The shape and size of the crystals of mordenite, as well the Si/AI ratio, have implications on industrial applications in hydrocarbon conversion and separation. The ratio between the incorporation yields of silicon and aluminium is inversely proportional to the alkalinity level. Increased solubility of silica at higher pH accounts for the decrease of incorporation of silicon. The source of silica and the ageing of the synthesis gel also influence the final Si/AI ratio. The alkalinity of the synthesis system is also the main factor affecting the morphology of the mordenite crystals, flatter crystals being formed at low alkalinity.

335

0 4 - Isomorphous substitutions (Thursday) 0 4 - P - 0 6 - Uniform distribution of nickel during the synthesis of Si-ZSM-5 through solid-state transformation M. Salou, Y. Kiyozumi, F. Mizukami,* S. Niwa, M. Imamura and M. Haneda

National Institute of Materials and Chemical Research, [email protected], Japan Ni-containing Si-ZSM-5 was prepared through solid-state transformation, from kanemite and from TEOS, by adding nickel nitrate directly to the synthesis mixture. For both silica sources, nickel was found to be present at the outer surface and in the main channels of the zeolite. The outer surface nickel could be highly dispersed for a given Ni/Si ratio. In the case of TEOS, most of the nickel was present at the surface whereas in the case of kanemite, the distribution of nickel was more balanced between the surface and the bulk. The comparison with impregnation showed that the interaction of nickel with the zeolite framework was increasing in the order impregnation 100 kJ/mol than the reference LZY-82. Steam-aging causes a drastic decrease in acid sites density. However, in the temperature range (760-815~ investigated, the strength of the strongest acid sites in the reference LZY-82 remains practically unaffected after hydrothermal treatment. a

341

1 3 - P - 0 8 - ESR investigations of the catalytic properties of Lewis acid sites in H-mordenite T.M. Leu and E. Roduner Institut fiir Physikalische Chemie der Universitdit Stuttgart, Germany, e. roduner@ipc, uni-stuttgart. de The formation and the properties of Lewis acid sites (LAS) in the zeolite H-MOR were investigated by means of ESR spectroscopy through the observation of the radical cation formed upon adsorption of 2,5-dimethylhexa-l,5-diene (DMHD). The following facts have been established: (i) LAS which bind ammonia are not the sites which are responsible for the formation of radical cations. (ii) The amount of DMHD + formed is directly related to the partial pressure of molecular oxygen present in the system. (iii) The addition of oxygen to Hmordenite containing DMHD+'leads to a superoxide radical anion; furthermore, there is strong evidence for a catalytic process involving DMHD+as a radical intermediate in the oxidation of DMHD.

13-P-09- External surface acidity of modified zeolites: ESR via adsorption of stable nitroxyl radicals and IR spectroscopy A.B. Ayupov a, G.V. Echevsky a, E.A. Paukshtis a, D.J. O'Rear b and C.L. Kibby b a Boreskov Institute of Catalysis, Ak. Lavrentieva Av. 5, Novosibirsk, 630090, Russia b Chevron Research and Technology Co., 1O0 Chevron Way, Richmond, CA 94802, USA The external surface Br~3nsted and Lewis acidity of modified zeolites were characterized by FTIR of OH groups and adsorbed CO molecules and ESR of adsorbed nitroxyl radicals. The catalytic properties of the samples were tested in reactions of aromatics conversion: toluene, pseudocumene, and triisopropylbenzene. The correlation between acidity and catalytic activity has been found and discussed. The three methods of external surface characterization can lead to the entire view on zeolite acidity.

13-P-10 - Very strong acid site in HZSM-5 formed during the template removal step; its control, structure and catalytic activity A. Kohara, N. Katada and M. Niwa Tottori University, Koyama, Tottori 680-8552 Japan mikiniwa@chem, tottori-u.ac.jp, Fax +81-857-31-5256 Conditions of a step for template molecule removal affected strongly the concentration of very strong acid site in HZSM-5. Treatment with ammonia water at ca 373 K was also studied as a procedure to affect the solid acidity, and a similarity of acid sites created by both methods was identified. From the quantitative measurements of acid sites, it was found that the very strong acid site consisted of two A1 cations. Catalytic activity for octane cracking was enhanced by the presence of very strong acid site.

342

13-P-I1- Correlation between ~B NMR isotropic chemical shifts and structural parameters in borates and boro-silicates J. P16vert, F. Di Renzo and F. Fajula

Ecole Nationale Sup~rieure de Chimie de Montpellier, Franc. [email protected] liB MAS NMR has been performed for a variety of borates and boro-silicates. Boron atoms in tetrahedral coordination exhibit sharp resonance lines. The l~B isotropic chemical shift displays dependence as a function of framework geometry parameters such as the mean angles and the mean distances . Such correlation can be useful to characterize the boron site in disordered zeolites.

13-P-12 - Investigation of the paramagnetic effect of oxygen in the 23Na MAS N M R and 23Na MQMAS N M R spectra of LiNaX R.J. Accardi (a), M. Kalwei (b) and R.F. Lobo (a)

a Center for Catalytic Science and Technology, Department of Chemical Engineering, [email protected], University of Delaware Newark, DE 19716, USA. b Institute for Physical Chemistry, University ofMfinster Mfinster, Germany 48149. The paramagnetic effects of oxygen molecules on the site III sodium cations in zeolite LiNaX (~70% Li; ~30% Na) were investigated using variable temperature 23Na MAS NMR and 23Na MQMAS NMR spectroscopy. The presence of the oxygen caused a down-field paramagnetic shift for the site III resonance, although smaller than what was expected. 23Na MQMAS NMR was used to calculate isotropic chemical shifts and 2 na order quadrupolar shifts. The quadrupolar shifts of the room temperature sodium resonance remain the same irrespective of the presence or absence of physisorbed oxygen, however, the quadrupolar shift was found to increase at lower temperatures.

13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laserinduced fluorescence of adsorbed quinoline A. Lassoued, J. Thoret, P. Batamack, A. G6d6on and J. Fraissard

Laboratoire de Chimie des Surfaces, UPMC-CNRS, ESA 7069, 4 place Jussieu, 75252 Paris cedex 05, E-mail.'[email protected], Fax : 33.(0)1.4427.5536, France. We report the characterization of acidic sites in HY zeolite, dealuminated or not, and Y zeolites exchanged with lanthanum (LAY), by the laser-induced fluorescence (LIF) method using an N-heteroaromatic base, quinoline, which is adsorbed on the surface and photoexcited at 240 nm. Spectra of quinoline reveal interactions between the adsorbate and surface sites. Unstructured broad bands with lifetimes less than 1 gsec are observed in all samples. Strong Bronsted acid sites interact with quinoline to form the quinolinum ion, that ion being revealed by a band peaking at 390 nm. The acidity of LaY samples is a function of the La 3+ exchange rate; this was fast highlighted by LIF spectroscopy.

343

13-P-14 - D y n a m i c behaviour of acetonitrile molecules adsorbed in ALPO45 and S A P O - 5 studied by solid N M R method S. Ishimaru, M. Ichikawa, K. Gotoh and R. Ikeda

Department of Chemistry, University of Tsukuba, Tsukuba 305-8571, Japan We studied characteristics of micropores in molecular sieves A1PO4-5 and SAPO-5 by observing IH and 2H NMR to detect dynamic behaviour of acetonitrile molecules adsorbed in the pores. From 2H spectra and ~H relaxation times, it was shown that the molecular motion was strongly affected by the existence o f - O H groups on the pore-wall of SAPO-5. The details of the motions are discussed from ~H NMR TI and T2 data.

13-P-15 - D e t e r m i n a t i o n of the Si/A! ratio of faujasite-type zeolites C.H. Rtischer l*, J.-C. Buhl I and W. Lutz 2

llnstitut fiir Mineralogie, Universit~itHannover, Welfengarten 1 Hannover, Germany. *C.Ruescher@mineralogie. uni-hannover,de 2WITEGA Angewandte Werkstoff-Forschungg. GmbHBerlin, Germany Zeolites Y dealuminated by Si/A1 substitution using SIC14 (DAY-S) and dealuminated thermochemically in steam (DAY-T) were investigated by X-ray powder diffraction, infrared spectroscopy and wet chemical methods. The dependence of lattice constants (a) on the molar ratio x = (I+Si/A1) z show non-ideal solid solution behaviour. In a first approximation the change in a (in nm) can be described as: a = 0.187x+2.412, for 0.1 < x < 0.5. For x < 0.1 the change in lattice constant saturates towards a = 2.425 nm. A similar shift in the double ring mode (WDR)is observed, tailing off.

13-P-16 - Theoretical investigation toluene adsorbed on zeolite X

of the chemical shift anisotropy

of

A. Simperler (a), A. Philippou (b), D.-P. Luigi (b), R.G. Bell (a) and M.W. Anderson (b)

a The Royal Institution of Great Britain, London, United Kingdom, [email protected] b UMIST Centre for Microporous Materials, Manchester, United Kingdom Adsorption of toluene on zeolites Li-X, Na-X, K-X, Rb-X, and Cs-X has been investigated with quantum chemical methods. Calculations of geometries, Mulliken partial charges, and 13C chemical shift parameters of clusters representing the catalytically active site are presented. The polarisation of the toluene carbons is the first step in alkylation reactions catalysed by zeolites and, at an early stage, will influence the outcome of the reaction. We show the simultaneous influence of the Lewis acidic cation and the basicity of the zeolite is responsible for altering the electron distribution within the toluene and thus affecting the outcome of an alkylation reaction.

344 13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR spectroscopy J. Datka, B. Gil and K. G6ra-Marek Faculty of Chemistry, Jagiellonian University, 30-060 Cracow, Ingardena 3, Poland. datka@chemia, uj. edu.pl Dehydroxylation was studied as one of methods of "tuning" the acid properties of ferrierite. The concentration and acid strength of both Br6nsted and Lewis acid sites were determined by IR spectroscopy. In non dehydroxylated ferrierite, the concentration of Br6nsted sites was the same as the value calculated from the composition of zeolite. The maximal concentration of Lewis acid sites in the most dehydroxylated zeolite was close to the stoichiometric value: i.e. half of the concentration of Br6nsted sites. The acid strength of OH groups remaining in partially dehydroxylated ferrierites decreased and the strength of Lewis sites formed increased with the extent of dehydroxylation. The hydroxyls inside 10-ring channels and hydroxyls in ferrierite cages are prone to dehydroxylation in the same degree.

13-P-18 - Aluminium species spectroscopy of the active sites

in activated

zeolites:

solid-state

NMR

B.H. Wouters (a), T.-H. Chen (b) and P.J. Grobet (a)

a Center for Surface Chemistry and Catalysis, Department oflnterphase Chemistry, K.U. Leuven, [email protected], Leuven, Belgium b Department of Chemistry, Nankai University, Tianjin, 300071, PR China Aluminium species in activated zeolites has been studied by solid-state NMR spectroscopy. Framework A1-OH defect species are at the origin of reversible tetrahedral-octahedral transformation in mild calcined zeolites. Depending on the calcination degree, the 30 ppm line in the 27A1 MAS NMR spectra of zeolites is a superposition of deformed tetrahedrally coordinated and penta-coordinated AI species.

13-P-19- Aluminium distribution in high silica pentasil ring zeolites B. Wichterlov~i, J. D~de6,ek, Z. Sobalik and J. 12ejka

J. Heyrovsl@ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic;cejka@3"h-inst.cas.cz Distribution of aluminium in the framework of ZSM-5 and Beta zeolites, represented by "A1 pairs" [A1-O-(Si-O)I,2-A1] and "single A1 atoms" far distant from each other, is estimated from the distribution of divalent Co ions at the individual cationic sites, as obtained from the Co(II) Vis spectra, and the changes in the concentration of OH groups and Lewis sites due to Co(II) exchange, monitored by FTIR. It is shown that the distribution of framework A1 is not random, but it is affected by the concentration of aluminium and procedure of zeolite synthesis.

345

1 3 - P - 2 0 - Effects of hydration on AIPO4-14 and AIPO4-18 structures: a~p M A S a n d 27A! 3 Q - M A S N M R s t u d y b C. V. Satyanarayanaa, R. Gupta, K. Damodaran, S. Sivasankera and S. Ganapathy b*

aCatalysisDivision bPhysical Chemistry Division,[email protected], NCL, Pune, India Structural transformations occurring in A1PO4-14 and A1PO4-18, upon calcination and rehydration, have been studied by 31p and 27A1 MAS/3Q-MAS NMR spectroscopy. Isotropic signals obtained from 31p MAS and 27A1 3Q-MAS aid in the direct detection of number of in equivalent T-sites, which could be assigned based on the correlation of the isotropic shifts with mean T-O-T angle. In calcined samples where only tetrahedral P and AI environments exist, AIPO4-18 results clearly show a constrained geometry with minimal tetrahedral distortion for the PO4 and AIO4 structure building units. Signal multiplicity in 3~p and 27A1 spectra of calcined-rehydrated samples of AIPO4-14 and -18 suggest that both respond to hydration in a similar fashion to yield structures with lower space group symmetry.

13-P-21 - Comparative study of the acidity of the structurally related faujasite type zeolites: FAU, EMT and ZSM-20 H. Kosslick (a), R. Fricke (a), H. Miessner (b), D.L. Hoang (a) and W. Storeck (c)

a Institute of Applied Chemistry Berlin-Adlershof kosslick@ aca-berlin.de, Germany b Institute of Environmental Technologies, I. U. T, [email protected], Germany c Federal Institute of Materials Research and Testing (BAM),Berlin, Germany Acidic properties of EMT and FAU type zeolites as well as their intergrowths with similar A1 content, which contain the same structural subunits but differ in stacking, have been studied by different physico-chemical methods like NH3-FTIR. Small finestructure differences have been found which might be the origin of different strengths of acid sites. Slight variations in the acidity of Bronsted acid sites are indicated by the low frequency shift of the OH stretching vibration band of hydroxy groups which are located in the large cavities. In consequence, the protonic acidity is slightly enhanced in the following order: HFAU < HZSM-20 < HEMT.

13-P-22 - The effect of flexible lattice aluminum in zeolites during the nitration of aromatics M. Haouas (a), A. Kogelbauer (a,b) and R. Prins (a)

a Laboratory of Technical Chemistry, Swiss Federal Institute of Technology (ETH), Zurich, [email protected], Switzerland," b Department of Chemical Engineering, Imperial College of STM, London, U.K. The nitration of toluene with nitric acid and acetic anhydride with zeolite catalysts was studied by means of multi-nuclear solid-state NMR spectroscopy in order to explain the enhanced para-selectivity observed with zeolite beta. The reversible transformation of framework aluminum from a tetrahedral into an octahedral environment was revealed by 27A1 NMR upon interaction of the zeolite with the different components of the nitrating system. The flexibility of the lattice seems to play an important role in the regio-selectivity of nitration catalyzed by zeolites.

346

13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double resonance solid state NMR S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux a and S. Ganapathy* National Chemical Laboratory, Pune 411 008, India LDSMM, CNRS-8024, Universite de Lille, F-59655, France The structural characterization of Br0nsted acid sites in zeolites can be investigated through heteronuclear double resonance NMR experiments under Magic Angle Spinning (MAS). With these experiments, we have recoupled the 1H-27AI heteronuclear dipolar interactions by using the Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) technique. The signal evolution was followed and monitored under MAS and the REAPDOR fraction was experimentally measured. Its time evolution is shown to reflect the differences in Br0nsted acidity of three well known zeolites, namely, LTL, LTY and MOR.

13-P-24- Measurement of M Q M A S heteronuclear correlation spectra in microporous aluminophosphates C. Fernandez (a) and M. Pruski (b). a) Laboratoire ale Catalyse et Spectrochimie, CNRS UMR 6506, ISMRA/Universit6 de Caen, France; b) Ames Laboratory, Iowa State University, Ames, USA Christian. Fernandez@ismra. ~. We present a solid-state nuclear magnetic resonance (NMR) experiment that allows the observation of a high-resolution two-dimensional heteronuclear correlation (2D HETCOR) spectrum between aluminum and phosphorous in aluminophosphate molecular sieve VPI-5. The experiment uses multiple quantum magic angle spinning (MQMAS) spectroscopy to remove the second order quadrupolar broadening in 27A1 nuclei. The magnetization is then transferred to spin-l/2 nuclei of 31P via cross polarization (CP) to produce for the first time isotropic resolution in both dimensions.

13-P-25 - FTIR studies of the interaction of aromatic and branched aliphatic compounds with internal, external and extraframework sites of MFI-type zeolite materials T. Armaroli (a), A. Guti6rrez Alejandre (b), M. Bevilacqua (a), M. Trombetta (a), F. Milella (a), J. Ramirez (b) and G. Busca (a). a DICheP, Universith di Genova, icibusca@csita, unige, it~ Italy b UNICAT, UNAM, [email protected], Mexico D.F, Mexico The interaction of different nitriles (acetonitrile, pivalonitrile and benzonitrile), of branched aliphatic compounds (2,2-dimethylbutane, tert-butyl-alcohol, methyl-tert-butylether, methyl and dimethylcyclohexanes) and of aromatics (benzene, toluene, ortho-, meta- and paraxylene, pyridine, picolines and lutidine) has been studied over four different ZSM5 zeolites, over silicalite-1 and titanium silicalite-1 and over boralite BOR-C. Internal, external and extraframework sites have been characterized and the access to the cavities discussed.

347

1 4 - Frameworks, Cations, Clusters (Thursday) 14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite T. Ohgushi and K. Ishimaru

Department of Materials Science, Toyohashi University of Technology, ohgushi@tutms, tut. ac.jp, Japan. Relaxation processes caused by Na § ion in Nala-A zeolite were studied by the dielectric technique. Two loss peaks (two relaxations) were observed in the dehydrated state, and were simultaneously influenced by the water adsorption in the extremely low vapor pressure or the extremely low adsorbed amount. From the way of the influence and a character in the cation distribution of the zeolite, both relaxations were related to the movements of Na + ion on the site near the 4-membered oxygen ring (4MR). It was concluded by considering the arrangements of some cation sites around 4MR that the loss observed in the higher frequency region was caused by the jump of Na § ion between 4MR and 6MR, and the loss in the lower frequency region by the jump ofNa + ion between 4MR and 8MR.

14-P-07 - Adsorption of DTBN at monovalent cations in zeolite Y as studied by electron spin resonance spectroscopy M. Gutjahr, W. B6hlmann, R. B6ttcher and A. P6ppl University of Leipzig, poeppl@physik, uni-leipzig, de, Germany. One major challenge in the research of microporous materials is the spectroscopic characterization of acid sites. A promising approach is their complexation with paramagnetic probe molecules and the subsequent characterization of the adsorption complex ESR techniques. We used the continuous wave ESR method and modem high resolution pulsed ESR techniques such as hyperfine sublevel correlation spectroscopy to study adsorption complexes formed by paramagnetic Di-tert-butyl nitroxide probe molecules and zeolite cations Li+, Na +, K +, Cs+ in Y zeolites. These investigations allow a determination of the geometrical structure of the adsorption complexes and provide information about the influence of the electronegativity of the various acid sites on the electron density distribution.

14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES studies at Mo K and Llll-edges F.G. Requejo (a,b), E.J. Lede (a), L.B. Pierella (c) and O.A. Anunziata (c)

a Dto. Fisica, Fac. Cs Ex, UNLP and IFILP (CONICET), La Plata, Argentina b Present address." Material.Sience Division., LBNL, Berkeley, CA, USA c centro de Investigaci6n y Tecnologia Quimica(CfTe), UTN-FC-Cordoba-Argentina. Molybdenum catalysts, prepared by incipient wetness impregnation of ammonium-MFI, MEL and BEA zeolites, have been studied by XANES at the Mo L2,3-edge and FTIR. The catalytic activity shows on the nature of Mo species. Due to the splitting at Mo La-edges obtain by XANES, Mo atoms are mainly in tetrahedral surrounding in the samples. Linear XANES fit provide information about concentration of Mo-sites related with their coordination. Differences between linear XANES fits at L3 and K-edges can be attributed to different measurement conditions, indicating different of Mo-sites according their hydration capability.

348

14-P-09 - EPR studies on nitrogen monoxide in zeolites H. Yahiro (a), N. P. Benetis (b), A. Lund (b) and M. Shiotani (c)

(a) Faculty of Engineering, Ehime University, Matsuyama, [email protected], Japan. (b) Chemical Physics Laboratory, 1FM LinkOping University, LinkOping, Sweden (c) Faculty of Engineering, Hiroshima University, Higashi-Hiroshima, Japan Nitrogen monoxide (NO) introduced into Na-A(Na-LTA), Na-mordenite(Na-MOR), and NaZSM-5(Na-MFI) zeolites was studied by X-band-EPR measurements. The EPR spectra of NO introduced into Na-LTA revealed the presence of two monoradicals with different rotational rates. The rotational motion of the NO monoradical formed in Na-LTA differed from that in Na-MOR and Na-MFI. A (NO)2 biradical was present in Na-LTA, while it was absent in the calcium ion-exchanged A-type zeolite, indicating that the pressure of Na + is essential for the (NO)2 biradical formation.

14-P-10 - Evidence of partially broken bridging hydroxyls in molecular sieves from IH MAS spin echo N M R spectroscopy T.-H. Chen (a,b), B.H. Wouters (b) and P.J. Grobet (b)

aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001 Heverlee (Leuven), Belgium, Piet. [email protected]. be By spin echo editing NMR method, combined with the lH{27Al}spin echo double resonance, a new IH signal was found in the thermally treated molecular sieves, reflecting the complexity of hydroxyls as well as the aluminum state in the dehydrated state. It represents an initial stage of the dehydroxylation, or may be related with the initial stage of dealumination.

14-P-11 - Structure change of molecular sieve SAPO-37 at high temperature studied by 27A! MQ MAS N M R T.-H. Chen (a,b), B. Wouters (b) and P. Grobet (b)

aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001 Heverlee (Leuven), Belgium, [email protected] When SAPO-37 was calcined at 1173 K, Si atoms become mobile and detached from the framework to aggregate to form polymorph silica, while AI-P dense phase was formed, corresponding to a new AI signal which can be distinguished by the 27A1 MQMAS spectrum. The move of atoms in SAPO-37 is the start of the collapse of the framework.

349

14-P-12 - Effects of molecular confinement on structure and catalytic behaviour of metal phthalocyanine complexes encapsulated in zeolite-Y S. Seelan, D. Srinivas*, M.S. Agashe, N.E. Jacob and S. Sivasanker National Chemical Laboratory, Pune 411 008, India, [email protected] Metal phthalocyanine complexes (MPc; M = V, Co and Cu) encapsulated in zeolite-Y were prepared by "in-situ ligand synthesis" and characterized by chemical and thermal analyses and FT-IR, diffuse reflectance UV-vis and EPR spectroscopic techniques. The studies provided evidence for the encapsulation of MPc inside the supercages of zeolite-Y. The Pc moiety distorts from square planarity as a consequence of encapsulation. The encapsulated complexes exhibited enhanced styrene epoxidation activity with tert-butylhydroperoxide compared to the neat complexes in homogeneous medium. The activity and product selectivity of the encapsulated complexes varies with the central metal atom.

14-P-13 - Investigations on isomorphous substitution and catalytically active centres in MeAPO-31 (Me = Mn, Co, Zn, Ti) N. Novak Tusar (a), A. Ristic (a), A. Ghanbari-Siahkali (b), J. Dwyer (b), G. Mali(a), I. Arcon (c) and V. Kaucic (a) a National Institute of Chemistry, Ljublj'ana, [email protected], Slovenia; b Centre for Microporous Materials, UMIST, Manchester, UK; c Nova Gorica Polytechnics, Nova Gorica, Slovenia An incorporation of manganese(II), cobalt(II), zinc(II) and titanium(IV) into the framework aluminium sites of A1PO4-31 is studied. Isomorphous aluminium substitution with cobalt and zinc was confirmed from static 3~p NMR spectrum and 31p MAS NMR spectrum, respectively. UV-VIS and XANES spectra revealed a partial oxidation of framework manganese(II) into manganese(III) in calcined MnAPO-31 and thus a presence of redox centres in the product. The generation of acidic sites (Bronsted and Lewis) in MeAPO-31 was supported by ammonia adsorption/desorption analysis. Strength of acid sites in the studied catalysts decreases as following: MnAPO-31 > CoAPO-31 > ZnAPO-31. Titanium(IV) is present in TAPO-31 as anatase and it is not incorporated into framework sites of AIPO4-31.

14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-I) synthetized by different methods N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. Cagnoli, S.G. Marchetti and A.A. Yeramian CINDECA, Fac. Cs. Exactas, Fac. Ingenieria, U.N.L.P., CIC, CONICET., [email protected]; Calle 47 N ~ 257 (1900) La Plata, Argentina. Three TS-1 zeolites were prepared by three different methods. In order to determine that all of them are "well manufactured", DRX, IR, SEM and DRS were used. The jointly use of probe molecules (H202 and C6H6) and DRS allowed us to detect differences in the population of the named "closed" and "open" Ti 4+ sites and in their geometries in the three zeolites. These differences lead to distinct catalytic behavior when these solids are tested in the oxidation of benzene with H202.

350

14-P-15 - Behaviour of F e ( l l l ) ions in Y zeolites in the presence of Cu(II) and Ag(I) ions: an ESR study A.L. Kustov (a), E.E. Knyazeva (a), E.A. Zhilinskaya (b), A. Aboukais (b) and B.V. Romanovsky (a)

a Chemistry Department Moscow State University, Moscow, V-234, Russia, bvromanovsky@mail, ru b Laboratory of Catalysis and Environment, EA 2598, Littoral University, 59140 Dunkerque, France, [email protected] Quenching effect of Cu(II) and Fe(III) paramagnetic ions when both present within NaY large cages is evidenced. On the contrary, the presence of the same quantity of diamagnetic Ag(I) ions in the NaY zeolite did not influenced on the EPR patterns of Fe(III). Observed quenching effect is supposed to be explained caused by the strong dipole-dipole interaction of paramagnetic species. Also, the catalytic activity of Fe-containing zeolite in methanol oxidation decreases after loading a Cu compound.

14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in zeolites Y. Huang,J.H. Leech and R.R. Poissant

University of Western Ontario, Department of Chemistry, London, ON, Canada N6A 5B7 FT-Raman spectroscopy is a powerful technique for investigating host-guest interactions in zeolitic systems via monitoring the guest species. In this presentation, we report our recent results on the investigations of host-guest interactions in two aspects of zeolite chemistry: (1) examining the dynamic and conformational properties of several closely related alkylcyclohexanes including cyclohexane, methylcyclohexane and trans-l,4-dimethylcyclohexane adsorbed inside ZSM-5 framework and (2) probing the reactivity of organometallic species such as (rl6-benzene)tricarbonylchromium(0) on the surface of zeolite Y.

14-P-17 - High-temperature MAS N M R investigation of the mobility of cations and guest compounds in zeolites X and Y M. Hunger, A. Buchholz and U. Schenk

Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany By high-temperature 23Na MAS NMR spectroscopy could be shown that the rapid exchange of sodium cations in dehydrated zeolite Na-Y starts at ca. 573 K and is characterized by an activation energy of EA = 20+2 kJ/mol. The ra~3id exchange of cesium cations in dehydrated zeolite CsNa-Y starts at ca. 423 K. Applying Cs MAS NMR spectroscopy, an activation energy for the cesium exchange in zeolite Y equal to that for the sodium exchange was determined. These activation energies are significantly lower than those estimated for cesium exchange processes observed at temperatures of 423 to 773 K for dehydrated zeolites CsNa-Y and CsNa-X impregnated with cesium hydroxide as guest compound (EA ca. 85 to 115 kJ/mol).

351

14-P-18 - Generation of long-lived electron-hole pairs through sorption of Biphenyl into acidic ZSM-5 zeolites I. Gener (a), A. Moissette (a), H. Vezin (a), J. Patarin (b) and C. Br6mard (a) a Universit6 des Sciences et Technologies de Lille, Villeneuve d'Ascq, France Claude. Br~mard@univ-lille 1.fr b Ecole Nationale Sup6rieure de Chimie de Mulhouse, France. The EPR, UV-visible investigations as well as Raman scattering results provide informative clues about the formation and nature of long-lived electron-hole pairs through spontaneous biphenyl ionization upon sorption in the void space of activated ZSM-5 zeolites. The transferred electron is trapped within the framework by electron accepting site, while biphenyl radical cation captures one electron from electron donating sites of zeolite framework to restore BP ground state and causes an electron deficient hole.

14-P-19 - Defects study in microporous materials by HRSEM, H R T E M and diffraction techniques G. Gonzalez*, Z. Lopez* and R. Reichelt** *Laboratorio de Materiales, Centro Tecnol6gico, lnstituto Venezolano de Investigaciones Cientificas, IVIC, Caracas 1020A, Venezuela. e-mail. [email protected]. **Institut fur Medizinische Physik und Biophysik der Universitat Munster, Munster, Germany Control synthesis of MFI, MEL and MFI/MEL intergrowth systems has been performed by a systematic variation of different parameters: SIO2/A1203, template/SiO2, Na20/SiO2, H20/ SiO2, templates ratio (TPABr/TBABr), temperature and crystallization time. The study of the relationship between synthesis parameters, crystal morphology, crystal size and density of defects has been carried out. Detailed characterization has been performed by HRSEM, HRTEM, x-ray diffraction, electron diffraction and sorption measurements.

14-P-20- The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites and their photocatalytic reactivity S. Higashimoto a, M. Matsuoka a, M. Che b and M. Anpo a* a Dept. Appl. Chem., Osaka Prefecture University, [email protected], Japan b Laboratoire de R6activit6 de Surface, Universit~ P. et M. Curie, UMR7609, CNRS, France XAFS (XANES and FT-EXAFS) and phosphorescence studies including lifetime measurements of several types of vanadium silicalite catalysts clearly showed the oxidation state and coordination geometry of the highly dispersed V-oxides as well as the local distortion structure of these species in their framework structures. Furthermore, dynamic quenching studies of the phosphorescence by adding reactant molecules showed that the charge transfer excited triplet state of these V-oxides, (V4+ - O-)*, acted as active sites for the photocatalytic decomposition reactions of NO both in the presence and absence of propane, their reactivity being strongly dependent on the framework structure of these catalysts.

352

14-P-21 -Characterization of aluminium and iron sites in MCM-22 J. (~ejka (a), J. D6de~ek (a), J. Kotrla (a), M. Tudor (a), N. Zilkovd (a) and S. Ernst (b)

a J. Heyrovsl~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic; cejka@l'h-inst.cas.cz b Department of Chemistry, Chemical Technology, University of Kaiserslautern, Erwin SchrOdinger Strasse 54, D-67663 Kaiserslautern, Germany Type and distribution of aluminium and iron in the framework of zeolite MCM-22 were investigated using adsorption of d3-acetonitrile, pyridine and 2,6-di-tertbutylpyridine followed by FTIR spectroscopy, sodium ion-exchange and UV-Vis spectroscopy of Co 2+ ions located in cationic positions. Detailed analysis of aluminium and iron distribution among single ions, ion pairs, Br6nsted and Lewis sites and internal and "external" surface is provided.

14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ MSssbauer

study K. L~zfir (a), N. Zilkovfi (b) and J. (~ejka(b)

a Institute of Isotope and Surface Chemistry, Chemical Research Center, P.O. Box 77, H1525 Budapest, Hungary; b 3{. Heyrovsl~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic; cejka@l'h-inst, cas. cz Distribution of Fe 2§ and Fe 3§ framework ions and their coordinations in FeAPO-11 structure were investigated employing M6ssbauer spectroscopy and X-ray powder diffraction. . . . . Simultaneous stablhzatlon of Fe 2 + and Fe 3 + ions in various coordination states was observed. It was shown that the structure of FeAPO-11 is rather flexible and the coordination of iron strongly depends on the form of pretreatment. Among ferrous ions, facile transition between octahedral and distorted trigonal coordinations was observed.

1 4 - P - 2 3 - Comparative properties of modified HEMT and HY zeolites from

the FTIR study of CO adsorption" effect of the dealumination amorphous debris on the Br~insted acidity

and

O. Cairon (a) and T. Chevreau (b)

a LCTPCM, UMR 5624, rue Jules Ferry, Pau, [email protected], France b Catalyse et Spectrochimie, ISMtL4-Universitd Caen, [email protected] Progressive CO adsorption has been studied by FTIR spectroscopy on two series of acidleached steamed HEMT and HY zeolites with various Si/A1F ratios. Acidity of structural OH groups of steamed hexagonal faujasites was determined and compared with the results already obtained with the cubic series. Moreover, quantitative estimation of Br6nsted acidity of extraframework phase (numbers and strength) was carried out and allowed to complete the comparison between the two structural varieties. Only minor differences were detectable.

353

14-P-24- Raman spectroscopic study of 2,2'-bipyridine sorbed into ZSM5 A. Moissette, C. Brdmard, I. Gener and N. Louchart

Laboratoire de Spectrochimie Infrarouge et Raman, Universit~ des Sciences et Technologies de Lille, 59655 Villeneuve d'Ascq cedex, France, [email protected] Sorption of 2,2'-bipyridine (bpy) into the void space of Mm/nZSM-5 (m = 0, 3, 6; M = Na +, Zn 2+, H +) zeolites was studied by Raman spectrometry. The differences in the spectra obtained from the loaded zeolites have been rationalized in terms of probable conformation within the zeolite channels. It appears clearly that bpy conformation depends on the aluminum content of the framework, nature of cations and zeolite acidity, bpy occluded in silicalite-1 was found to be in the trans conformation. The non bonding interactions between the extraframework Na + cation and occluded bpy stabilize the cisoid non-planar conformer, whereas the coordination bonding between Zn and N atoms constrains the cis planar conformation. In HZSM-5, bpy sorption results in both mono and diprotonation of bpy. 9

9

9

2+

9

14-P-25 - Fractals of silica aggregates Z. Li a, D. Wu a, Y.-H. Sun a*, J. Wangb, Yi Liu b and B. Dong b

aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China bSynchrotron Radiation Laboratory, Institute of High Energy Physics, Chinese Academy of Sciences, P.O.Box 918, Beij'ing 100039, P R China Small Angle X-ray Scattering was used to determine the fractal property of silica aggregates prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol. As-produced samples were found to be mass fractals. The fractal dimensions spanned the regime 2.1---2.6 corresponding to more branched and compact structures. Both RLCA and Eden models dominated the kinetic growth under base-catalyzed condition

14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3 studied by XAFS and UV-VIS spectroscopies H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi

Yokohama National University, Yokohama, [email protected], Japan Direct incorporation of Mo into template-directed mesoporous silica was carried out via acidic (S'X+I-) route. High Mo-loading was achieved (9 wt%, as MOO3) without destructing the regularity of SBA-1 and SBA-3. The local structural environment of Mo was analysed by UV-vis and EXAFS spectroscopies in comparison with that of Mo-impregnated mesoporous silicas. Edge energy of UV-vis spectra and coordination number obtained from EXAFS showed that Mo agglomerates more easily than in the case of impregnation while the local symmetry of Mo did not differ significantly among the molybdosilicates.

354

14-P-27 - Quantification of electric-field gradients in the supercage of Y zeolites by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I = 1/2) Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard Laboratoire de Chimie des Surfaces, CNRS ESA 7069, SystOmes Interfaciaux fi l'Echelle Nanomdtrique, Universit~ Pierre et Marie Curie, 4 Place Jussieu, Casier 196, Tour 55, 75252 Paris Cedex 05, [email protected], France In the supercages of HY zeolite, the difference in chemical shift (Scs(131Xe) - ~cs(129Xe)) of the two NMR-observable isotopes 131Xe, which is sensitive to the electric-field gradient (EFG), and i29Xe, which is not sensitive to EFG, is -5 ~lPm at room temperature. The latter value is due to the second-order quadrupole shift of I Xe and provides us with the EFG generated by the framework of this microporous material: 16.3xl 0 ~9V.m -2.

14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion exchange in aqueous medium or in the solid state M.S. Batista a, M.A.M. Tortes b, E. Baggio-Saitovich b and E.A. Urquieta-Gonzfilez a Dep. Chem. Eng./UFSCar, S6o Carlos- SP, Brazil. e-mail." [email protected] bBrazilian Center for Research in Physics, Rio de Janeiro, Brazil. The Fe species formed during the preparation of Fe/ZSM-5 catalysts by ion exchange in aqueous medium or in the solid state were studied. XRD, EPR, M6ssbauer spectrocopy (MOSS) and chemical analysis (AAS) were used to sample characterization. The catalysts were evaluated through the propane oxidation in the range from 373 to 773 K. The MOSS data evidenced the presence of Fe +3 species in charge-compensation sites and a more content of hematite (Fe203) in the catalysts prepared in aqueous medium. In the propane oxidation, the activity of the Fe/ZSM-5 can be correlated with the amount of Fe-cationic species, confirming that they are the responsible for the catalytic activity.

14-P-29 - Laser ablation mass spectrometry: a technique for observing zeolite occluded molecules S. Jeong(a), K.J. Fisher(a), G.D. Willett(a) and R.F. Howe(b)* a School of Chemistry, University of New South Wales, Sydney NSW 2052, Australia b Chemistry Department, University of Aberdeen, Aberdeen AB24 3 UE, UK, [email protected] Laser ablation mass spectrometry (LAMS) uses a pulsed laser to destroy zeolite structures, release and ionize molecules occluded within the zeolite pores. High resolution mass spectrometry can then be used to study the ions produced. This paper describes LAMS studies on two well defined model systems: hexamethylbenzene(HMB) adsorbed in NaFAU, and the tetrapropylammonium(TPA) template in MFI. It is shown that LAMS can be used to identify the adsorbed species.

355

1 4 - P - 3 0 - Characterisation of TS-I active sites by adsorption of organic probes C. Flego*, A. Carati and M.G. Clerici EniTecnologie S.p.A. [email protected] - S. Donato Mil. (MI) - Italy UV-Vis-IR spectroscopy shows the involvement of Ti sites of TS-1 in the adsorption of oxygenated probes (i-propanol, diethyl ether, propylene oxide, glycols) and pyridine. The interaction affects the IR signal at 3725 cm l, which is tentatively attributed to TiOH groups. In partially hydrated TS-1, lattice Ti is involved in the sorption of organic molecules directly through one OH group and indirectly influencing the environment through the nearest SiOH groups. S-1 shows in the comparison with TS-1 a lower density and a weaker strength of adsorption of the organic probes. The interaction of the probes with Ti sites is reinforced through co-operative H-bonds in MFI zeolitic structure, while in the amorphous mesoporous titanium-silicalite this phenomenon is less relevant.

14-P-31 - NIR FT-Raman spectroscopy on molecular sieves E. L6ffler and M. Bergmann Lehrstuhl Technische Chemic, Ruhr-Universiti~t Bochum, P.O. Box 102148, D-44780 Bochum, Germany The potential of NIR FT-Raman spectroscopy for the investigation of zeolites (vanadylcontaining MFI, TS-1) as well as alumophosphate-based molecular sieves (AEI, CHA, CLO) are described. In Raman spectra of template containing samples bands of the organic species dominate. By dispersive Raman microscopy a spatial distribution in a CoAPO-34 crystal is observed. The Raman spectra allow a very rapid and sensitive detection of anatase formed during thermal treatment of as-synthesised titanium-containing zeolites. Different vanadium species are detected in vanadium-containing ZSM-5.

14-P-32 - Characterization of Zn and Fe substituted mordenite by X A F S M. Dong, J.-G. Wang* and Y.-H. Sun State Key Laboratory of Coal Conversion, Taiyuan, Shanxi, [email protected], P.R. China The local structures of Zn (II) and Fe (III) in the lattice framework of mordenites have been characterized by means of X-ray Absorption Fine Structure. The main absorption structure of the XANES reveals the covalent bonding between the heteroatom and the lattice oxygen atom. The pre-edge structure appeared in XANES spectra of (Si, Fe)-MOR suggests a tetrahedral structure of Fe, which confirms the incorporation of Fe into the zeolite framework. Furthermore, the tetrahedral structure of the heteroatoms in the framework and their coordination distances are determined by using EXAFS technique.

356

14-P-33 - Identification of vanadium species in VAPO and V A P S O aluminophosphate by UV resonance raman spectroscopy Jia. Yu, Z. Liu*, Q. Xin and C. Li Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023, [email protected], China A sensitive UV resonance Raman spectroscopy has been used to characterize both VAPO-5 and VAPSO-5 aluminophosphate. UV-Raman spectra of VAPO-5 suggest that three different vanadium species exist in VAPO-5, but the framework vanadium species are not observed. However, the framework vanadium species exist in VAPSO-5 and are located in the matrix of framework silica.

14-P-34 - On the interaction of H20 with TS-I: a spectroscopic and ab-initio study A. Damin (a), G. Ricchiardi (a), S. Bordiga (a), F. Bonino (a), A. Zecchina (a), F. Ricci (b), G. Span6(b), F. Villain (c) and C. Lamberti (a)

a Dipartimento di Chimica 1FM, Via P. Giuria 7, 1-10125 Torino, Italy, [email protected] b EniChem S.p.A., Centro Ricerche Novara, "lstituto Guido Donegani d Laboratoire de Chimie lnorganique et Mat~riaux Mol&ulaires ESA CNRS 7071 Paris We report an IR, EXAFS and ab-initio study on the interaction of TS-1 with water. IR spectroscopy shows that water is reversibly adsorbed at RT, indicating a weak interaction between H20 molecules and TS-1. EXAFS has evidenced an elongation of the 4 Ti-O bonds of only 0.03 A upon water adsorption. On a theoretical ground, the adsorption of a water molecule has been investigated on three clusters of increasing size: [Ti(OH)4)], [Ti(OSiH3)4] and [TiOsSi6Hl2]. On the two bigger clusters a binding energy in the range of 10-15 kJ/mol has been obtained. Our study confirms that TS-1 is a rather hydrophobic material.

14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of the support (SiO2 and All] and SiB zeolites) S. Dzwigaj (a,*), M. Matsuoka (a), M. Anpo (b) and M. Che (a,c)

(a) Laboratoire de R~activit~ de Surface, Paris, France dzwie.ai(i~ccr./ussieu.fr; (b) Department of Applied Chemistry, Osaka Prefecture University, Osaka, Japan," (c) Institut Universitaire de France Diffuse reflectance UV-Visible and photoluminescence spectroscopies have been used to study the local environment of vanadium ions dispersed on the surface of amorphous (SiO2) and crystalline (non-dealuminated A1B and dealuminated SiB zeolites) supports. It is demonstrated that the molecular structure of vanadium (V) species depend strongly on the nature of the support. The application of photoluminescence spectroscopy allows to distinguish in as prepared VSiO2, VA1B and VSiB materials one, two and three kinds of tetrahedral vanadium (V) species, respectively.

357

14-P-36 - Characterization of Ni, Pt zeolite catalysts by TEM and EDX M.H. Jordgo and D. Cardoso

Chemical Engineering Department, Federal University orS. Carlos, S6o Carlos-SP, Brazil. Fax." (+55-16) 260-8264. [email protected] and [email protected] Bimetallic bifunctional catalysts containing different proportions of Ni and Pt supported in HUSY zeolite were prepared and characterized by TEM, punctual EDX analysis and n-hexane isomerization. The EDX analysis of the Ni and Pt bimetallic catalysts shows that the metal particles contain both metals and from HRTEM it was observed that the bimetallic particles have crystallographic parameters of metallic nickel. The presence of small platinum amounts in the nickel catalysts produces more active catalysts for the n-hexane isomerization, and presents also higher selectivity for the formation of dibranched hexane than the ones containing only platinum.

14-P-37 - N M R and ESR investigations of alkali metal particles in NaY zeolite F. Rachdi a*and L.C. de M6norval b

~GDPC, UMR 5581 CNRS, UM2, Montpellier, France, [email protected] bLMC30, UMR 5618 CNRS, ENSCM, Montpellier, France, [email protected] NaY zeolite loaded with sodium or rubidium metals vapor phase deposition has been investigated by ESR, 129Xe, 23Na and 87Rb NMR. Exposure of the zeolite to a high Na concentration leads to a single ESR line which is attributed to Na metallic particles inside the zeolite cavities. 129XeNMR spectrum of NaY zeolite loaded with Na shows three lines at 88, 94 and 134 ppm which are interpreted in terms of domains of nonuniformely distributed metal particles. By annealing at 670 K the spectrum collapses to a single line at 120 ppm, characteristic of a narrow particle size distribution. 23Na and 87Rb NMR spectra in the temperature range 260 K-300 K were obtained for Rb loaded NaY zeolite. The observed resonances can be explained by the presence of Na/Rb alloy phase in the zeolite cavities.

14-P-38- Topochemical changes in large MFl-type crystals upon thermal treatment in oxidizing and non-oxidizing atmosphere O. Pachtovfi (a), B. Bernauer (b), J.-A. Dalmon (c), S. Miachon (c), I. Jirka (a), A. Zikfinovfi (a) and M. Ko~ifik (a)

a *J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Praha, [email protected], Czech Republic; b Institute of Chemical Technology, Praha, Czech Republic; c Institute de Recherches sur la Catalyse (CNRS), Villeurbanne, France TPAOH removal from large as syntesized silicalite-1 crystals with internal morphology of 90~ has been investigated in regimes with gas flow in parallel to and through the crystal layer both in absence and presence of oxygen. The void space accessibility of crystals was estimated from sorption isotherms of N2 which exhibited as a rule two steps. The topochemical changes in crystals after a partial template removal were evaluated using light microscopy, ESCA measurements and elemental analysis of organic residues.

358

14-P-39- Structure of Fe(III) sites in iron substituted aluminophosphates: a computational and X-ray spectroscopic investigation C. Zenonos(a), A. Beale(a), G. Sankar(a), D.W. Lewis(b), J.M. Thomas(a) and C.R.A. Catlow(a) a Davy Faraday Research Laboratory, The Royal Institution ofGB, [email protected] United

Kingdom; b Department of Chemistry, University College London, United Kingdom We compare the structure of Fe(III) active sites in the small pore FeA1PO-18 and large pore FeA1PO-5 catalysts prepared using appropriate structure directing agents. The present study clearly points out that it is possible to substitute Fe(III) ions for tetrahedrally coordinated AI(III) in the framework of A1PO-5 and A1PO-18 to yield an active and selective oxidation catalysts. The use of atomistic simulations is again proven to provide accurate geometries which, when combined with the analysis of the EXAFS data, yield accurate models for the active sites.

14-P-40 - Possible formation of Cu +2(CO)2( H 20). complexes in a ZSM-5 zeolite prepared by direct synthesis: evidence for the occurrence of Cu+-Cu + pairs? F. Geobaldo 1, B. Onida ~, M. Rocchia l, S. Valange 2'3, Z. Gabelica 2 and E. Garrone l'*

/Dipartimento di Scienza dei Materiali e In~egneria Chimica, Politecnico di Torino, Torino Italy E-Mail [email protected]; Universitd de Haute Alsace, ENSCMu, GSEC, Mulhouse, France," 3LACCO, UMR CNRS 6503, ESIP, Poitiers, France Cu-ZSM-5 zeolite prepared by direct synthesis via a methylamine route show Cu + species as defined as those present in samples prepared by CuC1 vapour exchange. The IR study of the reversible interaction of water with presorbed CO shows a variety of bands, the most plausible interpretation of which is the formation of species (HzO)nCOCu+(OH)Cu+CO(HzO)m (n,m 0,1,2), which suggests the occurrence of Cu + species in pairs.

359

22 - A d v a n c e d Materials (Thursday) 22-P-06 - Tailored generation of titanium oxide species within porous Si-MCM-41 P. Prochnow (a), G. Schulz-Ekloff (a), M. Wark (a,b), J.K. Thomas (b), A. Zukal (c) and J. Rathousky (c) a Institute of Applied and Physical Chemistry, University of Bremen, Germany, [email protected]; b Department of Chemistry and Biochemistry, Notre Dame University, USA; c J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic It is elaborated, that the generation of titanium oxide species of tailored and uniform size into Si-MCM-41 as host material does not only depend on the amount of titanium compounds added in one step, but also on the repeated addition and hydrolysis of the titanium compound in consecutive steps. Anatase nanoparticles of a well-defined size of up to 3 nm, Ti(IV) oxide oligomers and mononuclear Ti(IV) oxide species, respectively, were generated without a substantial enrichment of titanium oxide particles on the extemal surface of the Si-MCM-41 host. Depending on the size and content of the Ti(IV) oxide species, the fluorescence of co-impregnated dye molecules was statically quenched to varying extent.

22-P-07 - Optical switching with photochromic dye molecules encapsulated in the pores of molecular sieves by in-situ synthesis C. Schomburg (a), D. W~hrle (a), G. Schulz-Ekloff (b) and M. Wark (b) a Institute of Organic and Macromolecular Chemistry, University of Bremen, Germany ; b Institute of Applied and Physical Chemistry, University of Bremen, Germany, mwark@chemie, uni-bremen,de Spiropyran or its configurational isomers (merocyanines), respectively, are incorporated in the supercages of faujasite (NAY, HY and DAY) by in-situ synthesis. Luminescence spectra of the colored isomers indicate the non-aggregated incorporation of merocyanine forms. Photochromism experiments exhibit high quantum yields for the photoinduced switching between the different configurational isomers. The strong retardation of the thermal relaxation rate from the cis isomer to the trans isomer in the faujasite hosts is attributed to an increase of the rotation barriers by the imposed spatial restrictions. A strongly increased stability towards photobleaching is found with respect to spiropyrans stabilized in organic polymers or SiO2 based MCM-41 matrices.

22-P-08 - F o r m a t i o n of carbon nanotubes on various molecular sieves supported metal oxides A.M. Zhang, Q.H. Xu, J.J. Zhao and J.M. Cao Department of Chemistry, Nanjing University, Nanjing, 210093, P. R. China The carbon nanotubes were formed on metal oxide-supported zeolite by the decomposition of acetylene hydrocarbon at 700~ The optimum reaction conditions of growth of nanotubes on various molecular sieve catalysts, including Y, A, MOR, ZSM-5 and MCM-41, were studied. Fe/Co-supported Y zeolite catalyst may be the best catalyst for growth of nanotubes in them. Masses of carbon nanotubes with uniform diameter of about 30 nm were obtained over pretreated Y zeolite. The states of iron in Fe-supported Y catalyst measured by M6ssbauer spectrum during three stages of original, hydrogen reduced and catalytic synthetic nanotubes indicated that the hydrogen generated during the reaction is enough to reduce the Fe(III) to sub-valence active state. The nanotubes of larger diameter may be as the template of GaN growth.

360

22-P-09 - Encapsulation of Tb[(CIBOEP)4P](acac) in Si-MCM-41 by the method of ship-in-bottle and its luminescent properties at 77 K Q. Xu(a), Z. Zhao(b), L. Li(a), G. Liu(b), H. Ding(a), J. Yu(a) and R. Xu(a)

a: Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China. E-mail:[email protected] b." Chemistry Department, Jilin University, Changchun 130023, People's Republic of China. Tb[5,10,15,20-tetra(para-(4-chlorobenzoyloxy)-meta-ethyloxyphenyl)Porphyrin] (acetylacetone) denoted as Tb[(C1BOEP)4P](acac) has been prepared by encapsulating Yb(acac)3 into (CIBOEP)4P-doped Si-MCM-41. The properties of the samples are studied by ICP, XRD, ESR, UV-vis, XPS and spectrofluorometry. It is found that the assembly has better luminescent properties than the pure complex at 77 K.

2 2 - P - 1 0 - A new adsorbent with magnetic properties based on natural clinoptilolite V. Pode (a), V. Georgescu (b), V. Dalea (a), R. Pode (a) and E. Popovici (b)

a University "Politehnica" of Timisoara, Romania, Email: [email protected] b University "AI. I. Cuza" oflasi, Bvd. Copou No. 11, 6600 Iasi, Romania The present research aimed to use the Romanian volcanic tuff as an adsorbent material with magnetic properties. The magnetic properties were induced by a chemical method for covering the volcanic tuff particles with magnetite. The modified volcanic tuff was synthesized by varying some parameters that could influence the adsorption and magnetic properties. The magnetic characteristics of the samples were investigated by induction using a Howling device. The adsorbent material could be used for pollution abatement in viscous media contaminated by highly toxic metal ions that could be separated afterwards based on their magnetic properties.

22-P-11 - Preparation of microcalorimetric gas sensors with C o A P O - 5 S. Mintova (a), J. Visser (b) and T. Bein (a)

aDepartment of Chemistry, University of Munich, Butenandtstr. 5-13 (E), 81377 Munich, Germany, svetlana, mintova@cup, uni-muenchen, de bFord Research Laboratory, MD 3028, Dearborn, M148121-2053, USA Microcalorimetric sensors were prepared by direct synthesis and impregnation of Co in the AFI type material. The synthesis of the CoAPO-5 samples was performed under hydrothermal conditions in a microwave oven using various concentrations of Co, organic template and different conditions of a microwave irradiation. The resulting powder samples used for further preparation of calorimetric sensors were characterized using XRD, TG, nitrogen sorption and UV-vis spectroscopy. The CoAPO-5 films were formed by a drop coating method and tested as gas sensors toward carbon monoxide and cyclohexane. The temperature-change of the sensors depends on the amount and the location of the Co in the AFI type structure and on the accessible pore volume.

361

22-P-12 - Study of cation-exchange properties of an organozeolite V.A. Nikashina, E.M. Kats, I.V. Komarova, N.K. Galkina and K.I. Sheptovetskaja

Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin str. 19, Moscow 117975, Russia."fax" (095)-938-2054, e-mail" elkor@geokhi, msk. su To evaluate the cation-exchange properties of organozeolite-Clinotsides obtained on the basis of the natural clinoptilolite-containing tufts of Tedzami (Georgia) and Holinskoye (Russia) deposits, an earlier developed method of determining their effective equilibrium and kinetic characteristics including the comparison of theoretical and experimental breakthrough curves was used. The quantitative characteristics of cation-exchange processes were obtained. It is shown that there is significant influence of the modification on the kinetic of the cationexchange on Clinotsides.

22-P-13 - A d v a n c e d electrode materials based on m e s o p o r o u s a l u m i n u m stabilized anatase A. Attia (a), S.H. Elder (b), R. Jir~isek (a), L. Kavan (a), P. Krtil (a), J. Rathousk~, (a) and A. Zukal (a) a J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolej~kova 3, 182 23 Prague 8, Czech Republic, rathous@/h-inst.cas.cz b The William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, U.S.A. A novel mesoporous molecular sieve was prepared whose framework is composed of anatase nanocrystals stabilized by aluminum. The material was characterized by X-ray diffraction, Raman spectroscopy, nitrogen adsorption and lithium insertion electrochemistry. The faradaic capacity and charge-transfer kinetics is considerably higher that those of analogous structures stabilized by Zr.

22-P-14 - Dye-zeolite assemblies for optical sensing applications J.L. Meinershagen and T. Bein* Department of Chemistry, Ludwig Maximilians Universit~it, Butenandtstr. 11-13 (E), 81377 Munich, Germany. Julia.Meinershagen@cup. uni-muenchen.de The aim of this work is to combine the shape selectivity of zeolites with the chemical sensitivity of solvatochromic dyes; this has been explored for the application of size-selective vapor sensing. Solvatochromic dyes are extremely sensitive to their surrounding environment and display large wavelength shifts in visible and fluorescence spectra reflecting changes in polarity. Dye / zeolite ensembles were prepared by ion exchange and inclusion synthesis as well as direct adsorption. Optical responses to various organic analytes have been measured using visible diffuse reflectance and fluorescence spectroscopy. Fast and reversible optical changes have been observed for a wide range of molecules.

362

2 2 - P - 1 5 - A new s o r b e n t based on c l i n o p t i l o l i t e - c o n t a i n i n g tuff modified by polyethylene I.N. Meshkova (a),V.A. Nikashina (b),T.M. Ushakova (a),V.G. Grinev (a) ,N.Yu. Kovaleva (a), A.A. Zaborskii (b), T.A. Ladygina (a) and L.A. Novokshonova (a) ~Semenov Institute of Chemical Physics RAS, [email protected], Russia. bVernadsky Institute of Geochemistry and Analytical Chemistry RAS, [email protected], Russia. Clinoptilolite-containing tuff (CT) dust was modified by the catalytic polymerization of ethylene on the surface of CT particles. The compositions with 3-5wt.% of polyethylene (PE) and 97-95 wt.% of CT were obtained. The thin PE coating formed on the CT particles was permeable to the filtrating water solutions. As a result of encapsulation of the CT particles, the filter properties of this sorbent were improved. The ion-exchange characteristics of the modified CT (powder and pressed tablets) with respect to NH4 + and Sr2+ cations were determined. It was shown that CT dust-PE compositions retained the ion-exchange properties of initial CT.

22-P-16 - M o l e c u l a r sieves from pillaring of s o m e r o m a n i a n bentonite E. Popovici a, I. Bedelean b, D. Pop b, G. Singurel a, D. Macocinschi c and H. Bedelean b

~"Al.I.Cuza" University of Iasi, Romania, [email protected]; b"Babes Bolyai" University of Cluj-Napoca, Romania; c "P.Poni" Institute of Macromolecular Chemistry We report here preliminary results of the physicochemical characterization of a composite material obtained by combining the cethyltrimethylammonium cations clay insertion procedure with the room temperature synthesis of mesoporous materials inside of clay layers. The Romanian bentonite, containing 64% montmorillonite was used. The organic cations are incorporated within the interlayer region of the clay, serving to prop open the layers and to allow incorporation of the silicon source for MCM-41 synthesis. The obtained materials display a high thermal stability and molecular sieve properties.

22-P-17 - Electronic states and a r r a n g e m e n t s of AgI and CuI clusters i n c o r p o r a t e d into zeolite L T A T. Kodaira a and T. Ikeda b aNational Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305-8565, Japan, kodairanimc.jp; bNational Institute for Research in Inorganic Materials, Tsukuba, Ibaraki 305-0044, Japan Both AgI and CuI clusters were successfully incorporated into the cages of Na-type LTA. The maximum loading densities of the AgI and CuI molecules per a-cage were 4.0 and 6.3, respectively. In the optical spectra, the lowest absorption bands of both kinds of clusters show a large shift to the higher energy side compared to that of the original bulks. It was found that the space group of the original Na-LTA, Fm3 c, changed to lower symmetry ones by incorporation of both kinds of clusters. These are determined by the appearance of new reflections in the X-ray powder diffraction patterns. The physical properties of these two kinds of clusters seem to be slightly different. CuI molecules adsorbed sparsely into the cage have the property to aggregate and form a cluster. The CuI clusters have large electron-vibration interaction.

363

22-P-18- PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical properties G. Telbiz(a),O. Shvets(a), V. Vozny(b) and M. Brodyn(b) a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, [email protected], Ukraine b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine We report on the development of host-guest interaction and optical properties in course of preparation procedures of semiconductor clusters PbI2 in the LTL matrix. For the samples with relatively high PbI2 content the narrow emission peak only slightly blue-shifted from Eex was observed. The gradual disappearance of this peak during the storage of the samples in the air is explained by assuming that originally formed long clusters undergo fragmentation into smaller species.

22-P-19 - Application of the molecular sieves as matrices for the pigments S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk Faculty of Chemistry, A. Mickiewicz University, Poznah, Poland. sko walak~m ain. am u. edu. 191 The uniform intracrystalline voids of the molecular sieves can be employed for encapsulation of molecules containing chromophore groups and they can result in forming pigments. Natural lazurite is a good example of zeolite (sodalite) containing sulfur anion-radicals encapsulated in ]3-cages. We demonstrate here that the above radical can be also introduced into AIPO4 sodalite (A1PO4-20), but the attempts to encapsulate it to zincophosphate sodalite were unsuccessful. The latter structure could, however, accommodate CdS molecules, when they are encapsulated during the dry crystallization of SOD. The organic cation-radicals generated in the MFI structure channels (HZSM-5, H-ferrosilicalite, H-zincosilicalite) as a result of oligomerization of styrene and its derivatives form very stable pigments of various colors.

22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction and fluorescence properties G. Telbiz(a), O. Shvets(a), S. Boron(a), V. Vozny(b), M. Brodyn(b) and G.D. Stucky (c) a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, [email protected], Ukraine b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine," c. Department of Chemistry, University of California,, Santa Barbara, CA, USA Transparent mesoporous fibers with excellent order and parallel pores and doped by laser dye are prepared with good reliability. Influence of the nature of laser dye on the host- guest interaction is shown. Optical properties of Rhodamine 6G and Coumarine 120 embedded in mesoporous fiber waveguide have demonstrated utility for new laser materials, microphotonic devices or microreactors with increasing thermostability of dye component. The opportunity of preparation of the composite materials mesoporous fiber / semiconductor is shown.

364

22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the structural type MCM-41 B. Onida l, B. Bonellil, M. Lucco-Borleral, L. Floral, C. Otero Are~.n2 and E. Garrone l

1Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Italy, [email protected]," 2Departamento de Qu[mica, Universidad de Las Islas Baleares, Palma de Mallorca, Spain. Dye-containing mesostructured silica and zeolitic materials are interesting for their potential application in optical devices and as chemical sensors. Congo Red and Curcumin, two pH indicators, have been incorporated in MCM-41, precursors, which have been characterised by means of X-ray diffraction, UV-Visible and FTIR spectroscopy. Dyes are located in the micellar phase of the silica-surfactant mesophase and their spectroscopic properties confirm that they are in a solvated state, where both surfactant and silica wall may act as a solvent. Dyes maintain their pH indicator properties and are accessible to gases such as HC1 and NH3.

365 27 - Selective Oxidation over Micro- and Mesoporous Catalysts (Thursday)

27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons: preparation, characterization and catalytic activity U. Arnold (a), R.S. da Cruz (b), D. Mandelli (c) and U. Schuchardt (a).

a Universidade Estadual de Campinas, ulf(-&iqm,unicamp, br, Brazil. b Universidade Estadual de Santa Cruz, Ilh~us, Brazil. c Pontificia Universidade Cat6lica de Campinas, Brazil. Metallosilicates containing Cr, Cu or Mo have been prepared by an acid-catalyzed sol-gel process. Structural information about the silicates were obtained by elemental analysis, TGA, XRD, XRF, N2-physisorption, EPR, UV/VIS and FTIR spectroscopy. The silicates are active catalysts for the oxidation of hydrocarbons with tert-butyl hydroperoxide. Catalyst stabilities with regard to metal leaching during catalytic oxidations were investigated.

27-P-07 - High catalytic activity of Fe (Ill)-substituted aluminophosphate molecular sieves (FeAPO) in oxidation of aromatic compounds X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D, Jiang, S. Qiu and F.-S. Xiao* Dept. of Chemistry, dilin Univ., Changchun 130023, China, E-mail.'[email protected] Iron substituted aluminophosphate molecular sieves (Fe-A1PO4-11, Fe-AIPO4-5 and Fe-VPI5) are catalytically active in oxidations of aromatic compounds such as hydroxylation of phenol, benzene, and naphthol, as well as epoxidation of styrene. Catalytic data show that the activities of Fe-A1PO4-11, Fe-AIPO4-5 are comparable with that of TS-1 in the oxidation of aromatic compounds. Furthermore, Fe-VPI-5 shows high activity in naphthol hydroxylation by H202, while TS-1 is completely inactive due to the small pore size. By comparison of various catalysts, Fe (III) in the framework is considered to be the major active site in the catalytic reactions.

27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with cations of the transition metals A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev, T.N. Shakhtakhtinsky, G.A. Ali-zade and K.I. Matiyev

Institute of Theoretical Problems of Chemical Technology of the Academy of Sciences of Azerbaijan, 370143, Baku, H.david ave., 29, Azerbaijan, E-maih [email protected]. Activity and selectivity of natural (pure and dealuminated clinoptilolite and mordenite) and A synthetic zeolites modified with cations of the transition metals (Cu 2+, Co/+, Cr 2+, Zn 2+ and Pd 2+) have been tested in vapor phase oxidation of iso-propyl and n-propyl alcohols. The efficient catalyst, CuPdH-mordenite has been selected for the oxidation of iso-propyl alcohol to acetone. It has been shown that this catalyst is not efficient in the oxidation of n-propyl alcohol. The catalyst prepared from A synthetic zeolites and containing Pd 2+ and Cu 2+ shows the highest activity in this reaction.

366

27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation of thioethers with hydrogen peroxide M. Ziolek, A. Lewandowska, M. Renn, I. Nowak, P. Decyk and J. Kujawa

Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Poznan, Poland E-mail: [email protected] Micro- and mesoporous materials containing niobium in the framework or extra framework positions were studied in the oxidation of dibutyl sulphide with H202. Leaching of Nb from the solid to the liquid phase was considered. Some of the catalysts prepared via the impregnation with Nb-salts show some leaching of Nb to the liquid phase and the oxidation partially occurs homogeneously in the liquid phase. The reaction proceeds mainly on the catalyst surface when the mesoporous molecular sieves containing Nb in the framework are used.

27-P-10- Biomimetic oxygen transfer by Co and Cu complexes immobilized in porous matrices K. Hernadi (a), I. Pfilink6 (b), E. B6ngyik (a) and I. Kiricsi (a)

a Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tdr 1, Szeged, H-6720 Hungary, [email protected]; b Department of Organic Chemistry, University of Szeged, D6m tdr 8, Szeged, H-6720 Hungary Co(II) or Cu(II) histidine or imidazole complexes were immobilized in porous matrices (montmorillonite and MCM-41) via two methods (introduction of preformed complex or complex formation within the ion-exchanged host substances). It was found that immobilization in general and the latter method in particular increased catalytic activity and catalyst life time in the decomposition reactions of hydrogen peroxide relative to the matrixfree complexes. The immobilized materials were characterized by experimental and computational methods and the structures of the guest molecules inside the hosts were also investigated.

27-P-11 - Titanium molecular sieves convert hydrogen peroxide into 102 F.M. van Laar, a D.E. De Vos, a P. Grobet, a J.-M. Aubry, b L. Fiermans c and P.A. Jacobs a

Centre for Surface Chemistry and Catalysis, Leuven, Belgium, [email protected], bEquipe de Recherches sur les Radicaux Libres et l'Oxygbne Singulet, Lille, France," ~Department of Solid State Sciences, Gent, Belgium The interactions of Ti molecular sieves with H202 were investigated with near infrared luminescence spectroscopy to detect the characteristic 1270 nm emission of the short-lived excited singlet molecular oxygen (IO2). From these experiments it was concluded that (1) for all titanium molecular sieves tested, part of the H202 is converted to 102, (2) higher H202 concentrations result in more singlet molecular oxygen, (3) increasing titanium content of the molecular sieve does not result in more 102 production and (4) particularly the hydrophilic (Ti,A1)-13 produces 102 at a high rate.

367

27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: The effect of copper and aluminum content in the reducibility and in the activity of Cu active species M.S. Batista and E.A. Urquieta-Gonzfilez Dep. Chem. Eng./UFSCar, S~o Carlos- SP, Brazil. e-mail: [email protected] The effect of Cu and A1 content in Cu/ZSM-5 catalysts on the nature of the formed Cu species was studied. The samples were characterized by XRD, AAS, DRIFTS, EPR and Hz-TPR and the activity was checked in the propane oxidation. The samples, irrespective of their Si/A1 ratio and Cu content, show a reduction peak at 210~ which, as evidenced by DRIFT of CO adsorption, corresponds to the reduction of Cu +2 to Cu +l. The reduction peak of Cu +! shifts to higher temperatures with the increase of Si/A1 ratio or with the diminution of Cu/A1 ratio, evidencing that isolated Cu cations present a higher interaction with the zeolite structure. The propane conversion, irrespective of Si/A1 ratio, increased with Cu content in the solid and the TOF number correlated inversely with the Cu/A1 atomic ratio in the zeolite.

2 7 - P - 1 3 - Oxidizing conversion of isobutanol on zeolites S.Zulfugarova

Institute of Inorganic and Physical Chemistry Azerbaijan Academy of Sciences [email protected] Oxidizing conversion of isobutanol on Na, Cu, Co and F e - forms of zeolites of Y, erionite and mordenite types was studied. Zeolite CuY shows the greatest activity in the formation of isobutyric aldehyde (--30%); other samples are suitable for stronger oxidization and dehydration reactions. It was demonstrated by thermodesorption that there is one form of adsorbed oxygen with maximum temperatures of 100 -130~ on Na-erionite and Namordenite. There are high-temperature adsorbed forms of oxygen with maximum temperatures of 120-150, 400-450 and above 600~ on Ni-erionite and Cu-mordenite

27-P-14 - Photocatalytic production of H202 over heterogenized quinone in zeolite J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park*

Catalysis Centerfor Molecular Engineering, KRICT, Taejon 305-606, Korea; separk@pado, krict,re. kr The photocatalytic production of H202 from ethanol and 02 is studied by using zeoliteheterogenized quinone catalysts under UV light of 300-400 nm. The photochemical reaction between ethanol an~ 02 initiated by quinone catalysts produces H202 and acetaldehyde equivalently. The/qflinone compounds are heterogenized by both encapsulation method in zeolite pore and anchoring method on zeolite surface. The anthraquinone-2-carboxylic acid (AQCA) catalysts anchored on Pd~ zeolite exhibit enhanced catalytic activity in the formation of H202 from ethanol and 02 as compared with encapsulated quinone catalysts of the Pd~ The anchored AQCA does not leach out and prevent leaching of encapsulated AQCA during the reaction.

368 - Liquid-phase oxidation of cyclohexane chromium and iron ETS-10 materials 27-P-15

in the presence of

A. Valente a, P. Brand~o b, Z. Lin a, F. Gon~alves a, I. Portugal a, M.W. Anderson b and J. Rocha a

a Departamento de Quimica, Universidade de Aveiro, 3810-193 Aveiro, Portugal [email protected], Portugal.

b Department of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK The introduction of chromium or iron in microporous titanosilicate ETS-10 provides interesting redox properties for cyclohexane oxidation, using H202 as oxidant, under moderate reaction conditions, that ETS-10 alone does not possess. The main reaction products are cyclohexanol and cyclohexanone. Selectivity to the latter is maximum when acetonitrile is the solvent. The observed reactivity trend for these catalysts towards cyclohexane oxidation decreases when the trapping efficiency of the solvent towards hydroxyl radicals increases. Cyclohexane conversion increases with HEOE/cyclohexane ratios. Metal leaching from these materials during oxidation accounts for loss of catalytic activity upon recycling.

2 7 - P - 1 6 - Effect of oxygen concentration on catalyst deactivation rate in vapor phase Beckmann rearrangement over acid catalysts T. Takahashi and T. Kai

Department of App. Chem. and Chem. Eng., Kagoshima Univ., Kagoshima 890-0065, JAPAN E-mail." [email protected], FAX +81-99-226-8360 The addition of a small amount of oxygen (up to 1000 ppm) in helium was effective to improve the catalytic activity in vapor phase Beckmann rearrangement over HZSM-5 modified with precious metals. The catalyst life time increased using oxygen as the diluent gas. When the amount of oxygen exceeds 1.0 %, the dehydrogenation of the coke precursor is accelerated. The combination of oxygen as the diluent gas and methanol as the diluent solvent was effective to increase the life time of the acid catalysts including an amorphous SIO2-A1203, HZSM-5 type zeolite and porous silica glass.

the role of the titanium active site in the phenol/anisole hydroxylation over titanium substituted crystalline silicates

27-P-17 - On

U. Wilkenh6ner 1, D.W. Gammon 2 and E. van Steen 1

Catalysis Research Unit, 1Dept. Chemical Engineering, 2Dept. Chemistry, University of Cape Town, South Africa Hydroxylation of phenol and anisole was investigated using TS-1, a silanised TS-1 and Alfree Ti-Beta. Pore geometry, solvent, external surface and substrate govern the selectivity of the hydroxylation reaction. In medium pore TS-1 the formation of hydroquinone in phenol hydroxylation is favoured due to the geometric constraint on the formation of catechol in the pores. A similar effect is observed for formation of ortho- and para hydroxy-anisoles in A1free Ti-Beta. Solvents affect activity and selectivity of the hydroxylation reactions through adsorption and co-ordination to the titanium active site. The external surface of TS-1 plays a substantial role in hydroxylation reactions.

369 31 - Environment-Friendly Applications of Zeolites (Thursday)

31-P-05 - Application of sorbing composites on natural zeolite basis for heavy metals contaminated territories rehabilitation W. Sobolev (a), V. Ilyin (b), F. Bobonich (b) and S. B~ir~ny (c)

a S & P Department "Flegmin" ("Sventana" Ltd.), [email protected], Ukraine b Institute of Physical Chemistry of the National Academy of Sciences, Ukraine c University of Miskolc, Institute of Chemistry, Hungary Various compositions of natural zeolites modified for the remediation of soils contaminated by heavy metals and radionuclides are discussed. Modified zeolites are selective adsorbents in respect to bivalent cations including Sr, Cd, Cu, Pb, Zn. Incorporation of modified zeolites into soils reduces the content of lead and other heavy metals by a factor of 4-5 and prevents or diminishes the transport processes from soil into ground water and plant biomass. Using of organo-mineral composites, containing 1-5 % selective sorbent "Zeolite P", is efficient to get ecologically cleaned harvests of corn, bean and vegetable cultures under low contamination.

Investigation of lead removal from wastewater by Iranian natural zeolites using 212pb as a radiotracer

31-P-06-

H. Kazemian(a), P. Rajec(b), F. Macasek(b), and J.O. Kufacakova

a Jaber Ibn Hayan Research Labs., AEOI,, Tehran, IRAN- [email protected] b Faculty of Natural Science, Comenius University, Bratislava, Slovak Republic The uptake of lead from its aqueous solutions (1'10 .5 and 1'10 "2 mol.dm 3, buffered at pH=3.7), by three clinoptilolite-rich tufts from Meyaneh, Firouzkouh, and Semnan; and a natrolite-rich ore from Zahedan (Hormak) region of Iran, was investigated by plotting the ionexchange isotherms and calculating distribution coefficients (Ko). 212 Pb radioisotope was used as a radiotracer. The results provide information on the suitability of the individual zeolites for radioactive and industrial wastewater treatment. The removal of lead by the clinoptilolitesrich tufts was effective and the uptake sequence was Meyaneh > Firouzkouh > Semnan; whereas the take up of lead on the natrolite material was negligible.

3 1 - P - 0 7 - Purification of the waste liquid hydrocarbons using cationexchanged forms of clinoptilolite M.K. Annagiyev, S.G. Aliyeva and T.M. Kuliyev.

Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaijan Republic, Baku. The use of adsorbents obtained on the basis of natural zeolites has a large practical and theoretical importance for different branches of a national economy. Presence of even small quantities of water and iron ions in liquid hydrocarbons of influences negatively upon the quality of the products produced under manufacture of synthetic detergent- sulfonol; corrosion of the industrial and transport equipment takes place too. Usually synthetic adsorbents, which are deficient and expensive are used when drying liquid hydrocarbons.

370

3 1 - P - 0 8 - The use of transcarpathian zeolites for concentrating trace contaminants in water V.O. Vasylechko (a), L.O. Lebedynets (a), G.V. Gryshchouk (a), Y.B. Kuz'ma (a), L.O. Vasylechko (b) and V.P. Zakordonskiy (a). (a) Ivan Franko National University of L 'viv, L 'viv, Ukraine [email protected] (b) Lvivska Polytechnika National Universitat, L 'viv, Ukraine The adsorption properties of Ukrainian Transcarpathian natural zeolites (clinoptilolite and mordenite) and of their chemically and acid-modified forms towards Cd, Cu and chloroform have been investigated. The optimum conditions of concentrating trace contaminants of Cd, Cu and chloroform in water were found. The possibility of the use Transcarpathian zeolites in analyses of water has been demonstrated.

31-P-09 - Ammonia removal from drinking water using clinoptilolite and lewatit S100 H.M. Abd E1-Hady, A. Grtinwald, K. Vlckova:[: and J. Zeithammerova

Civil Engineering Department, Department of Sanitary Engineering, Czech Technical University In Prague - [email protected], fax." 0042 02 24354607, Czech Rep. High concentrations of ammonium in surface water make it unsuitable as drinking water, and this is becoming a major problem in the world. The purpose of this study is to investigate the possibility of removing ammonium from drinking water by means of an ion exchange process. We used one material of natural origin: clinoptilolite and one synthetic material: Lewatit S 100. Experimental results show that Lewatit S 100 has almost 4 and 1.7 times weight capacity for ammonia removal compared to the capacity of clinoptilolite for concentrations 10 and 5 mg NH4+/L respectively, but for 2 mg NH4+/L the weight capacity of clinoptilolite was found to be 1.9 times that of Lewatit S 100.

31-P-10 - Pilot plant of ammonium removal from nitrogen industry waste waters by an Ukrainian clinoptilolite Y.I. Tarasevich and V.E. Polyakov Institute of Colloid Chemistry & Chemistry of Water, [email protected], Ukraine Laboratory studies and industrial tests had shown that to remove the ammonium ions from nitrogen industry waste water, the application of the clinoptilolite is most promising. Sulphuric acid involved in the industrial cycle can be conveniently used for the regeneration of the worked-out clinoptilolite. Optimum conditions for water cleaning using the clinoptilolite filter and for the subsequent regeneration of the filter by sulphuric acid were determined. Eleven sorption/regeneration cycles were performed in industrial conditions; it was shown that the dynamic exchange capacity of clinoptilolite, 0.52 geq/g, remains almost unchanged. The 'hungry' regeneration is shown to be most efficient, enabling the recovery of 60-70% of the clinoptilolite exchange capacity. Cleaned industrial waste water can be used as the make-up water in closed systems of industrial water supply. The worked-off regenerative solutions, after their neutralisation and boiling down, are used as fertiliser.

371

31-P-I I- Croatian clinoptilolite and montmorillonite-rich tuffs for ammonium removal M. Rozic (a) and S. Cerjan-Stefanovic (b)

(a)Faculty of Graphic Arts, Zagreb, Croatia, fax:385~1~2371-077 (b)Faculty of Chemical Engineering and Technology, Zagreb, Croatia Clinoptilolite- and montmorillonite-rich tufts from Croatian deposits were examined to evaluate their ability for ammonium ions uptake. Both tested materials have potential for removing ammonium from waters. However, the montmorillonite-rich tuff is not as effective as clinoptilolite-rich tuff, particularly in the presence of competing Ca 2+ cation. In all experiments, the clinoptilolite-rich tuff exchanged a far more ammonium compared to the montmorillonite-rich tuff.

31-P-12 - Ammonia removal from water by ion exchange using South African and Zambian zeolite samples and its application in aquaculture M. Mwale and H. Kaiser

DIFS, Rhodes University, Grahamstown [email protected], RSA The possibility of improving aquaculture water quality using a Zambian zeolite identified as laumontite and a South African clinoptilolite sample is discussed. These were tested under laboratory conditions and in a fresh water recirculating system. There were significant differences in average ammonia CEC between clinoptilolite (14.94 rag/g) and laumontite (2.77 mg/g). The average cation exchange capacity (CEC) values in the fresh water system (5.80 mg/g and 4.12 mg/g for the 0.7-1.0 and 1.0-1.4 mm particle sizes, respectively) were significantly lower than the column estimates for the same particle sizes. Mass balance of nitrogen (N) indicated that only 22% of the 60% NH4+-N available for adsorption was adsorbed by the zeolite. It was concluded that N budget studies make it possible to determine the amount, nature and effect of the dissolved N load in a fish culture system and on the ion exchange process. The results suggest that both samples can be used in water treatment.

31-P-13 - Permanent storage of chromium in hardened FAU-type zeolite /cement pastes C. Colella, D. Caputo and B. de Gennaro

Dipartimento d'Ingegneria dei Materiali e della Produzione, Universith Federico II, Napoli, Italy Cr removal from wastewater by ion exchange using FAU-type zeolites and the subsequent stabilization of the resulting sludges in a cement matrix is reported. Amounts of 5 g/1 of synthetic faujasite-like zeolite X or 8 g/1 of a faujasite- and phillipsite-rich tuff were able to bring the Cr ~+ concentration in a wastewater of an electroplating plant, below the law limits allowed for discharge in times of practical significance. The compressive strengths of the compacts containing 10% to 75% of zeolitic materials were much higher than the value of 0.44 MPa, suggested by international protocols for handling and landfilling the solidified wastes. Moreover, suitable leaching tests on the hardened pastes resulted in a Cr 3+ concentration in the leachates lower than the law limits allowed for discharge in water bodies (2 mg/1).

372

31-P-14 - Phosphorus removal from wastewater in upgraded activated sludge system with natural zeolite addition J. Hrenovic a, y. Orhan b, H. Btiyiikgting6r b and D. Tiblja~

a

~Faculty of Science, University of Zagreb, Zagreb, [email protected] bOndokuz Mayis University, Environment Eng. Dept.,, Samsun, Turkey- [email protected] A new application of natural zeolites (NZ) in sewage treatment is presented in this paper. The aim of this study was to investigate the enhanced performances of upgraded activated sludge system with NZ addition; particularly as far as phosphorus removal, chemical oxygen demand (COD) and sludge characteristics. Two experimental studies were run; an upgraded activated sludge system with NZ addition and a conventional activated sludge system, run as a control unit. The results point to the possibility of successful phosphorus and COD removal from wastewater by activated sludge bioaugmented with phosphorus accumulating bacteria using NZ as a support material.

31-P-15 - Application of natural zeolites to purify polluted river water M. Okamotoa and E. Sakamotob

aDivision of Earth Sciences, Kyushu International University,, Yahata-higashi ku, Kitakyushu, Japan, [email protected]; b Department of Biological and Environmental Chemistry, Kyushu School of Engineering, Kinki University, Kayanomori, Iizuka, Japan We have attempted to remove the ammonium ions contained in waste river water using natural zeolites in an oxidative atmosphere using a laboratory-scale circulatory apparatus. The ability of zeolites to purify waste-water was compared with that of regular river gravel, which has no ion exchange ability. The results show that Ca-rich mordenite is superior to normal river gravel to purify waste river water polluted by ammonium ions. The decrease of ammonium ions in polluted water was a result not only of ion exchange with calcium ions in zeolite, but also of microbiological oxidation on the surface of zeolite. The ability of natural zeolites to oxidize ammonium ions into nitrate ions is a function of the zeolite contents of minerals and the type of zeolite species.

31-P-16- Elimination of ammonium in seawater by zeolitic products J.M. Lopez-Alcal~. and J.L. Lopez-Ruiz

Centro Andaluz Superior de Estudios Marinos. Departamento de C. Navales. Grupo Zeolitas, C~tdiz University, Puerto Real (Cddiz) Spain. [email protected] The problem of ammonium elimination by zeolites in seawater is studied in this paper. By preparation of new zeolitic products, elimination of 20% of initial ammonium is reached. This is the best result referenced in the literature up to date.

373

32 - Zeolite Minerals and Health Sciences (Thursday) 32-P-06 - Effects of dietary inclusion of natural zeolite on broiler performance and carcass characteristics E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos, and P. Fortomaris

Department of Animal Production, Veterinary School Aristotle University of Thessaloniki, 54006 ThessalonikL [email protected], gr, Greece The addition of 2% and 4% natural zeolite (NZ) to broiler diet was studied in a 42-day experiment. Body weight gain, feed consumption, feed consumption ratio, some carcass characteristics and chemical analysis in the muscular mass of breast and legs were determined. The supplementation of 2% NZ in the broiler diet resulted in an improvement of the feed conversion ratio and an increase of body weight, carcass yield as well as linoleic and a-linolenic acid content, without any adverse effect on the other measured parameters. The addition of 4% natural zeolite resulted in a significantly higher feed conversion ratio.

32-P-07Interaction clinoptilolite

studies

between

aspirin

and

purified

natural

A. Rivera (a), L.M. Rodriguez-Albelo (b), G. Rodriguez-Fuentes (a) and E. Altshuler (c)

a Zeolites Engineering Laboratory, University of Havana, jea@in[bmed.sld, cu, Cuba b Organic Materials Laboratory, University of Havana, Cuba c Superconductivity Laboratory, University of Havana, 10400 Havana, Cuba Taking into account the antacid properties of a purified natural clinoptilolite, NZ, we have examined its effects on aspirin (ASA) in an aqueous medium. We have studied by UV spectroscopy the ASA in solution before and after the addition of NZ. Our results suggest that the concentration of ASA is only affected by the interaction at high pH values (pH=8), at which the ASA also starts to decompose. These results match the IR spectroscopy studies of the incorporation of ASA to NZ. We also exchanged NZ with Ca, Cu and Na ions, and studied the interaction of the modified zeolites with ASA. While no ASA was detected in the zeolite in the first two cases at any pH value, the third one showed some incorporation for all the pH values.

32-P-08 - Channel model for the theoretical study of aspirin adsorption on clinoptilolite. W a t e r influence A. Lain and A. Rivera

Zeolites Engineering Laboratory, University of Havana, anabel@laeJf oc.uh.cu, Cuba A new zeolite model, that features the a and c channels of clinoptilolite has been used to study the possible interactions of aspirin-water-zeolite, in order to know the behavior of the drug in a more complex system and the influence of water present in the zeolite channel. The calculations have been performed using the AM1 semi-empirical method and acid and sodic clinoptilolite models. The results showed that the adsorption entalphy of aspirin in the acid structure is in the same order than that obtained for the sodic structure, although the nature of the interaction is different in each structure. The ester and aromatic groups were preferentially oriented to the model. In any case the chemical stability of aspirin is affected by the presence of water molecules in the system.

374

32-P-09 - In vitro and in vivo effect of natural clinoptilolite on m a l i g n a n t tumors M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak, V. Sverko, T. Balog and K. Pavelic Division of Molecular Medicine, Rudjer Boskovic Institute, pavelic(~rud/er.irb.hr, Croatia Many biochemical processes are closely related to ion exchange, adsorption and catalysis. Zeolites reversibly bind small molecules such as oxygen or nitric oxide, they possess size and shape selectivity, the possibility of metalloenzyme mimicry, and immunomodulatory activity. These properties make them interesting for pharmaceutical industry and medicine. In vitro experiments showed inhibition of tumour cell proliferation as well as MZ to be the possible scavenger of HNE. After i.p. application of MZ, the number of peritoneal macrophages was increased as well as their production of oxide anion. NO generation was totally abolished. At the same time translocation of p65 subunit of NF~:B in spleen cells was observed. Thus, here we report anticancer effect of MZ in vitro and immunostimulatory effect in vivo.

32-P-10 - Effects of natural c l i n o p t i l o l i t e - rich tuff and sodium bicarbonate on milk yield, milk composition and blood profile in Holstein cows A. Nikkhah, A.R. Safamehr and M. Moradi- Shahrbabak Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran An experiment was conducted to evaluate the effects of different levels of clinoptilolite- rich tuff (CP) and sodium - bicarbonate (SB) on milk yield and its components in Holstein cows. A balanced change - over design with 4 rations, 4 periods (28 days and 4 cows per ration) was employed. Ingredients of the control ration (1) were alfalfa hay (17.1%), corn silage (16.2%) and concentrate (66.7%) on dry matter basis. Experimental rations contained, 1% SB (2) : 0.5% SB + 3% CP (3) and 6% CP (4), respectively. The actual means of daily milk yield of the cows that received rations 1,2,3 and 4 were 23.53, 24.2, 25.24, 25.45 kg/d and milk fat 3.18, 3.39, 3.3 and 3.44%, respectively. The average dry matter intake per kg fat corrected milk (4%fat) for rations 1-4 were, 0.9, 0.95, 0.96 and 0.95, respectively.

32-P-11 - Effect of natural clinoptillolite-rich tuff on the p e r f o r m a n c e of V a r a m i n i male lambs A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran In order to determine the effects of different levels of clinoptilolite-rich tuff (CP) on performance of fat tail Varamini male four rations containing 0 (control), 2, 4 and 6% CP which were named 1,2,3 and 4, were prepared, respectively. The rations were fed to four groups of the lamb (12 lambs/group) individually for 100 days. Feed intake, average daily gain (ADG), feed conversion rate (FCR), carcass dressing percentage and carcass quality were measured. The obtained results were as follows: feed intake for rations were 1.32, 1.34, 1.38 and 1.41 kg DM/day, ADC were 166.0, 177.9, 196.9 and 184.8 g/day and FCR were 8.0, 7.6, 7.1 and 7.76, respectively. Dressing percentage of lamb which were fed ration 3, washighest (53.9vs 52.5, 52.7 and 51.2).

375

32-P-12 - Ciinoptilolite and the possibilities for its application in medicine N. Izmirova (a), B. Aleksiev (b), E. Djourova (b), P. Blagoeva (d), Z. Gendjev (d), Tz. Mircheva (d), D. Pressiyanov (c), L. Miner (c), T. Bozhkova (c), P. Uzunov (c), I. Tomova (e), M. Baeva (f), A. Boyanova (f), T. Todorov (g) and R. Petrova (g)

a Sofia University, Faculty of Chemistry; b Faculty of Geology and Geography," c Faculty of Physics, d National Oncological Center," e Sofia Sanitary Inspection,"f BAS Solid Body's Physics Institute, g BAS Applied Mineralogy Inst. Central Mineralogy & Crystallography, Laboratory, Sofia, Bulgaria. Part I. Clinoptilolite (Cpt) is widespread in the NE part of the Rhodopes mountains in Bulgaria. In respect to the possibilities of use of Bulgarian clinoptilolite in medicine, its toxic, genotoxic and carcinogenic effects on laboratory animals, were studied. In the same relation, the natural radioactivity of Cpt, of the animals' food, containing Cpt and of the animals' faeces, was measured. The contents of 226Ra in drinking water, percolating through Cpt rocks and the concentration of 222Rn in Cpt-built houses were also measured. Part II. Products of biocrystallization in human urine dry residue after Cpt application per os were observed too.

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377

AUTHOR INDEX

A Abasov, S.I. 25-P- 15 26-P-20 Abbasova, G.G. 25-P- 15 Abd EI-Hady, H.M. 3 l-P-09 Abe, Y. 24-0-02 Aboukais, A. 14-P- 15 30-P-26 Aboul-Gheit, A.K. 30-P-20 Abraham, A. 13-P-23 Abramova, A.V. 11-P-23 Abramson, S. 29-0-02 Accardi, R.J. 13-P- 12 Afanassiev, I.S. 11-P-26 Agashe, M.S. 14-P- 12 Agayeva, S.B. 26-P-20 Agger, J.R. 02-0-05 Aguado, J. 24-P-13 ,~,gueda, V.I. 18-P- 11 Aguilar-P, J. 25-P-13 Ahedi, R.K. 25-P-06 Ahmed, S.M. 30-P-20 Ahn, W.S. 01-P-14 02-P-19 23-P-14 29-P-13 Ahn, Y.-S. 29-P-27 Aiello, R. 02-P-29 04-P-17 04-P-18 06-P-28 11-P-27 Aika, K. 30-P-34 Aizawa, T. 26-P-07 Akhalbedashvili, L. 23-P-09 30-P-10 Akiyama, Y. 02-P-25 Akporiaye, D. 03-K-01 Akporiaye, D.E. 03-P- 18 Akramzadeh Ardakani, M. 01-P-08 Alberti, A. 01-K-01 Aleksiev, B. 32-P- 12 Aliyev, A.M. 27-P-08 Aliyeva, S.G. 3 I-P-07 Ali-zade, G.A. 27-P-08 AI-Khowaiter, S. 06-P-21 AI-Megren, H. 06-P-21 Altshuler, E. 32-P-07 Alvarez, A.M. 14-P- 14 24-P- 11 Amokrane, S. 23-P-07 Amoureux, J.P. 13-P-2/3 Ananias, D. 0 5 - P - ! ~ Anderson, M. 04-0-05 Anderson, M.W. 02-0-05 13-P-16 21-P-07 27-P-15 Andrade, H.M.C. 30-P-13 Andreev, V.V. 28-P-12 Andr6s, J.M. 18-P- 10 Andrews, R.D. 31-O-02 /

Anfilov, B.G. 01-P-12 Angelescu, E. 24-P-29 Annagiyev, M.Kh. 3 l-P-07 Anpo, M. 30-K-01 14-P-20 14-P-35 15-P-07 15-P-08 28-P-07 30-P-16 30-P-24 Antoni, T. 02-P-24 Antoshin, G.V. 10-P-05 Antunes, A.P. 30-P-23 Anunziata, O.A. 04-P-07 06-P-08 14-P-08 Aoyagi, J. 18-P- 12 Arabindoo, B. 25-0-02 Arafat, A. 02-P-38 Aranzabal, A. 30-P-I 8 Arcon, I. 14-P- 13 Arends, I.W.C.E. 30-0-02 Ariyuki, M. 28-P-07 Armaroli, T. 13-P-25 Armbruster, T. PL-2 Arnold, A.B.J. 29-P-22 Arnold, U. 27-P-06 Asaftei, I. 24-P-30 Asafiei, S. 04-P-09 Atal'yan, O.K. 10-P-05 Attia, A. 22-P- 13 Attou, M. 04-P-09 Aubry, J.-M. 27-P-11 Auerbach, S.M. 16-0-04 Auroux, A. 13-P-07 Avalos, M. 1 l-P-20 Avalos-Borja, M. 0 I-P- 15 Avgouropoulos, G. 29-P-14 Avil, P. 30-P-22 Ayupov, A.B. 13-P-09 Azuma, K. 11-P- 10 Azzouz, A. 04-P-09

B B.Nagy, J.

02-P-29 04-0-03 04-P-14 04-P-I 6 04-P- 17 04-P-I 8 11-P-27 29-P-18 29-P-31 30-P-19 Bahlala, M. 26-P- 15 Baba, T. 24-0-02 Babapoor, A. 32-P-11 Babonneau, F. 07-0-02 Baek, S.-W. 24-P-26 Baerlocher, C. 09-P-14 09-P-11 Baerns, M. 12-P-15 30-P-33 Baetens, D. 04-P-11 Baeva, M. 32-P-12

378

Baggio-Saitovich, E. 14-P-28 Bai, N. 07-P-07 Bakakin, V.V. 0 l-P- 11 Balmer, W. 23-P-06 Balog, T. 32-P-09 Bandyopadhyay, R. 03-P- 10 Bao, X. 30-P-28 B~ir~iny, S. 3 I-P-05 Barbosa, L.V. 24-P-17 Barker, C.M. 15-P- 18 Barnes, P. 01-O-03 Barrault, J. 07-P- 16 Barroudi, M. 06-P- 15 Barsnick, U. 23-P-27 Barth, J.-O. 10-0-02 Basaldella, E I. 20-P-14 20-P-13 Basler, W.D. 11-P-23 Bataille, T. 17-P-09 Batamack, P. 13-P- 13 Batista, M.S. 14-P-28 27-P-12 Battiston, A.A. 12-O-02 Bauer, F. 28-P-06 Bazzana, S. 03-P-13 Beale, A. 14-P-39 Beck, L.W. 03-0-04 Bedard R.L. 05-P-16 Bedekar, A.V. 24-0-04 Bedelean, H. 22-P- 16 Bedelean, I. 22-P- 16 Behrens, P. 02-P-41 06-P-25 10-O-03 Bein, T. 03-P-12 I1-P-15 20-0-04 22-P-11 22-P-14 Belanova, E.P. 10-P-05 Bell, R.G. 13-P-16 16-P-13 16-P-14 Bellat, J.P. 17-O-02 17-P-I 1 Bellussi, G. 25-0-03 29-O-01 Bem, D. 03-K-01 03-P-I 8 05-P-16 Ben T~arit, Y. 10-P-08 13-P-05 Benazzi, E. 26-P-11 Benco, L. 15-0-02 15-P-12 Benetis, N.P. 14-P-09 Bengoa, J.F. 14-P- 14 20-P- 13 24-P- 11 Bengueddach, A. 03-P-19 17-P-14 Benmohammadi, I~. 21-O-04 Bergmann, M. 14-P-31 Bernaue, B. 14-P-38 Berndt, H. 10-O-01 30-P-15 Berthomieu, D. 15-P-23 Bertrand, O. 17-0-02 17-P-11 Bessho, H. 15-P-07 Beta, I.A. 12-P-08 Bevilacqua, M. 13-P-25 Beyer, H.K. 07-0-03 10-P-06 Bharathi, P. 15-P-09 Bichara, C. 15-P- 26 Bilba, N. 24-P-30 04-P-09 Binet, C. 27-0-05

Birjega, R. 07-P-14 Bischof, C. 26-P-18 Bitter, J.H. 12-O-02 19-P-08 Blagoeva, P. 32-P-12 Blanc, A.C. 29-0-02 29-P-10 29-P-31 Blanco, C. 03-P-06 Blanco, M.N. 23-P-19 Blasco, T. 12-P-12 29-P-23 Bliek, A. 28-P-14 Bobonich, F. 31-P-05 Boenneman, H. 29-P-22 Bogdanchikova, N. 0 l-P- 15 1l-P-20 B6hlig, H. 12-P-08 B6hlmann, W. 06-P-I 7 14-P-07 BOhringer, W. 11-O-02 28-P-15 Boissi6re, C. 08-O-01 08-P-05 Bonardet, J.-L. 19-K-01 19-P-09 Bonelli, B. 22-P-21 BOngyikand, E. 27-P-10 Bonino, F. 14-P-34 Bonneviot, L. 06-0-03 Bonnin, D. 11-O-01 Bordiga, S. 14-P-34 15-O-05 24-P-15 Borello, L. 13-0-04 Borges, C. 02-P-33 Boron, S. 22-P-20 Borovkov, V.Y. 12-O-04 Bosnjak, B. 32-P-09 Botavina, M.A. 30-P-09 B6ttcher, R. 14-P-07 Boutin, A. 16-0-03 Bouvier, F. 17-P-I 1 Boyanova, A. 32-P- 12 Bozhkova, T. 32-P- 12 Bradley, S.A. 26-P-06 Brand~io, P. 04-0-05 27-P-15 Brandmair, M. 30-P-30 Braos-Garcia, P. 23-P-28 Bratu, C. 03-P-18 Br/iuer, P. 28-O-01 Brehm, M. 21-O-03 Br6mard, C. 14-P-18 14-P-24 Bricker, M. 03-K-01 Brieler, F. 21-O-03 Broach, R.W. 05-P-16 Broclawik, E. 15-P- 13 Brodyn, M. 22-P-18 22-P-20 Broersma, A. 19-P-08 Bronic, J. 02-P-24 02-P-29 Brtihwiler, D. 14-0-04 Brunel, D. 29-0-02 29-P- 10 29-P-31 Buchholz, A. 14-P- 17 Budneva, A.A. 11-P-26 Buhl, J.C. 02-P-07 13-P-15 Buijsse, E.J.W. 20-P-18 Bulow, M. 12-O-04 03-0-05 18-O-03 Burtica, G. 01-P-09 06-P-22

379

Busca, G. 13-P-25 Buschmann, V. 02-0-01 02-P-06 Busco, C. 15-0-05 Bussaia, C. 15-P-28 Bustamante, F. 30-P-22 Buttefey, S. 16-0-03 Buttersack, C. 18-0-02 BtiyfikgtlngOr, H. 3 I-P- 14 Byggningsbacka, R. 24-P- 16

C Caceres, C. 23-P- 19 Cadoni, M. 30-P-31 Cagnoli, M.V. 14-P- 14 24-P- 11 Cai, T.-X. 25-P-09 Cairon, O. 14-P-23 Calb, I. 01-P-09 Calder6n, M. 26-P-12 Callanan, L.H. 11-P-25 Calleja, G. 07-P-12 Calzaferri, G. 14-O-04 Camblor, M.A. 05-P-07 13-O-01 Campelo, J.M. 25-P-11 Cao, G. 1 l-P- 19 Cao, J.M. 22-P-08 Cappelletti, P. 01-O-02 Caputo, D. 01-O-05 3 l-P-13 Carati, A. 14-P-30 Cardoso, D. 14-P-36 Carlos, L.D. 05-P-12 Carlsson, A. 03-0-02 Carlsson, K.A. 02-P- 16 Carluccio, L. 29-0-01 Carpentier, J. 30-P-26 Cassiers, K. 06-P-11 Castagnola, N. 28-0-03 Castanheiro, J.E. 23-P- 19 Catlow, C.R.A. 01-O-03 14-P-39 15-P-18 16-0-02 Caullet, P. 09-O-01 25-0-04 Caumo, L. 24-P-17 t~ejka J. 06-P-20 13-0-02 13-P-19 14-P-21 14-P-22 25-P-10 Centi, G. 31-O-03 Cerjan-Stefanovic, 3 l-P-11 0 l-P-17 Cerri, G. 01-O-02 Cesteros, Y. 23-P-16 Chai, H.S. 27-P- 14 Chanda, B. 24-0-04 Chandwadkar, A.J. 07-P-20 Chang, J.-S. 03-P-15 22-0-03 Chang, S.H. 02-P-19 Chao, K.J. 07-P-13 20-0-05 29-P-25

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380

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381

Duncan, W.L. 19-0-03 Dunne, L.J. 16-P- 10 Dutta, P.K. 28-0-03 Dwyer, J. 14-P- 13 Dzwigaj, S. 14-P-35

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F Fajula, F.

03-P-19 06-P-27 06-P-28 1 l-P-06 13-P-11 23-P-13 24-0-03 29-0-02 29-0-04 29-P-31 Falamaki, C. 02-P-09 Fan, B. 02-P-14 07-P-10 21-P-11 Fan, J. 08-P-11 Fan, W. 04-P-13 07-P-10 F~isi, A. 23-P- 15 Fatullayeva, S.S. 27-P-08 Fechete, I. 25-0-04 Fejes, P. 04-P- 17 04-P-I 8 Fenelonov, V.B. 08-P- 14 Feng, S. 22-0-02 Fenoglio, I. 32-0-02 Ferchiche, S. 02-P- 17 Ferey, G. 22-0-03 05-P-19 16-P-15 Fermann, J.T. 16-0-04 Fernandez, C. 09-P-11 13-O-03 13-P-24

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382

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Gisselquist, J. 05-P- 16 Gl~tser, R. 23-0-03 Gobin, K. 30-P- 17 Goddard III, W.A. 16-P-09 Goddeeris, M. 23-P-20 Goh, N.K. 05-P-20 Goldwasser, M.R. 03-P-11 Goletto, V. 07-0-02 G6mez, J.M. 18-P- 11 G6mt~ry, A. 23-P-15 Gon~alves, F. 27-P- 15 Gong, Y. 08-P-08 Gonzalez, G. 14-P- 19 Gonz~lez, F. 03-P-06 Gonz~ilez, L. 28-P-13 Gonz~lez-Pefia, V. 06-P-23 Gonz~ilez-Velasco, J.R. 30-P- 18 Goossens, A.M. 02-P-06 Gopal, S. 26-P-16 Gopinath, C.S. 07-P-20 Gora, L. 20-0-02 20-P-18 G6ra-Marek, K. 13-P- 17 Gorbatkina, I.E. 26-P-23 Gorshkov, V.I. 1 l-P- 18 Goryainov, S.V. 16-P- 19 Goto, Ya. 02-P-27 17-0-04 Goto, Yu. 17-0-04 Gotoh, K. 13-P- 14 Goursot, A. 15-P-23 15-P-24 15-P-25 Graffin, P. 23-P-13 Gray, A.E. 16-P- 11 Green, M.L.H. 06-P-21 Grigoryan, A. 23-P-08 Grigoryan, F. 01-P-16 Grill, W. 02-P-37 Grillet, Y. 17-P-05 Grimm, A. 31-O-04 Grinev, V.G. 22-P-15 Grobet, P. 13-P-18 14-P-10 14-P-11 23-P-33 27-P-11 Groen, J.C. 17-P-08 Groothaert, M.H. 15-P- 11 Grtinert, W. 10-O-01 30-P-15 30-P-27 Grianwald, A. 3 l-P-09 Gryshchouk, G.V. 3 l-P-08 Gualtieri, A.F. 01-O-04 Guan, N. 12-P-15 30-P-33 Guillemot, D. 11-O-01 Guimon, C. 25-0-04 Guisnet, M. 25-P-08 30-0-05 30-P-23 Guo, C.J. 18-0-03 Guo, H.C. 28-P-08 Guo, J. 29-P-08 Guo, S. 20-P-07 Guo, W. 02-P-35 Guo, X. 27-0-02 24-P-14 Guo, Y. 1l-P-11

383

Guo, G.-Q. 03-P-09 18-P-08 Gupta, A. 16-0-05 Gupta, R. 13-P-20 Guth, J.-L. 18-P-06 Guti6rrez Alejandre, A. 13-P-25 Guti6rrez-Ortiz, J.I. 30-P- 18 Gutjahr, M. 14-P-07

H Ha, B.-H. 02-P- 10 Ha, K. 20-O-01 Haberlandt, R. " 15-P-28 16-P- 18 Haddad, E. 08-P-14 Hafner, J. 15-O-02 15-O-03 15-P-12 15-P-20 Hajnal, Z. 15-P-25 Hal,'tsz, J. 29-P- 18 Hailer, G.L. 06-P- 12 23-P-16 Halsall-Whitney, H. 18-0-01 Hamada, H. 02-P-26 02-P-30 Hamdan, H. 25-P-12 Hambartsumyan, A. 0 I-P- 16 Hamidi, F. 03-P- 19 Han, M. 1l-P-21 Han, M.-H. 29-P-27 Han, Y. 05-P-09 06-P-07 Han, Y.W. 09-P-06 Hanaoka, T. 02-P-30 28-P-09 Hancs6k, J. 26-P- 19 Handan Tezel, F. 18-0-01 Haneda, M. 04-P-06 Hanif, N. 02-0-05 04-0-05 Hanika, J. 25-P-10 Hannongbuai, S. 15-P-28 Hannus, I. 30-P- 19 Hantzer, S. 26-0-04 Hao, J. 1 l-P- 13 Haouas, M. 11-P-28 13-P-22 29-P-28 Harlick, P.J.E. 18-0-01 Haroyan, H. 0 l-P- 16 Harrison, W.T.A. 05-0-01 Hartl, M. 10-0-03 Hartmann, M. 04-0-02 26-P-18 28-P-10 29-P-19 Hashimoto, K. 17-P- 13 Hattori, T. 24-P-25 30-0-03 Hayashi, H. 07-P-06 Hayashi, S. 1 l-P-07 13-P-06 He, H. 16-P-16 He, M.-Y. 02-P-34 26-O-01 He, Y.J. 12-P- 11 He, B. 30-P-24 Hecht, T. 29-P-19 Hedlund, J. 02-P-12 20-P-08 20-P-09 20-P-10

Heimbrodt, W. 21-O-03 Heine, T. 15-P-25 Heinrich, F. 30-P-27 Henriques, C. 02-P-33 Henriques, C.A. 24-0-05 Heo, N.H. 09-P-10 Herman, S. 0 l-P-09 Hernadi, K. 27-P-10 Hernfindez, I. 25-P-13 Hem~ndez, J.C. 28-P- 13 Hern~indez, S. 18-P- 10 Herrier, G. 08-0-02 Herrmann, R. 02-P-37 Heydenrych, H. 11-P-24 Hidajat, K. 06-P-26 Higashimoto, S. 14-P-20 28-P-07 30-K-01 Hilbrandt, N. 03-P- 12 Hoang, D.L. 13-P-21 Ho~evar, S. 19-P-06 Hodnett, B.K. 23-P-17 HC~lderich, W.F. 23-P-27 25-P-14 29-P-22 29-0-03 Hol16, A. 26-P-19 Holmes, S.M. 21-P-07 Holmgren, J. 03-K-01 Holmqvist, A. 13-P-05 Honda, T. 02-P-27 Hong, S.B. 05-P-07 02-P-10 Hoogesteger, A.W. 03-P-17 Horiuchi, T. 12-P- 11 Horniakov~i, J. 25-P-07 29-P-11 Houssin, C.J.Y. 02-0-01 Hou~vieka, J. 03-0-02 26-0-02 Hovnanian, N. 08-P-05 Howe, R.F. 14-P-29 Hrenovic, J. 31 -P- 14 Hronec, M. 25-P-07 Huang, L. 08-P-13 20-P-I 1 22-0-04 Huang, W. 06-P-14 Huang, W.Y. 18-P-07 Huang, Y. 14-P- 16 HUbner, G. 12-P-09 Hudec, P. 24-P-10 29-P-26 Hudson, C.W. 26-0-04 Hufnagel, V.J. 02-P-41 Hugeunard, C. 05-P-19 09-0-02 Hulea, T. 25-0-04 Hulea, V. 25-0-04 29-0-02 Hunger, B. 12-O-03 12-P-08 Hunger, M. 14-P-17 23-P-12 23-P-23 Hutschka, F. 15-O-02 15-O-03 15-P-12 15-P-20 15-P-22 Hwang, J.S. 27-P- 14

384

Iborra, S. 23-P-21 Ibrahim, K.M. 31-O-01 Ichikawa, M. 13-P- 14 22-0-05 Igarashi, N. 17-P- 13 Ihm, S.-K. 24-P-26 26-P-21 ljiri, H. 1 l-P- 17 Ikeda, R. 13-P- 14 Ikeda, T. 02-P-25 21-P-18 22-P-17 Iiiev, Tz. 01 -P- 13 Illgen, U. 30-P-33 Ilyin, V. 3 l-P-05 Imada, Y. 17-O-04 28-P-09 Imamura, M. 04-P-06 lmbert, F.E. 28-P- 13 Imp6ror, M. 07-0-02 08-0-03 Inagaki, S. 03-P-14 22-0-05 Inaki, Y. 24-P-25 Inversi, M. 30-P- 14 Ioannides, T. 29-P- 14 Iofcea, Gh. 24-P-30 lojoiu, E.E. 30-P- 12 lone, K.G. 02-P-23 Iovi, A. 01-P-09 lshimaru, K. 14-P-06 lshimaru, S. 13-P- 14 ltabashi, K. 01-P-07 lto, S. 1 I-P-07 30-P-I 1 Ivanov, V.A. 11 -P- 18 lvanova, I.I. 1 l-P-06 23-P-12 25-0-05 lvanova, R. 0 l-P- 13 Iwasaki, T. 07-P-06 15-P-06 Izard, V. 29-0-02 Izmirova, N. 32-P- 12 Izuhal, S. 29-P-29 Izumi J. 18-P- 12

Jacob, N.E. 14-P- 12 Jacobs, P.A. 02-0-01 02-0-04 12-P-10 23-002 23-P-20 23-P-33 27-P-11 Jacobsen, C.J.H. 03-0-02 26-0-02 Jfinchen, J. 31-O-04 Janicke, M. 29-P-17 Jankowska, A. 22-P-19 Jansen, J.C. 02-P-38 03-P-17 20-0-02 20-P- 18 Janssen, A.H. 14-0-01 Jentys, A. 11-P-24 26-P-13 27-0-04 30-P-30 Jeong, S. 14-P-29 Ji, S.-F. 06-P-21

Jiang, D. 27-P-07 29-P-07 Jiang, Y.-S. 05-P- 11 Jim6nez-L6pez, A. 23-P-28 Jin, Q. 16-P-07 Jing, X. 1 l-P-13 21-P-09 Jing, Z. 16-P-16 Jir~isek, R. 22-P- 13 Jiratova, K. 26-P-22 Jirka, I. 14-P-38 Jobic, H. 12-P-08 17-P-09 Joffre, J. 16-P-08 25-P-07 Johnson, L. 18-P- 13 Johnson, M.N. 01-O-03 Joo, S.H. 07-O-01 29-P-13 Jord~io, M.H. 14-P-36 Jorik, V. 29-P-11 Joshi, V.N. 24-0-04 Josien, L. 11-O-03 Jost, S. 15-P-28 Ju, W.-S. 30-P-16 Juan, R. 18-P-10 Jun, S. 07-0-01 29-P-27 Jung, S.W. 09-P- 10 Jungsuttiwong, S. 15-0-04 15-P-10 Juttu, G. 27-0-03

K Kai, T. 27-P-16 Kaiser, H. 31-P-12 Kale, S.M. 23-P-30 Kaliaguine, S. 06-0-03 Kalinin, V.P. 10-P-05 Kail6, D. 26-P-19 Kallus, S. 02-P- 18 Kaltsoyannis, N. 15-P- 18 Kalwei, M. 13-O-01 13-P-12 Karnalakar, G. 28-0-04 Kameoka, S. 30-P-11 Kang, K.-K. 29-P-09 Kao, C.H. 20-0-05 Kao, C.-P. 08-P-07 29-P-16 Kapteijn, F. 18-O-04 30-0-02 Karapetyan, A. 01-P-16 Karetina, I.V. 02-P-42 K~irger, J. 19-0-04 28-0-01 Karlsson, A. 03-K-01 03-P-I 8 Kartikeyan, S. 25-P-17 Kashia, L.D. 23-P-26 Kaskel, S. 29-P-17 Kasture, B.B. 24-0-04 Kasture, M. 04-0-04 Katada, N. 13-P- 10 Kath, H. 23-0-03

385

Katic, M. 32-P-09 Kato, M. 01-P-07 Katovic, A. 04-0-03 04-P-14 Kats, E.M. 22-P- 12 Kaucic, V. 14-P- 13 29-P- 14 Kavan, L. 22-P-13 Kawamura, K. 06-P-05 Kawamura, Y. 30-0-03 Kawi, S. 06-P-26 Kayiran, S. 09-O-01 17-P- 10 Kazakov, A.V. 10-P-05 Kazansky, V.B. 12-0-04 Kazemian, H. 0 l-P-08 3 l-P-06 Keindl, M. 10-P-06 Kennedy, G.J. 02-P-22 Kessler, H. 21-P-15 25-0-04 Kevan, L. 24-P-07 Khaddar-Zine, S. 10-P-08 Khavkin, V.A. 26-P-23 Khelifa, A. 17-P- 14 Khelkovskaya-Sergeeva, E.G. 26-0-03 Khongpracha, P. 15-0-04 15-P- 10 Khoury, H.N. 31-O-01 Khvoshchev, S.S. 02-P-42 Kibby, C.L. 02-P-20 13-P-09 Kieger, S. 30-P-06 Kikot, A. 20-P-13 20-P-14 Kikuchi, E. 03-P-14 07-P-24 ll-P-30 20-0-03 Kim, A.M. 25-P-12 Kim, D.S. 03-P- 15 22-0-03 Kim, G.-J. 23-P-10 23-P-11 Kim, J.-H. 23-0-04 23-P-11 25-P-16 Kim, J.M. 03-P-15 08-P-12 Kim, K.-S. 23-0-04 Kim, K.Y. 01-P-14 Kim, M.H. 01-P-14 23-P-18 Kim, M.-W. 25-P-16 Kim, N.-K. 23-P- 14 Kim, S.J. 23-P- 18 Kim, T.J. 02-P-37 Kim, W.-G. 25-P- 16 Kim, Y. 09-P-06 Kimi, S.B. 31-O-02 King, L.M. 05-P-16 Kiperman, S.L. 30-P-09 Kiricsi, I. 04-P-18 23-P- 15 27-P- 10 29-P- 18 30-P-19 11-P-27 Kirik, S.D. 08-P-14 Kirschhock, C. 02-0-01 02-0-04 Kita, K. 30-P-11 Kitaev, L.Ye. 11-P-23 Kiyohara, P.K. 04-P- 10 Kiyozumi, Y. 02-P-25 04-P-06 Klar, P.J. 21-O-03 Klein, D.P. 26-0-04 Klimova, T. 26-P-12 Klinowski, J. 16-P- 13

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386

Kujawa, J. 27-P-09 Kukovecz, A. 04-P- 18 11-P-27 Kulak, A. 20-0-01 Kuliyev, A.R. 27-P-08 Kuliyev, T.M. 3 l-P-07 Kulkami, S.J. 23-P-24 28-0-04 Kulprathipanja, S. 18-0-05 Kumakiri, I. 20-P- 16 Kumar, N. 23-P-25 24-P-16 Kumar, P. 26-P- 17 Kumar, R. 02-P-40 07-P-23 25-P-17 Kunieda, K. 29-P-29 Kunimori, K. 1 l-P-07 30-P-11 Kurata, Y. 02-P-30 Kuriyavar, S. 10-0-04 Kurpan, E. 02-P- 12 Kustov, A.L. 14-P- 15 Kustov, L.M. 26-0-03 26-P-23 Kuz'ma, Yu.B. 31-P-08 Kuznicki, S. 11-O-04 Kwon, S.P. 02-P- 10

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387

Liu, C.-O. 20-P-06 Liu, G. 22-P-09 Liu, H.-O. 20-P-06 Liu, Min 27-0-02 Liu, Ming 02-P-15 18-P-09 29-P-12 Liu, N.N. 28-0-02 Liu, S. 06-P-14 30-P-33 Liu, S.-B. 29-P- 16 Liu, X. 02-P-39 Liu, Y.-H. 29-P-16 Liu, Yi 14-P-25 Liu, Yu 08-P-06 Liu, Yun. 05-0-02 05-P-08 Liu, Z. 05-P-17 05-P-18 14-P-33 21-P-17 24-O-01 24-P-28 Liu, Z.-Q. 02-P-13 Llabr6s i Xamena, F.X. 24-P-15 Lledos, B. 09-0-01 Llewellyn, P.L. 17-0-03 17-P-15 17-P-16 Lo Jacono, M. 30-P- 14 Lobo, R.F. 13-O-01 13-P-12 27-0-03 Loeser, T. 14-0-02 L6ffler, E. 14-P-31 30-P-27 Loiseau, T. 05-P-19 Long, J. 26-0-01 Long, Y.-C. 03-P-09 17-P-06 18-P-08 Lopes Bhering, D. 15-P-21 Lopez, B. 18-P-06 Lopez, Z. 14-P- 19 L6pez, F. 28-P- 13 Lopez-Alcal~t, J.M. 3 I-P- 16 L6pez-Fonseca, R. 30-P- 18 Lopez-Ruiz, J.L. 31 -P- 16 Lou, S. 29-P-12 Louchart, N. 14-P-24 Lourenqo, J.P. 02-P-33 Lu, D. 07-P- 15 Lu, G.Q. 07-0-05 07-P-18 Lu, H. 29-P-07 Lu, L. 30-P-29 Luan, Z. 24-P-07 Lucco-Borlera, M. 22-P-21 Lt~chinger, M. 29-P-28 Ltlcke, B. 10-O-01 Luigi, D.-P. 13-P- 16 Luna, D. 25-P- 11 Lund, A. 14-P-09 Luo, Q. 08-P-08 Luo, Y. 02-P-35 Luteijn, C. 20-P-18 Lutz, W. 13-P-15

M Ma, B. 1 l-P-08 28-0-02 Ma, L.L. 18-P-07 30-P-07 Macasek, F. 3 I-P-06 Macocinschi, D. 22-P-16 Macquarrie, D.J. 29-P-10 29-P-31 Madriz, S. 03-P-11 Maeda, K. 09-P-14 Maesen, T.L.M. 16-0-01 Magner, E. 23-P-17 Magnoux, P. 25-P-08 30-0-05 30-P-23 Maireles-Torres, P. 23-P-28 Maisuls, S.E. 30-P-34 Majolo, F. 24-P-17 Mfiki-Arvela, P. 23-P-25 Makkonen, J. 26-P-09 Malek, A. 02-P-22 Mali, G. 14-P- 13 Malova, O.V. 11 -P- 14 Man, P.P. 14-P-27 Mandelli, D. 27-P-06 Manoli, J.-M. 26-P- 15 Manos, G. 16-P-10 30-P-17 Manstein, H. 10-P-09 Mantein, H. 11-O-02 Marchese, L. 14-O-05 29-P-30 30-P-31 Marchetti, S.G. 14-P- 14 24-P- 11 Marcilly, C. PL-4 Marcon, G. 23-P-07 Margotti, M. 29-O-01 Marichal, C. 07-P-08 09-P-11 Marie, O. 12-P- 14 Marinas, J.M. 25-P-11 Marlow, F. 06-0-02 Marotti, T. 32-P-09 Marques, A.L.S. 05-P- 14 Marques, M.F.V. 24-0-05 M~rquez-Alvarez, C. 06-P-23 Martens, J.A. 02-O-01 02-0-04 02-P-06 Martin, C. 17-P-05 Martin, T. 29-0-02 Martinez, A. 15-P-23 Martinez, C. 24-P-20 Martos, C. 06-P- 13 Martra, G. 14-0-05 Martucci, A. 09-P-13 Marturano, P. 11-O-05 Mascarenhas, A.J.S. 30-P- 13 05-P- 14 Maschmeyer, Th. 02-P-38 20-0-02 20-P-18 Masloboishchikova, O.V. 26-0-03 26-P-23 Massiani, P. 12-P- 14 Mathieu, M. 06-0-04 06-P-06 Matieva, Z.M. 11-P-23 Matijasic, A. 11-O-03

388

Matiyev, K.I. 27-P-08 Matsukata, M. 03-P-14 07-P-24 1 I-P-30 20-0-03 Matsunaga, I. 03-P- 14 Matsuoka, M.

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Mizukami, F. 02-P-25 04-P-06 Mizuno, R. 1 I-P- 10 Moheswari, R. 26-P- 14 Mohino, F. 07-P- 17 08-P- 10 Mohd Muhid, M.N. 25-P-12 Moissette, A. 14-P-18 14-P-24 Mojet, B.L. 02-0-01 MOiler, K.P. 10-P-09 11-O-02 19-O-03 28-P-15 28-P-16 Monteiro, J.L.F. 24-0-05 Montes de Correa, C. 30-P-22 Montouillout, V. 13-0-03 Moon, G. 28-P-15 Moradi- Shahrbabak, M. 32-P-10 32-P-11 Morais, C.M. 05-P-12 Moreau, C. 23-P-06 Moreau, P. 16-P-08 25-P-07 29-P-11 Moreau, V. 25-P-08 Moreno, N. 18-P- 10 Moret, S. 17-P- 15 Moretti, G. 30-P-14 30-P-21 Morishige, K. 17-0-01 Moroz, N.K. 11-P-26 Morris, R.E. 22-0-01 Mosqueda-Jim6nez, B.I. 30-P-30 Mota, C.J.A. 15-P-21 24-P- 19 Mou, C.-Y. 08-P-07 29-P-16 Mougenei, JC. 09-0-01 Moulijn, J.A. 18-O-04 30-0-02 Mouloungui, Z. 23-P-32 Mravec, D. 16-P-08 25-P-07 29-P-11 Mskhiladze, A. 23-P-09 Mukherjee, P. 02-P-40 07-P-23 Mul, G. 30-0-02 Munhoz Jr., H. 04-P- 10 Mufioz, G. 25-P-13 Mufioz-Pallares, J. 32-0-05 Munsch, S. 28-P-10 Munshieva, M.K. 24-P-24 Munsignatti, M. 05-P-14 Murali Dhar, G. 26-P-08 26-P-17 Murray, R.C. 03-P- 18 Murugesan, V. 25-0-02 Murzin, D.Yu. 23-P-25 24-P-16 Mwale, M. 31 -P- 12

N Naccache, C. 10-P-08 Nachtigall, P. 14-0-03 Nachtigallov~t, D. 14-O-03 Nagai, M. 12-P-17 29-P-29 Nagase, T. 07-P-06 Nair, S. 02-P-28 Naitza, S. 01-O-02

389

Nakai, K. 17-P- 13 Nakao, S.-I. 20-P- 16 Nakata, S. 03-P- 10 Nam, I.-S. 02-P-10 Namba, S. 18-P- 12 26-P-07 Narender, N. 23-P-24 Nastro, A. 04-P- 16 Naumov, M.V. 0 l-P-06 Navarro, M.T. 11-P-29 Nawata, S. 1 I-P- 10 Nekrasov, N.V. 30-P-09 Nenoff, T.M. 05-0-01 Nenu, C. 07-P- 14 Nesterenko, S.N. 25-0-05 N'Gokoli-Kekele, P. 19-K-01 19-P-09 Nibou, D. 23-P-07 Nicolaides, C.P. 26-P-09 Nie, C. 08-P- 13 Niederer, J.P.M. 29-P-22 Nieminen, V. 24-P-16 Nigro, E. 04-P-18 11-P-27 Niimi, T. 24-P-08 Nikashina, V.A. 01-P-12 22-P-12 22-P-15 Nikkhah, A. 32-P-10 32-P-11 Nishide, T. 02-P-25 Nishimura, M. 15-P-07 Nishimura, T. 1 l-P-17 Niwa, M. 13-P-10 Niwa, S. 04-P-06 Nobukawa, T. 30-P-11 Noh, J.S. 09-P- 10 Nokbin, S. 15-0-04 Nordgren, U. 20-P-09 Norefia, L. 25-P- 13 Noronha, F.B. 23-0-05 Novak Tusar, N. 14-P- 13 Novokshonova, L.A. 22-P- 15 Nowak, I. 07-0-04 27-P-09 Nulens, K.H.L. 12-0-03 Nyman, M. 05-0-01 O' Brien, A. 16-P- 11

O O'Connor, C.T.

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390

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Q Qi, X. 02-P-39 Qi, Y. 21-P-17 24-P-28 Qian, B. 17-P-06 Qiu, S. 03-P-08 06-P-07 09-P-08 21-O-05 27-P-07 Qu, z. 30-P-28 Quartieri, S. 01-K-01 09-P-09 Querol, X. 18-P- 10 Quoineaud, A.-A. 13-0-03

R Rachdi, F. 14-P-37 Radha Kishan, M. 28-0-04 Raghavan, K.V. 28-0-04 23-P-24 Raichle, A. 26-P-10 Rainho, J.P. 05-P- 12 Rajamohanan, P.R. 02-P-40 Rajec, P. 3 I-P-06

391

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392

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393

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Weisweiler, W. 30-P-12 Weitkamp, J. 19-O-04 23-0-03 23-P-12 23-P-23 26-P-10 Wendelbo, R. 03-K-01 03-P-18 Wesolowski, T.A. 15-P-24 Wichterlovh, B. 10-O-04 13-P-19 Wie, A.C. 29-P-25 WilkenhOner, U. 27-P- 17 Willett, G.D. 14-P-29 Wingen, A. 29-P-25 Wirnsberger, G. 10-0-03 Wloch, J. 24-P-22 WOhrle, D. 21-O-02 22-P-07 Wolfsberg, M. 16-P- 18 Wong, K.H. 21-P-08 Wouters, B.H. 13-P- 18 14-P- 10 14-P- 11 Wright, P.A. 05-0-03 07-P-17 Wu, D. 07-P-09 08-P-08 14-P-25 Wu, F. 1 l-P-13 Wu, J. 18-P-09 Wu, P. 27-0-01

X Xi, C.-Y. 1 l-P- 12 Xia, J.R. 30-P-08 Xia, Q.-H. 06-P-26 Xiang, S. 02-P-15 05-P-15 12-P-15 18-P-09 20-P-12 29-P- 12 30-P-33 Xiao, F.-S. 06-P-07 12-P-07 21-O-05 27-P-07 29-P-07 Xiao, T.-C. 06-P-21 Xiao, Y.-Z. 06-P-10 Xie, G. 30-P-08 Xie, K. 02-P- 14 Xie, L. 1 l-P-13 Xin, J. 24-P-12 Xin, Q. 14-P-33 Xiong, C. 29-P-08 Xiong, G. 12-P-07 Xiu, J. 27-0-02 Xu, H. 1l-P-13 Xu, L. 05-P-17 05-P-18 24-O-01 24-P-28 Xu, Q. 22-P-09 Xu, Q.H. 1 l-P-09 22-P-08 30-P-07 Xu, R. 02-P-11 02-P-13 05-0-04 05-P-09 05-P-10 22-P-09 05-P-11 Xu, W. 11-P-I 1 Xu, Xian. 09-P08 Xu, Xin 05-P-06 Xu, Y. 05-P-20 30-P-07 Xue, J. 30-P-07 30-P-08

396

Y

Z

Yahiro, H. 14-P-09 Yamaguchi, H. 18-P- 15 Yamaguchi, T. 06-P-05 20-P-16 Yamakita, S. 02-P-28 Yamamoto, K. 2 l-P- 16 Yamashita, H. 15-P-07 28-P-07 30-P-24 Yamazaki, S. 11 -P- 17 Yan, A.-Z. 1l-P-09 Yan, B. 05-P-20 Yan, D. 18-P-07 Yan, H.S. 24-P-14 Yan, L.-J. 26-0-01 Yan, W. 05-P-09 05-P-10 Yan, Y. 20-P-11 22-0-04 Yanev, Y. 0 l-P- 13 Yang, W.-L. 21-P-06 Yang, C.M. 07-P- 13 Yang, H. 02-P-14 Yang, L. 24-P-12 Yang, M. 27-P-07 Yang, S. 12-P-06 Yang, Xu. 30-P-28 Yannakopoulos, A. 32-P-06 Yao, J. 02-P-35 Yashima, T. 27-0-01 Ye, X. 1 l-P-09 Yeramian, A.A. 14-P-14 24-P-11 Yin, Do. 29-P-08 Yin, Du. 29-P-08 Yogoro, Y. 06-P-05 Yomoda, D. 18-P- 12 Yoo, J.W. 23-P-32 Yoon, B.A. 02-P-22 Yoon, K.B. 20-0-01 Yoon, S.B. 07-P-22 York, A.P.E 06-P-21 Yoshida, H. 24-P-25 Yoshimura, M. 02-P-28 Yoshitake, H. 14-P-26 Yoshizawa, K. 28-P-07 Yu, C. 08-P-II Yu, J. 02-P-11 05-0-04 05-P-09 05-P-10 09-P0-8 22-P-09 Yu, J.-S. 07-P-22 Yu, Jia. 14-P-33 Yu, N.-T. 12-P-10 Yu, S.-F. 1l-P- 12 Yu, Y. 12-P-07 27-P-07 Yuan, H.-M. 05-P- 11 1l-P-12 Yuan, Z.Y. 06-P-09 Yue, Y. 08-0-04 08-P-08 Yuschenko, V.V. 1 l-P-06 Yushchenk, V.V. 1 I-P-23

Zaborskii, A.A. 22-P-15 Zadrozna, G. 04-P-12 24-P-22 Zakarina, N.A. 15-P- 14 Zaki, T. 18-P- 14 Zakordonskiy, V.P. 3 l-P-08 Zanardi, S. 01-K-01 Zanibelli, L. 29-0-0 Zarbaliyev, R.R. 25-P- 15 Zarkovic, N. 32-P-09 Zavoianu, R. 24-P-29 Zecchina, A. 14-P-34 15-O-05 24-P-15 Zeithammerova, J. 3 l-P-09 Zeng, X. 12-P-15 30-P-33 Zeng, Y. 17-P-06 Zenonos, C. 14-P-39 Zerbino, J.O. 20-P-14 Zeuthen, P. 26-0-03 Zha, J. 07-P-09 Zhang, A.M. 22-P-08 Zhang, D. 22-0-02 Zhang, H. 05-P-06 07-P-09 Zhang, H.Y. 12-P- 11 Zhang, J. 30-P-24 Zhang, J.Y. 11-P-22 Zhang, L. 05-P-08 22-0-02 Zhang, Luxi 29-P-08 Zhang, P. 05-P-08 07-P-07 Zhang, W. 08-P-06 Zhang, X.F. 20-P-06 Zhang, X.T. 28-0-02 Zhang, Xia. 24-P-12 Zhang, Xio. 20-P-07 Zhang, Yi. 21-P-10 Zhang, Yu. 21-P-09 Zhang, Zh. 07-P-09 Zhang, Zo. 06-P-07 Zhanpeisov, N.U. 15-P-08 Zhao, D. 05-P-06 06-P-07 07-P-09 08-P-I 1 08-P-13 Zhao, H. 22-0-02 Zhao, J.J. 22-P-08 Zhao, L. 27-P-07 Zhao, W. 29-P-08 Zhao, X.S. 07-0-05 Zhao, Z. 22-P-09 Zheng, S. 11-P-24 Zhilinskaya, E.A. 14-P- 15 Zholobenko, V.L. 12-P-16 24-P-21 Zhong, B. 06-P- 10 Zhou, H. 16-P- 16 Zhou, L.-P. I1-P-21 11-P-22 Zhou, W. 06-P-09 07-P- 17 Zhou, Y. 05-P-06

397

Zhu, G. 03-P-08 09-P0-8 Zhu, H.Y. 07-P- 18 Zhu, J.H. 18-P-07 30-P-07 30-P-08 Zhu, L. 29-P-07 Zhu, W. 18-0-04 Zhu, Z. 24-P-06 Zidek Z. 29-P-26 Zik~inov~, A. 14-P-38 24-P- 10 ~ilkov~ N. 14-P-21 14-P-22 Ziolek, M. 07-0-04 27-P-09 Zones, S.I. 02-0-05 03-0-03 1 l-P-16 17-P-07 26-0-05 Zong, B. 30-P-29 Zou, X. 09-0-03 09-P-12 Zou, Y. 02-P-11 05-0-02 05-0-02 05-P-08 II-P-11 Zu, Z. 12-P-05 Zubowa, H.-L. 2 l-P- 14 Zukal, A. 06-P-20 22-P-06 22-P-13 Zulfugarova, S. 27-P-13 Zvolinschi, A. 04-P-09

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399

SUBJECT

A AASBU method, structure prediction 07-P-21 Ab initio calculations 15-0-01 Ab initio calculations, molecular orbital 15-P-07 Ab initio cluster calculation 15-P-08 15-P-21 Ab initio simulation, dynamical processes 15-O-02 ABW beryllophosphate 05-P-06 Acetal formation 23-P-21 Acetaldehyde, aqueous 23-P-06 Acetic acid purification 18-O-05 Acetone dimerisation to MIBK 23-0-05 Acetonitrile adsorption, NMR study 13-P- 14 Acetonitrile hydrogenation 23-P-28 Acetonitrile, synthesis 10-P-08 Acetylene 19-P-07 Acetylene oligomerisation 24-P- 15 1-Acetyl-2-metoxynaphthalene isomerisation 25-P-08 Acid/base properties 10-0-02 Acid dealumination,BEA 11-P-22 Acid, hybrid mesoporous 08-P- 10 Acid leaching, zeolite Y 1 I-P-08 Acid sites 13-O-01 13-0-04 11-P-26 Acid site, enhanced strength 13-P- 10 Acid sites, FAU 13-P- 13 Acid site location, MOR 12-P-16 Acid sites, MCM-48 29-0-04 Acid sites, mesoporous silica 24-P-25 Acid strength, MeAPO-31 14-P-13 Acid treatment, clinoptilolite 0 I-P-09 Acidity 13-0-04 23-P- 15 24-0-01 Acidity-activity relationship 15-P- 16 Acidity, aluminophosphate 05-P-09 Acidity, dealuminated FAU 1 l-P-21 Acidity, EMT 13-P-21 Acidity, external surface 13-P-09 Acidity, FAU 13-P-07 13-P-21 Acidity, M4 ls 29-0-03 Acidity, mesoporous silica 08-P-06 Acidity, mordenite 12-P-05 13-P-08 Acidity, MTS 06-P-07 29-P-07 Acidity, by NH3 TPD 30-P- 18 Acidity, Pt/K-LTL 1l-P-07 Acidity, SAPO 23-P-31 Acidity, SAPO-34 24-P-26 Acidity, zeolites 19-P-07 28-P- 15 Acidity, zeolites by NMR 13-P-23 Acidity, zeolite Y 15-P- 16

INDEX

Acidity, Zr-HMS Activated sludges Activation, catalyst, by plasma Activation energy, proton jumps Activation, MFI large crystals Active sites Activity profile, granular catalyst Activity-acidity relationship Adjuvant in therapy Adsorbate configuration, bipyridine/MFI Adsorbed phase ordering, AEL Adsorbed phase, phase transition Adsorption 17-0-03 Adsorption on adsorbed surfactant 06-P-27 Adsorption, alkanes, silicalite- 1 Adsorption, Ar/N2 mixtures Adsorption, aromatics 19-0-02 Adsorption, aspirin on clinoptilolite Adsorption, binary, organics Adsorption, chloroalkanes, Ag-FAU Adsorption, chloroalkenes Adsorption, chloroform Adsorption, CO 15-P-10 Adsorption, CO2 18-0-01 Adsorption, CO2 on Cu, Zn-FAU Adsorption complexes Adsorption complexes, geometry Adsorption, dibenzothiophene Adsorption dynamics Adsorption enthalpies, Ar/N2 Adsorption, H2 Adsorption, H20, MCM-41 Adsorption, human bile Adsorption, hydrocarbons 17-P-07 18-0-04 Adsorption, isosteric heats Adsorption isotherms, modelling Adsorption, liquid phase 18-O-02 18-P-07 Adsorption, mesoporous silicas Adsorption models 16-O-03 Adsorption, modelling 19-O-02 16-P-06 Adsorption in MOR, modelling Adsorption, mycotoxins Adsorption, p-nitroaniline Adsorption, N-nitrosamine Adsorption NMR, toluene/Na-X ,Adsorption, organics 14-P-30 Adsorption, pheromones

26-P-22 31-P- 14 1 l-P- 14 15-0-01 14-P-38 12-P-08 28-P-12 15-P- 16 32-P-09 14-P-24 17-O-03 17-0-02 17-P- 17 32-0-04 19-P- 10 17-P- 15 18-P-08 32-P-08 18-P- 15 24-P- 19 17-P- 11 16-P- 14 12-P-13 18-P- 10 17-P-14 12-P-08 14-P-07 18-P- 11 19-P-07 17-P- 15 17-P- 10 17-P- 13 32-0-03 30-P-32 17-P- 14 16-P- 10 28-P-10 17-P- 12 26-P-20 16-P-14 15-P-12 32-0-04 13-P-06 18-P-07 13-P- 16 17-P-06 32-0-05

400

Adsorption of probe molecules 13-0-04 Adsorption properties, Na,Ca-LTA 17-P-09 Adsorption, proteins 23-P- 17 Adsorption, reactive 18-0-05 Adsorption, supercritical 17-P-05 17-P- 16 AEL, commensurate phases 17-0-03 Affinity index 17-P-06 AFI, Co 04-P- 13 AFI single crystal 2 l-P-08 AFM PL-2 02-0-05 AFM, growth surface SSZ-24 13-P- 16 Ag diffuse reflectance 0 l-P- 15 Ag dispersion, effect on SCR 30-P-28 Ag-clinoptilolite 0 l-P- 15 Ag-FAU 18-O-05 24-0-02 24-P-19 Ag-FER spectroscopy 14-0-03 AgI clusters in LTA 22-P- 17 Ag-LTA 14-O-04 Ag-MFI 30-0-03 30-P-28 30-P-34 Ag-MFI spectroscopy 14-0-03 Ag-MFI, adsorbent for CO 15-P- 10 Ag-MFI, deNOx catalyst 30-P-34 AgS2 clusters in LTA 14-O-04 Ag§ local structure 30-P- 16 Agglomerated nanocrystals, reactivity 03-P- 14 Aggregates, silica, fractal 14-P-25 Aging 02-0-02 Aging, effect on synthesis 02-P- 19 02-P-21 Aging, MCM-41 synthesis 06-P-21 27A1-13Cdipole interaction 13-0-01 27A1chemical shifts 15-P-21 27A12D NMR 13-P- 19 27Al(19F) WISE NMR 08-0-04 27A1MQ MAS NMR 13-O-03 13-P-20 14-P-11 27A1 NMR 07-P-08 06-P- 17 09-0-02 09-P- 11 1 I-P- 10 11-P-28 13-P- 18 13-P-22 13-P-24 18-P-13 21-P-17 30-P-19 AI coordination, AIPO4-20 09-P-11 AI distribution by cation siting 13-P-19 AI distribution in MFI 13-O-02 AI, extraframework 13-P- 18 AI, extra-framework, modelling 15-P-21 AI insertion, CON and DON 1 I-P-16 AI isopropoxide, MCM-41 secondary treatment 23-P-33 beta-Al methylphosphonate, crystallisation 21-P-17 AIMepO-beta, water adsorption 09-P- 14 AI-MCM-22 14-P-21 AI-MCM-41, catalyst support 24-P-08 AI-MCM-41, stability 06-P- 19 AIOH hydroxyls 14-P- 10 AI ordering 13-0-01 AI ordering, dachiardite 0 l-P-07 AI pentacoordinated 13-P- 18 A1 phosphites, microporous 05-P- 15 AIPO4, s e e a l s o aluminophosphate

AIPO4 deNOx catalysts 30-P-31 AIPO4 heteronuclear NMR 13-P-24 AIPO4 substituted, multipole moment 15-P-27 AIPO4 synthesis, templates 02-P-33 AIPO4, synthesis intermediate 02-P-11 AIPO4-5 13-P-14 AIPOa-5/DCM resin composites 21-O-04 AIPO4-5 with Fe 14-P-39 AIPO4-5 host 21-O-05 21-P-08 A1PO4-11, adsorbed phase ordering 17-O-03 AI PO4-14, hydration 13-P-20 AIPO4-18 with Fe 14-P-39 AI PO4-18, hydration 13-P-20 AIPO4-20 09-P- 11 AIPO4-20, host 22-P- 19 AIPO4-31, substituted 14-P- 13 AIPO4-34, hydration 15-P- 17 AIPO4-CJ2, NMR crystallography 09-0-02 AI quantification 13-0-03 AI-SBA- 15, synthesis 08-0-04 AI sources, MCM-41 06-P- 17 AI support, MFI films 20-P-I 7 AI-Mn phosphate 05-P-11 AI, traces in TS-1 27-0-02 Alcohol oxidation 27-P-08 Aldehyde, unsaturated 29-P- 15 Aldol condensation 23-P-23 Alkali cations, effect on adsorption 32-0-05 Alkali cations, effect on photocatalysis 15-P-07 Alkali cations, effect in synthesis 03-0-05 Alkali cations in FAU, EPR 14-P-07 Alkali cations in fluoride media 04-P-17 Alkali cation templates 03-P- 18 Alkali-exchanged LSX 14-0-02 Alkali-exchanged MCM-22 and MCM-36 10-O-02 Alkali metal particles/FAU 14-P-37 Alkali treatment, bentonite 03-P-06 Alkali treatment, MFI 1 l-P-30 Alkaline earth in LTL synthesis 02-P-17 Alkalinity, effect on crystallisation 03-P-19 Alkane activation 25-0-05 25-P-15 Alkane conversion 15-P- 15 Alkane cracking 15-P- 15 Alkane diffusion, silicalite- 1 19-P- 10 Alkane formation, free energy 16-0-01 Alkane hydroconversion 16-0-01 Alkane isomerisation 26-0-02 n-Alkanes, long chain, isomerisation 26-P-23 Alkanes, oxidation 27-0-01 27-P-06 Alkene, s e e Olefin Alkoxy surface species from dechlorination 24-P-19 Alkoxysilanes 1 l-P-09 Alkoxysilane CVD 11-O-02 Alkylamine 06-P-23 Alkylammonium in AIPO4 synthesis 02-P-33 Alkylation 06-P-06 24-P-09 25-P-16 Alkylation, aniline 23-P- 12 25-P- 11

401

24-P-06 25-P-15 29-0-01 Alkylation, benzene 25-0-05 Alkylation, benzene, by alkanes 25-P-0 29-P-11 Alkylation, biphenyl 25-P-12 Alkylation, bulky aromatics 28-P-08 Alkylation, ethylbenzene 24-P-20 Alkylation, isobutane 25-P-16 Alkylation, isopropylnaphthalene 25-0-03 25-P-13 Alkylation, naphthalene 28-P-15 Alkylation, orthoAlkylation, phenol 23-P-31 25-P-09 28-P-15 Alkylation, polyaromatics 25-O-01 25-P-06 25-P-09 25-P-14 Alkyl hydroperoxide, decomposition 27-P- 10 Alkyl ketone photolysis 15-P-07 N-alkylphenothiazines, photoionisation 24-P-07 Alumina, anatase stabilizer 22-P- 13 Alumina membrane support 20-0-03 Alumina, mesoporous 06-P-23 07-P- 16 07-P- 18 07-P-08 Alumina, mesostructured 02-P-19 Alumina source 30-P-19 Alumina support 07-P-09 Alumina-zirconia, mesoporous 11-P-22 Aluminate, sodium reagent 1I-P- 10 11-P-22 Alumination, BEA 23-P-33 25-P-12 Alumination, MCM-41 29-0-04 Alumination, MCM-48 11-P-28 Alumination of siliceous zeolites Aluminophosphates, s e e also AIPO4 03-P-16 14-P-22 14-P-33 Aluminophosphate, anionic 05-P-09 Aluminophosphate, chiral 05-P- 10 Aluminophosphates, hydration 15-P- 17 Aluminophosphate, lamellar 02-P- 11 Aluminophosphates, lattice vibrations 14-P-31 Aluminophosphate MIL-34 05-P- 19 Aluminophosphates, Ni 09-P-08 Aluminosilicate MCM-41 06-P-08 07-P-14 24-0-05 24-P-22 Aluminosilicate, mesoporous 06-P-07 06-P-15 06-P-22 06-P-27 08-P-06 08-P-14 29-0-04 1 I-P-16 Aluminosilicate UTD- 1 1l-P-16 Aluminosilicate SSZ-33 04-0-05 AM- 13, vanadosilicate 04-0-05 AM- 14, vanadosilicate 02-P-33 Amides in phosphate synthesis 11-P-25 Amination, methanol 23-P-07 Amination, octanoi 05-P-06 Amines in beryllophosphates synthesis 06-0-04 Amine expander for MCM-48 06-P- 11 Amine extraction from HMS 02-P-33 Amines in phosphate synthesis Amine, template 02-P-41 03-0-03 07-0-05 Amine, zeolite template 05-0-02 Amino acids 18-0-02 Amino acids separation 28-P- 10 3-Aminopropylsilane grafting 29-P-31 Ammonium exchange, clinoptilolite 0 I-P- 12

Ammonium removal 3 I-P-09 31-P-11 31-P-12 31-P-15 Ammoxidation, ethylene Amorphisation at high pressure Amorphous aluminosilicate Amorphous aluminosilicate, zeolitic Analcime crystal chemistry Analcime from fly ash Anatase, aggregated nanocrystals Angle BOT-chemical shift correlation Aniline methylation Aniline, N-methylation Animal feeding 32-P-06 32-P-10 Anion exchanger Antarctica, zeolite occurrences Anthraquinone/BEA photocatalyst Anticancer activity Apatite, crop enhancement APO-CJ3 APO-CJ4 Apple fragrance Aquaculture Aqueous solution Ar adsorption Ar adsorption, AEL Ar, supercritical adsorption, zeolites Ar/N2 adsorption, FAU Ar/N2 adsorption, LTA Armenia, natural mordenite Aromatics, adsorption Aromatics, adsorption on MFI Aromatics, bulky, alkylation Aromatic chloro compounds Aromatics, diffusion Aromatics disproportionation Aromatics hydroalkylation Aromatics hydrodecyclisation Aromatics, hydrogenation Aromatics hydroxylation Aromatics, nitration Aromatics oxidation Aromatics oxyhalogenation Aromatisation, C4 hydrocarbons 24-P-30 Aromatisation, cyclohexane Aromatisation, cyclohexene Aromatisation, n-hexane 15-P-09 Aspirin Aspirin adsorption on clinoptilolite ATO, substituted ATO, substituted, synthesis Au nanoparticles Au, bimetallic clusters in FAU Au2CI6 encapsulated AV-6, stannosilicate AV-7, stannosilicate Avoidance rule Azamacrocycles in synthesis

3 l-P- 10 31-P-16 10-P-08 16-P- 19 02-P-32 29-P- 12 01 -P- 11 18-P- I 0 22-P- 13 13-P-I 1 23-P- 12 25-P-11 32-P-11 22-P- 12 0 l-K-01 27-P- 14 32-P-09 31-O-02 02-P- 11 05-P- 10 23-P-22 3 l-P- 12 01 -P- 17 17-P-05 17-0-03 17-P-I 6 17-P- 15 17-P- 15 0 I-P- 16 19-0-02 13-P-25 25-P- 12 23-P- 16 19-0-02 11-O-02 23-P-21 26-P- 13 26-P- 10 2 I-P-07 13-P-22 2 l-P-07 23-P-24 24-P-31 24-P-27 24-P-27 28-0-02 32-P-07 32-P-08 14-P- 13 04-P-09 11-O-01 11-O-01 10-0-03 05-P- 13 05-P- 13 0 I-P-07 05-0-03

402

Aziridination, olefins Azo dyes

24-0-04 21-O-02

B liB NMR 13-P-11 11B, quadrupolar interaction 13-P- 11 B distribution in MFI 13-O-02 BN nanoparticles 21-O-05 B ordering 13-0-01 B-substituted zeolites 13-P- 11 B-treated zeolites 11-P-23 Ba in alkaline synthesis 02-P-17 Ba-X, adsorbent 16-0-03 Basic catalysis 02-P-22 04-0-02 10-O-02 23-P-13 23-P-23 Basic catalysis, zincophosphates 29-P-23 Basic catalyst, immobilised 23-0-04 Basic catalysts, mesoporous 29-P- 10 Basic catalyst, MIBK synthesis 23-0-05 Basic probe molecules 13-P- 13 Basic zeolites 10-O-02 23-P-12 23-P-13 23-P-29 29-P-20 Basic zeolites, synthesis 04-0-02 Basicity of zeolites by NMR 13-P-23 Basicity, zeolite oxygen 14-O-02 BEA, adsorbent 18-0-02 BEA, A! distribution 13-P- 19 BEA, alkylation catalyst 24-P-06 24-P-20 25-0-02 25-P-07 25-P-09 25-P-13 25-P-14 02-P-35 BEA, all-silica, synthesis 20-P-18 BEA/alumina membranes 1 I-P-10 11-P-28 BEA, alumination 27-P-14 BEA, anthraquinone photocatalysts 24-0-04 BEA, aziridation catalyst 28-P- 11 28-P- 15 BEA, catalyst 20-P-12 BEA/ceramic composite membrane 04-P-08 BEA, Cr 02-P-23 BEA, crystallisation kinetics 11-P-22 BEA, dealumination and realumination 30-P-26 BEA-DLH oxidation catalyst 32-0-05 BEA, drug carrier BEA, effect of hydrophobicity on activity 28-P-14 28-P-14 BEA, esterification catalyst BEA, Fe 04-P-07 10-O-04 30-P-11 30-P-27 BEA, Fe, DeNOx catalyst 30-P-06 BEA, flexible lattice 13-P-22 BEA, Ga 03-P- 10 BEA, hydroconversion catalyst 24-0-03 BEA, In deNOx catalyst 10-O-01 BEA, isomerisation catalyst 24-P-16 25-P-0 26-O-01 28-P-13 BEA, lattice vibrations 12-P-07 BEA, macroporous structures 2 l-P- 15 BEA, Mo 14-P-08

BEA, NiMo hydrotreatment catalyst 26-P-15 BEA, partially crystalline 29-P-12 BEA, photocatalyst 30-P-20 BEA, polystyrene beads 2 l-P-12 BEA, polytypism 0 l-K-01 BEA, Pt 17-P-08 BEA, Pt aromatisation catalyst 15-P-09 BEA, Pt hydrogenation catalyst 26-P-13 BEA, Pt isomerisation catalyst 20-P-18 BEA, Pt/Cs 26-0-05 BEA, ring opening catalyst 26-0-03 BEA, silylation 1 l-P-09 BEA, synthesis, with DLH 30-P-26 BEA, Ti 27-P- 11 27-P- 17 BEA, V 14-P-35 Beckmann rearrangement 15-0-05 23-0-03 23-P-18 23-P-21 23-P-27 27-P-16 Bentonite adsorbent 32-0-04 Bentonite application 18-P- 14 Bentonite, pillared 22-P- 16 Bentonite zeolitisation 03-P-06 Benzaldehyde-ethylcyanoacetate condensation 23-0-04 Benzaldehyde, trimethylsilylcyanation 23-P- 11 Benzene adsorption 14-P- 14 18-P- 15 Benzene adsorption, MFI 17-0-02 18-P-08 Benzene alkylation 24-P-06 25-0-05 25-P- 15 29-O-01 Benzene diffusion, NMR imaging 19-K-01 Benzene hydroconversion 26-P- 15 Benzene hydrogenation 27-0-04 Benzene oxidation to phenol 27-0-03 Benzene removal, membrane 20-P- 12 Benzothiophene HDS 26-P-07 N-benzyl- l-azoniumbicyclo[2,2,2]-octane template 03-0-04 Beryllophosphate synthesis 05-P-06 Beryllosilicates 05-O-05 Beta cage, encapsulation modelling 15-P-08 Bifunctional catalysis 23-0-05 23-P-14 23-P-28 24-0-03 25-P-15 26-P-06 Bifunctional catalysts, MCM-41 26-P-18 Bifunctional catalysts, Pt,Ni-USY 14-P-36 Bile, adsorption 32-0-03 Bilirubin 32-0-03 Bimetallic catalysts 22-0-05 29-P-15 Bimetallic catalyst, Pt,Ni-USY 14-P-36 Bimetallic clusters with Au 11-O-01 Bimodal pore structure 06-P-20 Bimodal porosity, MFI 03-0-02 Binary adsorption 17-P- 15 18-P- 15 Binder, polymeric 22-P- 15 Biological wastewater treatment 3 l-P- 14 Biomedical applications 32-O-01 32-P-09 Biomimetic oxidation transfer 27-P- 10 Biphasic system, membrane separation 23-P-10 Biphenyl adsorption, MFI 14-P- 18

403

Biphenyl alkylation 25-P-07 25-P-09 25-P-14 29-P- 11 29-P-11 Biphenyl isopropylation 16-P-08 Biphenyl isopropylation, models 14-P-24 2,2'-Bipyridine adsorption/MFI 24-P-29 Bipyridine complex, encapsulated 08-P-12 Block copolymer surfactants 16-0-05 Boggsite, Xe-SF6 diffusion, modelling 13-P-11 Borates NMR 09-P-12 Borogermanates, layered 13-P-11 Borosilicates NMR 1 l-P-16 Borosilicate zeolites 26-0-05 Borosilicate zeolite reforming catalyst 13-P-25 Branched paraffins, adsorption on MFI Breakthrough curves 18-P- 15 19-P-06 24-0-04 Bromamine-T Bronsted acid sites 12-P-16 13-O-01 13-P-17 13-P-18 14-P-21 Bronsted acid sites in ZSM-5 13-P- 10 30-P-25 Bronsted acidity 05-P-09 1 I-P-07 13-P-19 14-P-23 Br~nsted acidity, EMT 24-P-15 Br~nsted acidity, ETS- 10 14-P-23 Bronsted acidity, FAU 13-P-05 Bronsted acidity, HPA Bulgaria, zeolite occurrences 0 l-P- 10 01-P-13 Bulk-material dissolution in MFI synthesis 02-P-26 22-0-03 Butadiene dehydrocyclodimerisation 24-P-09 Butane activation 24-0-01 n-Butane dehydroisomerisation n-Butane isomerisation 24-P- 16 29-P-17 24-P-20 2-Butene in alkylation Butene isomerisation 14-P-22 24-P-21 24-P-17 l-butene synthesis 05-P-17 Butylamine templates 23-P-23 n-Butyraldehyde aldol condensation

C 13C chemical shift anisoptropy 13C MAS NMR ~3C MAS NMR, molecular dynamics 13C NMR 03-0-04 09-P-11 13-P-16 23-P-12 ~3CNMR, MFI synthesis ~3CNMR probe, nitromethane t3C-27AI dipole interaction C4 hydrocarbons aromatisation C5-C7 olefins isomerisation C5-C6 hydroisomerisation C6 isomer diffusion C60 CF4-CH4 diffusion in FAU, modelling CH4 activation CH4 adsorption, AEL CH4 conversion

13-P-16 13-P-06 30-P-19 02-P-40 23-P-13 13-O-01

24-P-30 26-P-09 20-P-18 19-P-10 1 l-P-12 16-O-05 24-0-02 17-O-03 24-0-02

CH4 in deNOx SCR 10-O-01 30-P-28 CH4, photocatalytic oxidation 24-P- 12 CH4, supercritical adsorption, zeolites 17-P- 16 CH4-CF4 diffusion in FAU, modelling 16-O-05 Ca in LTL synthesis 02-P-17 Ca promoters, DeNOx 30-P-25 CaClz/Silica Gel 31-O-04 Ca,Na-LTA 17-P-09 Cadmium clusters 09-P-06 Cadmium exchange 3 l-P-08 Cafeine separation 20-0-05 Calcination, exchanged zeolites 10-P-07 Calcination, mordenite 12-P-05 Calcination, by ozone 11-P-27 Calcination, partial 1l-P-12 Calculations, ab initio 15-P- 14 Calculation, framework vibrations 14-P-34 Calculations, semiempirical 15-P- 14 Calixpyrrole synthesis 28-0-04 Calorimetric sensors 22-P-11 Calorimetry 31-O-04 Cancrinite synthesis 02-P-07 03-P-I 1 Cancrinite/sodalite overgrowth 02-P-28 Capillary columns, LTA 18-P-09 Caprolactam 23-P- 18 23-P-27 27-P-16 Carbanium cation 24-P-09 Carbenium ions 12-P-06 Carbocation 15-P- 15 Carbon intercalation 1 l-P-11 Carbon nanotubes 21-P-08 Carbon nanotubes, formation 22-P-08 Carbon number, effect on SCR 30-0-03 Carbon replica 07-P-22 Carbon templates for MFI mesopores 03-0-02 26-0-02 Carbon, mesoporous PL-1 07-O-01 07-P-22 29-P-13 Carbonisation 07-P-22 Catalyst deactivation 27-P- 16 Catalyst engineering 28-P- 12 Catalyst heterogeneity 23-0-02 Catalytic activity, external surface 13-P-09 Catalytic cracking 08-P- 13 Catalytic tests of acidity and basicity 13-P-23 Catalytic test reactions 26-P-11 Catalysis, see individual reactions Catalysis, effect of microwaves 28-0-02 Catechol 27-P- 17 Cation distribution, MOR 16-P-11 Cation distribution, Na,Ca-LTA 17-P-09 Cation effect on aromatisation 15-P-09 Cation effects in gas separation 18-O-03 Cation effect in microwave heating 11-P-I 3 Cation exchange 0 I-P- 17 09-0-05 10-0-02 10-P-05

1 l-P- 18 1 l-P- 19 2 l-P-07 3 l-P-05

31-P-06 31-P-08 31-P-10 31-P-15 31-P-16

404

Cation exchange, clinoptilolite 01-P-12 01-P-17 22-P-12 Cation exchange, drying effect Cation exchange, ETS-4 Cation exchange, FAU Cation exchange, indium Cation exchange, PHI Cation exchange, solid state 10-O-01 10-P-06 10-P-08 Cation exchange, SOMS Cation impurities, EPR Cation location Cation location, clinoptilolite Cation location, In-X Cation location, MOR Cation mobility, high temperature Cation properties, modelling Cation radicals Cation radicals, biphenyl/MFI Cation sites Cation sites, MFI Cation sites, modelling Cations sites by UV-visible spectroscopy Cd clusters Cd(l-x)Mn(x)S Cd-X Ce,EU silicates Ce and Pd promoter Ce-MCM-41 Ce-MCM-41, stability Ce-MFI Ce-MFI, oxihalogenation catalyst Ce-MOR Cellular reactions Cement-zeolite composite Ceramic support Ceramic from zeolites CHA CoAPO CHA from fly ash CHA, acidity, modelling Chabazite, rare earth Chabazite/sodalite overgrowth Chelate post-treatment Chelators, Fe Chemical liquid deposition Chemical shift and electric gradient Chemical shift-geometry correlation Chemical shift ~70-angle relationship Chemisorption Chiral hydrogenation Chiral molecular sieve Chiral templates Chiral Ti (IV) Salen complex Chlorination, diphenylmethane Chloroalkane adsorption, Ag-FAU Chloroalkenes on MFI Chloroaromatics dechlorination

22-P-15 1 l-P-20 1 l-P- 15 17-P-14 30-P- 15 01-O-05 30-P-27 05-0-01 14-P- 15 15-P- 11 01-O-03 09-P- 10 09-P- 13 14-P- 17 15-P-08 13-P-08 14-P- 18 03-0-03 15-P-24 15-P-23 14-O-03 09-P-06 21-O-03 09-P-06 05-P- 12 30-P-22 07-P-23 06-P- 19 23-P-24 23-P-24 29-P-11 32-P-09 3 l-P- 13 20-P-09 10-P-07 04-P- 13 18-P- 10 15-0-01 1 I-P-19 02-P-28 11-O-04 32-0-02 11-P-24 14-P-27 13-P- 11 14-O-02 17-P-08 23-P-25 05-P- 10 05-0-04 23-P-11 23-P-30 24-P- 19 17-P-I 1 23-P- 16

Chlorocarbon oxidation 30-P- 18 Chlorocarbon removal 30-0-05 Chiorofluorocarbon decomposition 30-P- 19 Chlorofluorocarbon-zeolite interaction 30-P- 19 Chloroform adsorption 3 l-P-08 Chloroform, adsorption in Na-Y 16-P- 14 Cholesterol 32-0-03 Chromatography, LTA column 18-P-09 Chromatography, MSU-X application 08-O-01 Chromatography, stationary phases 18-P-06 Cigarette smoke 30-P-07 Cinchonidine 23-P-25 Cinnamaldehyde hydrogenation 07-P- 16 Cinnamate ester synthesis 23-0-02 Cinnamyl alcohol 25-P-12 Circular crystals, mesoporous silica 06-0-02 CIT-5 (CFI), Fe 16-P-09 Citology 32-0-02 Citric acid, complexing agent 04-P- 15 CI-CIO hydrocarbons in SCR-NOx 30-0-03 Clays, polymer degradation catalyst 30-P-17 Clear solution synthesis 02-0-04 Clinoptilolite, acid sites 11-P-26 Ciinoptilolite, acid treatment 0 l-P-09 Clinoptilolite, acidity 23-P-09 Clinoptilolite adsorbent 32-P-08 Clinoptilolite, Ag 0 l-P- 15 Clinoptilolite, applications PL-2 3 l-P-07 3 l-P-08 3 l-P-10 31-P- 14 31-P-15 32-0-03 32-P-10 32-P-11 0 l-P- 10 Clinoptilolite, Bulgaria 32-0-03 Clinoptilolite, Ca Clinoptilolite, cation exchange 01-P-12 31-P-12 32-0-04 3 l-P-09 Clinoptilolite, cation exchanger 31-O-02 Clinoptilolite, crop enhancement 1 l-P-20 30-P- 10 Clinoptilolite, Cu 23-P-09 Clinoptilolite, dehydration 23-P-08 Clipnotilolite dehydration catalyst 30-P-10 Clinoptilolite, deNOx catalyst 19-0-04 Clinoptilolite, diffusion 32-P-09 Clinoptilolite and health 22-P-10 Clinoptilolite, host Clinoptilolite, hydrothermal transformation 32-P-07 3 l-P-06 Clinoptilolite for lead removal 32-P-12 Clinoptilolite, medical applications 32-0-04 Clinoptilolite, modified, adsorbent 01-O-02 Clinoptilolite, occurrences Clinoptilolite, organic-modified 22-P- 12 22-P-15 27-P-08 Clinoptilolite, oxidation catalyst PL-2 Clinoptilolite properties 32-P-07 Clinoptilolite, purified 01 -O-03 Clinoptilolite stability PL-2 Clinoptilolite, structure 11-P-26 Clinoptilolite thermal behaviour Clinoptilolite tuff 01-P-09 01-P-12 01-P-13 31-P-11

405

Cloverite, host 2 l-P- 14 Cluster calculations 15-P-09 Clusters, in LTA 22-P-17 CMK- 1 mesoporous carbon PL-1 J33Co MAS NMR 09-0-05 Co 2+ in AIPO4 04-P- 11 04-P- 13 CoAPO, deNOx catalysts 30-P-31 CoAPO-5 04-P-13 CoAPO-5, sensors 22-P-11 CoAPO- 18, Co site 14-0-05 CoAPO-31 14-P-13 CoAPO-31, synthesis 04-P-09 CoAPO-34 29-P-14 CoAPO-34, Co site 14-0-05 CoAPO-44 04-P- 13 CoAPSO-31, synthesis 04-P-09 Co, cation site 15-P- 11 Co-ERI, oxidation catalyst 27-P- 13 Co-FER catalyst 30-P-35 Co histidine complexes 27-P- 10 Co-HMS 29-P-08 Co 2§ ion probes 14-P-21 Co-MCM-22 14-P-21 Co-mesoporous silica 08-0-02 Co-MFI 04-P- 18 13-0-02 30-0-03 Co-MFI, deNOx catalyst 30-P-34 Co-MFI, by solid state ion exchange 10-P-08 Co-MOR, oxidation catalyst 27-P- 13 Co, Ni promotion 26-P-17 Co, Pd, Ce trimetallic catalysts 30-P-22 Co 2§ probe of AI distribution 13-P- 19 Co Salen complexes on MCM-41 23-P-10 Co site in CoAPO 14-O-05 Co spinel from zeolites 10-P-07 Co, tungstophosphates 05-P-20 Co UV-Vis 04-P-18 13-P-19 Co XPS 04-P- 18 Co-zeolites, oxidation catalysts 27-P-08 Co-zeolite Y, oxidation catalyst 27-P-13 CO adsorption 13-0-04 CO adsorption equilibria 12-P- 13 CO adsorption, AEL 17-O-03 CO adsorption, Ag-MFI 15-P- 10 CO adsorption/cation MFI 15-P-24 CO adsorption, Cu-MFI 14-P-40 CO adsorption, EMT 14-P-23 CO adsorption, FAU 14-P-23 CO adsorption, Pt-zeolites 17-P-08 CO hydrogenation 24-P-11 CO oxidation 29-P- 14 30-P- 10 CO reduction, MeAPO-34 29-P-14 CO2 adsorption, Cu, Zn-FAU 17-P-14 CO2 adsorption isotherms 17-P- 14 CO2 adsorption on zeolites 18-P- 10 CO2+H2 reaction 24-P-26 CO2 and refining PL-4 CO2 removal 18-0-01

CO2 separation CO2, supercritical solvent Coating Coating by LTA Coating, MFI/gold Coating by zeolites, Al alloy Coating, zeolites/diatoms Coke Coke, effect on catalysis Coke, effect on isomerisation Coke formation, MFI Coke selectivation Coke tolerance Coking, in MTO Cold start exhaust gases Colloidal FAU crystals 02-0-03 Colloidal MFI crystals Colloidal offretite Colloidal templates Combinatorial chemistry Combinatorial methods in synthesis 03-K-01 03-P-13 03-P-16 03-P-18 Commensurate phases, in AEL Compass forcefield Complexing agent Complexing agent, citric acid Composite, BEA/polystyrene 2 l-P- 12 Composite, diatom/zeolite Composite, LTA/polystyrene Composite, LTL/FAU Composite membrane, BEA/ceramic Composite membrane, MFI/ceramic Composite nanotube/AIPO4-5 Composite, resin-silicate Composite, zeolite-cement Composite, zeolite/polymer Composite zeolitisation Composite, ZSM-5/Raney metal Computational analysis 16-P-08 Confined system, 1-dimensional Confined systems, phase transitions

18-0-01

20-0-05 20-P-09 20-P-15 20-P-14 22-0-04 21-P-07 24-P-06 30-P-21 25-P-08 24-P-31 28-P-06 26-P-16 24-P-28 30-P-32 02-P-14 02-0-04 02-P-12 07-P-22 03-P-12 06-P-25 17-O-03 16-P-06

03-P-08 04-P- 15 21-P-15 21-P-07 21-P-12 07-P-10 20-P-12 20-P-12 2 l-P-08 03-P-07 31-P-13 19-0-05 21-P-07 30-P-29 16-P-15 17-P-17

17-O-01 17-P-17

Conformational analysis Congo red in MCM-41 Connectivities, by MQ MAS NMR Contaminant concentration Continuous microwave synthesis Conversion, polyethylene Cordierite support 12-P- 15 20-P- 13 Correlation functions Corrosion pevention 06-P-09 Cosurfactants CrAPO-5, synthesis Cr-BEA Cr cation exchange Cr ETS- 10 Cr-HMS

16-P-17 22-P-21 13-P-24 31-P-08 03-P-15 24-P-13 30-P-33 16-P-18 22-0-04 06-P- 18 04-P-12 04-P-08 31-P-13 27-P-15 28-P-07

406

06-P-12 Cr-MCM-48 23-P-24 Cr-MFI 27-P-06 Cr, oxidation catalyst 31-P-13 Cr removal from wastewater 31-P-13 Cr storage 27-P-08 Cr-zeolites, oxidation catalyst 23-P-24 Cr-ZSM-5, oxihalogenation catalyst 15-P-15 Cracking, alkanes 11-P-23 Cracking catalyst, treated USY Cracking, cumene 03-P- 14 04-P- 14 1 l-P-30 28-P- 16 29-P-07 26-P-10 Cracking, cyclic oils 26-P-11 Cracking, methylcyclohexane 24-P-06 Cracking, n-heptane 08-P-13 Cracking, n-hexadecane Cracking, n-hexane 26-0-01 29-P-26 24-P-13 Cracking, polyethylene 30-P-17 Cracking, polymers 15-P-22 Cracking, thiophene, modelling 29-P-07 cracking, 1,3,5-trisopropylbenzene 28-P-13 m-Cresol transformation Croatian clinoptilolite 0 I-P- 17 31-P-11 Crop enhancement 31-O-01 31-O-02 29-P-15 Crotonaldehyde, hydrogenation 29-P-15 Crotyl alcohol, synthesis 06-0-02 Crystals, circular, mesoporous silica 01-P-11 Crystal chemistry, analcime 20-P-16 Crystal growth, FAU 20-P-16 Crystal growth, LTA 02-P-09 Crystal growth, MFI 02-P-08 Crystal growth rate 02-P-37 Crystal growth, ultrasound monitoring 19-O-04 Crystal morphology, effect on diffusion 02-P- 17 Crystal morphology, LTL 16-P-16 Crystal morphology, TS- 1 20-0-04 Crystal orientation 02-P-23 Crystal size, BEA 24-P-16 Crystal size, effect on catalysis 02-P- 17 Crystal size, LTL Crystal size, MFI 02-P-09 02-P-15 04-P-10 Crystal size, Nb-MFI 04-0-04 Crystal size tayloring 09-P-14 Crystal structure, AlMepO 09-P- 11 Crystal structure, AIPO4-20 09-P-06 Crystal structure, Cd-FAU 09-P-07 Crystal structure, Cu molybdate Crystal structure determination 01-K-01 05-P-19 09-P-13 09-P-12 Crystal structure, layered germanate 05-0-01 Crystal structure, SOMS 29-P-12 Crystallinity, partial, BEA 02-P-20 Crystallisation 21-P-17 Crystallisation, AIMepO 03-P-18 Crystallisation fields 03-0-05 Crystallisation fields, K-Na system 02-P-37 Crystallisation, in-situ monitoring 02-P-23 Crystallisation kinetics, BEA

04-P- 16 Crystallisation kinetics, ETS-4 02-P-21 Crystallisation kinetics, KFI 02-P-29 Crystallisation, LTA 02-P-40 Crystallisation, MFI, phosphate-affected Crystallisation models 02-P-24 02-P-31 03-P-19 Crystallisation, mordenite 02-P-40 Crystallisation promotor, phosphate 02-P-30 Crystallisation, rapid 02-P-16 Crystallisation, silicalite- 1 02-O-05 Crystallisation, SSZ-24, AFM 16-P-06 Crystallography 133CsNMR 14-P-17 26-0-05 Cs-BEA, Pt 1 l-P-18 Cs cation exchange 23-0-05 Cs-FAU, Pt catalyst Cs,Na-FAU 14-P-I 7 29-P-20 29-P-20 Cs,Na-MFI 23-P-29 Cs-zeolite condensation catalyst 30-P-31 Cu in AIPO4, deNOx catalyst 14-P-40 Cu carbonyl complexes 1 l-P-20 Cu § cation Cu, cation exchange 1 l-P-20 31-P-08 15-P-11 Cu § cation site Cu 2+, cation site 15-P-11 30-P-10 Cu-Clinoptilolite Cu+-Cu2+ pairs in Cu-MFI 14-P-40 27-P-13 Cu-ERI, oxidation catalyst 12-P-09 Cu-exchanged zeolites 17-P-14 Cu-FAU Cu-FAU oxidation catalyst 27-P-13 30-P-23 24-P-23 Cu-FAU reforming catalyst 14-O-03 Cu-FER spectroscopy 27-P-10 Cu histidine complexes 29-P-08 Cu-HMS 07-0-04 Cu-MCM-41 04-0-01 Cu methylamino complexes Cu-MFI 04-0-01 12-P-15 13-O-02 15-P-13 30-0-03 30-P-09 30-P-33 24-P-30 Cu-MFI, aromatisation catalyst Cu-MFI, deNOx catalyst 16-P-20 30-P-14 30-P-21 Cu-MFI diffuse reflectance spectroscopy 15-P-13 Cu § in MFI framework 15-P-13 Cu 2+ in MFI framework 27-P-12 Cu-MFI oxidation catalyst 14-O-03 Cu-MFI, spectroscopy 14-P-40 Cu-MFI, synthesis 09-P-07 Cu molybdate structure 1 l-P-20 Cu-MOR 27-P-13 Cu-MOR, oxidation catalyst 12-P-09 Cu,Na-Y 24-P-26 CuO-ZnO-ZrO2 27-P-06 Cu, oxidation catalyst 07-P-19 Cu oxides in MCM-41 30-P-21 Cu 2+ reduction in Cu-ZSM-5 07-P-07 Cu/silica 1 l-P-20 Cu, UV-visible 15-P-11 Cu-zeolites

407

Cu-zeolites, oxidation catalysts 27-P-08 Cu, Zn mesoporous alumina 07-P-16 Cubic mesoporous silica, functionalized 07-0-02 CuI clusters in LTA 22-P-17 Cumene cracking 03-P- 14 04-P- 14 1 l-P-30 29-P-07 Cumene cracking on H-ZSM-5 28-P-16 Cumene, diffusion in MFI 19-O-03 Curcumin dye in MCM-41 22-P-21 CVD 11-P-24 CVD alkoxysilane 1 l-P-09 CVD alkoxysilane/MFI 10-P-09 11-O-02 CVD FeC13 11-O-05 CVD passivation 27-P- 17 CVOC abatement 30-0-05 Cycloalkane conversion 26-P- 10 Cyclobutylamine template 05-P- 19 Cyclohexane aromatisation 24-P-27 Cyclohexane isomerisation 26-P- 19 Cyclohexane oxidation 02-P-14 07-P-10 27-P-06 27-P-15 Cyclohexane, oxidation, total 30-P-09 Cyclohexane ring opening 26-0-03 Cyclohexanol, diffusion in ZSM-5 19-0-03 Cyclohexanone oxime 15-O-05 23-0-03 23-P-18 23-P-27 27-P-16 02-P-42 Cyclohexene aromatisation 24-P-22 Cyclohexene conversion 26-P- 17 29-P-29 Cyclohexene hydrogenation 2 l-P- 13 29-P-30 Cyclohexene oxidation 23-P-13 Cyclohex-2-en- 1-one condensation 26-P-16 Cyclopentane hydroconversion 23-P-17 Cytochrome C, adsorption 29-P-23 CZP zincophosphate

D D-AI-MCM-41 D-ZSM-5 1D confined system 2D correlation IR spectroscopy 2DNMR 13-P-18 13-P-19 DABCO-based template Dachiardite, AI ordering DC polarisation DCM resin/AIPO4-5 composites Deactivation, alkylation catalyst Deactivation, reforming catalyst Dealkylation, trimethylbenzene Dealuminated mordenite Dealuminated zeolite Y, Si/AI ratio Dealumination 05-P-14 11-P-25 12-P- 16 13-P-07 Dealumination, BEA 1 I-P-10 Dealumination, EMT

23-P- 15 23-P- 15 17-P- 17 12-O-01 13-P-24 02-P-27 0 l-P-07 22-0-04 21-O-04 24-P-06 24-P-23 25-P- 10 29-P-11 13-P-15 24-P-21 11-P-22 14-P-23

Dealumination, FAU 14-P-23 Dealumination, FAU, chemical 1 l-P-21 Dealumination, FAU, hydrothermal 1 l-P-21 Dealumination, FER 13-P- 17 Dealumination, MFI 29-P-06 29-P-26 Dealumination, MOR 12-P-05 Deboration 1 l-P- 16 n-Decane 26-P- 18 Decane conversion 13-0-02 n-Decane hydroconversion 26-P-06 29-P- 19 Decane, swelling agent 06-P-27 Deca(oxyethylene)oleyl ether, surfactant 08-0-02 Decomposition of water, photochemical 28-0-03 Defects, MFI 14-P- 19 Degradation, polyethylene 24-P-25 Degradation, polymers, catalytic 30-P- 17 Dehydration, Cd-FAU 09-P-06 Dehydration, clinoptilolite 11-P-26 Dehydration, isopropanol 29-P-06 Dehydration, K-LSX 09-0-01 Dehydration, MOR 09-P- 13 Dehydrocyclodimerisation, butadiene 22-0-03 Dehydrogenation, ethylbenzene 20-P-06 Dehydrogenation, methanol 10-P-05 Dehydroisomerisation, n-butane 24-0-01 Dehydroxylation, phenol 29-P-08 Delaminated zeolites 23-P-21 De novo simulation 16-P-09 DeNOx catalyst 30-P-29 DeNOx catalyst, aluminophosphate 30-P-31 DeNOx catalyst, Fe-zeolites 30-P-27 DeNOx catalyst, MCM-22 30-P- 13 DeNOx on Cu-MFI 16-P-20 DeNOx SCR ' 30-P- 10 DeNOx SCR by NH3 30-P-12 30-P-29 DeNOx SCR by CH4 10-O-01 30-P-I 5 30-P-22 30-P-28 30-P-35 DeNOx SCR by hydrocarbons 30-0-03 30-P-25 DeNOx SCR by propene 30-P-14 30-P-30 30-P-34 Densification, zeolite, thermal 10-P-07 Design of experiments (DOE) method 03-P- 16 Desulfurisation, modelling 15-P-22 Deuterium exchange 23-P- 15 Dewaxing 26-P-23 Dewaxing on Pt/AI-MCM-41 26-P-21 DFT (density functional theory) 15-P-11 DFT calculations 15-0-04 15-P-06 15-P-17 15-P-21 15-P-24 15-P-25 DFT calculations, alkene epoxidation 15-P- 18 DFT cluster calculations 15-O-03 15-P-11 15-P-13 15-P-20 15-P-22 DFT periodic calculations 15-0-03 Diagenetic zeolites 0 l-P-06 Diamond anvil cell 09-P-09 Diaromatics hydrodecyclisation 26-P- 13 Diatomite, coating by zeolites 21-P-07 Diazine adsorption, FAU 12-0-03

408

Dibenzothiophene adsorption 18-P-11 12-P-17 Dibenzothiophene hydrodesulfurisation Diblock copolymer surfactants 08-P-12 Dichloromethane degradation 30-0-05 Dielectric constant, zeolite films 20-P- 11 Dielectric spectroscopy 21-P-14 PL-4 Diesel pool 26-P-13 Diesel upgrading Diethylenetriamine template 02-P-41 Diffraction, anomalous 17-P-09 Diffraction, microcrystal 22-0-01 01-P-15 Diffuse reflectance, Ag 1I-P-20 30-P-21 Diffuse reflectance, Cu 04-P- 11 Diffuse reflectance, in situ Diffuse reflectance spectroscopy 07-P-14 15-P-11 26-P-14 26-P-22 Diffusion 16-P- 12 20-P-15 13-P-14 Diffusion, acetonitrile Diffusion, acetylene 19-P-07 19-0-02 Diffusion, aromatics Diffusion coefficients 19-P-08 20-P-15 Diffusion coefficients, reaction conditions 28-P-16 28-P-16 Diffusion constraints 19-0-04 Diffusion, effect of crystal morphology 19-K-01 Diffusion, hydrocarbons Diffusion, hydrocarbons, by 129XeNMR 19-P-09 19-P-09 Diffusion, MFI Diffusion, MFI, organics 19-0-03 19-P-10 19-P-08 Diffusion, MOR, n-hexane 20-P-15 Diffusion, PFG NMR 28-0-01 Diffusion, single file 20-P-15 Diffusivity, LTA coating 19-O-03 Diffusivity, MFI, organics 12-P-08 2,5-Dihydrofuran adsorption 24-P-29 Dimerisation, olefins 28-0-05 2,2-Dimethylbutane isomerisation 18-P-14 Dimethyldisulfide HDS 23-P-30 Diphenylmethane, chlorination 25-0-03 2,6-Dimethylnaphthalene 14-P-15 Dipole-dipole coupling 11-O-02 Disproportionation, aromatics 28-P-13 Disproportionation, cresols 29-P-19 Disproportionation, ethylbenzene Disproportionation, toluene 10-P-09 11-P-24 24-P-06 29-P-26 Dissolution, MFI 07-P-24 1l-P-30 DLH (double layered hydroxides), Fe,Co 30-P-26 n-Dodecane hydroisomerisation 08-P- 13 Dodecyl dimethyl benzylammonium surfactant 06-P-09 Dodecylamine, template 29-P-08 Dodecylphosphate surfactant 07-P-08 DON, see U T D - 1 Donor-acceptor interactions 22-P-06 Double bond isomerisation 23-P-26 Double-mesopore silica 06-P- 10 DRIFT spectroscopy 12-O-04 12-P-09

DRIFTS, in-situ 30-P-27 DRIFTS/PY 30-P- 18 Drinking water, deammoniation 3 l-P-09 Drug carriers 32-O-01 32-0-05 Drug carrier clinoptilolite 32-P-08 Drying, effect on ion exchange 1 I-P-20 Dual temperature ion exchange I l-P-18 Dubinin-Radushkevich equation 26-P-20 Dust, health effect 32-0-02 Dye molecules, encapsulation 21-O-02 22-P-06 Dyes in MCM-41 22-P-21 Dyes in mesoporous silica 22-P-20 Dyes, photochromic, encapsulated 22-P-07 Dyes in zeolites 22-P- 14 Dynamic pulse method 17-P-08 Dynamical processes, modelling 15-0-02

E-Caprolactam 23-P-27 Edingtonite from fly ash 18-P- 10 Edingtonite, lattice vibrations 16-P- i 9 EDS 09-P-10 Effect of H20 and SO2 on catalytic activity 30-P-22 Effluents, nitric oxide industry 30-P-34 Electric field gradient, FAU 14-P-27 Electrochemistry 20-P- 14 Electrode, anatase 22-P- 13 Electron density, SBA- 15 walls 08-0-03 Electron diffraction, HREM 14-P- 19 Electron-hole pairs, biphenyl/MFI 14-P- 18 Electron microscopy PL-5 Electron transfer in zeolite Ru-Y 28-0-03 Electron transfer, biphenyl/MFl 14-P- 18 Electronic materials 02-P-25 Electronic states 22-P- 17 EMT, acidity 13-P-21 14-P-23 EMT, transalkylation catalyst 25-0-04 EMT-MAZ overgrowth 02-P-06 Enantioselective catalysis 23-P-11 Enantioselective hydrogenation 23-P-25 Enantioselective synthesis, terminal epoxides 23-P-10 Encapsulation 07-P- 10 2 l-K-01 21 -O-05 22-P- 17 Encapsulation, AgI/LTA 14-0-04 Encapsulation, AgzS/LTA 27-P-14 Encapsulation, anthraquinone/BEA 11-O-01 Encapsulation, Au/FAU 24-P-29 Encapsulation, bipyridine/FAU 14-P-24 Encapsulation, bipyridine/MFI 22-P- 17 Encapsulation, CuI/LTA 21-0-02 Encapsulation, dyes 22-P-21 Encapsulation, dyes, MCM-41 02-P-14 Encapsulation, Fe complexes/FAU 10-O-03 Encapsulation, halides

409

23-P-19 HPA metal oxide photocatalysts 30-K-01 21-P-13 Mn complexes/FAU 21-P-11 Mn-bipyridyl/FAU 22-P- 18 PbI2/LTL 22-P-07 photochromic dyes 14-P-12 phthalocyanines 22-P-19 pigments Rb clusters, LTA 2 l-P-18 Tb[(CIBOEP)4P](acac)/MCM-41 22-P-09 14-P-07 ENDOR spectroscopy 31-P-10 Environment control Environmental catalysis 30-P-08 30-P-32 02-P-28 Epitaxial overgrowth CAN/SOD 02-P-28 Epitaxial overgrowth CHA/SOD 02-P-06 Epitaxial overgrowth MAZ/EMT 23-P-10 Epoxide, terminal, hydrolysis Epoxidation 2 l-P-07 27-P-06 29-P-30 Epoxidation, cyclohexene 24-P-14 Epoxidation, fixed bed Epoxidation, olefins 11-P-29 14-P-12 15-P-18 23-P-14 Epoxidation, alpha-pinene 24-P-14 27-0-02 Epoxidation, propylene 29-P-08 Epoxidation, styrene EPR spectroscopy 04-P- 10 04-P-I 1 05-P-I 1 13-P-08 13-P-09 14-O-05 14-P-12 14-P-20 14-P-37 15-P-11 30-P-26 14-P-15 EPR, cation impurities EPR, nitroxide 14-P-07 32-0-02 14-P-09 EPR, NO 14-P-18 EPR, polyaromatic ionisation 27-P-13 Erionite, Co 27-P-13 Erionite, Cu 27-P-13 Erionite, Fe 32-0-02 Erionite, health effect 27-P-13 Erionite, Ni 27-P-13 Erionite, oxidation catalyst 01-P-13 Erionite, in zeolitic tuff 29-0-01 ERS- 10 alkylation catalyst 29-O-01 ERS- 10, pore structure ESR (see EPR) 08-P-10 Esterification 28-P-14 Esterification, effect of hydrophobicity 28-P-11 ETBE 18-P-15 Ethanol adsorption 23-P-09 Ethanol conversion 27-P-14 Ethanol, in H2Oz synthesis 24-P-23 Ethanol, steam reforming 23-P-08 Ethanolamine, dehydration 18-P-12 Ethyl acetate adsorption 23-P-29 Ethyl acetoacetate condensation 29-0-01 Ethylbenzene 28-P-08 Ethylbenzene alkylation 20-P-06 Ethylbenzene dehydrogenation 29-P-19 Ethylbenzene disproportionation Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation,

Ethylcyanoacetate-benzaldehyde condensation 23-0-04 Ethylene adsorption 12-P-09 Ethylene ammoxidation 10-P-08 Ethylene conversion 24-P- 10 Ethylene dimerisation 24-P-29 Ethylene glycol in sodalite cage 16-P-17 Ethylene polymerisation 24-0-05 24-P-17 Ethylenediamine template 05-P-08 09-P-08 Ethyleneimine, formation 23-P-08 ETS-4 11-P- 15 ETS-4, morphology 04-P- 16 ETS-4, synthesis 04-P- 16 ETS-4, Zr 04-P- 16 ETS- 10, acid site NMR 13-P-23 ETS-10, Bronsted acidity 24-P-15 ETS-10, Cr 27-P-15 ETS-10, Fe 27-P-15 ETS- 10, HRTEM PL-5 ETS- 10 modification 11-0-04 ETS- 10, oligomerisation catalyst 24-P- 15 p-Eugenol isomerisation 23-P-26 Europium cerium silicates 05-P- 12 EXAFS 01-O-03 11-O-05 13-P-32 14-P-39 21-O-03 23-0-05 EXAFS/XANES 07-P-13 29-P-25 Exhaust gas treatment 30-P-10 30-P-32 External sites, probing 13-P-25 External surface acidity 13-P-09 External surface properties 16-O-02 Extraframework AI, modelling 15-P-21 Extra-large pore zeolites PL-3

19F NMR 08-0-04 09-0-02 11-O-03 30-P-I 9 Factorial design 03-P- 13 FAPO (Fe-AIPO4) 2 l-P-07 FAPO, deNOx catalysts 30-P-31 FAPO-5 14-P-39 FAPO- 11 14-P-22 FAPO-18 14-P-39 Fatty acids, selective adsorption in MFI 23-P-20 Fatty oils, hydrogenation 23-P-20 FAU, see also LSX, LZ-210, SAPO-37, USY 13-P-21 FAU, acid sites 13-P-13 FAU, acid site NMR 13-P-23 FAU, acidic and basic 23-P-12 FAU, acidity 13-P-07 13-P-21 14-P-23 15-P-16 23-P-09 FAU, acidity, modelling 15-0-01 FAU adsorbent 12-O-03 16-O-03 16-P-14 18-P-07 18-P-11 18-P-15 FAU adsorbent, Ar/N2 17-P-15

410

FAU, adsorption 12-P-08 FAU, adsorption models 16-O-03 FAU, Ag 18-0-05 24-0-02 24-P- 19 FAU, A1 site in activated 13-P-18 FAU, alkylation catalyst 24-P-09 25-0-02 25-P-07 25-P-09 25-P-13 28-P-15 FAU, B-treated 11-P-23 FAU, Ba, adsorbent 16-O-03 FAU, Cd 09-P-06 FAU, Co 27-P-13 FAU, colloidal 02-0-03 02-P- 14 FAU, Cr exchange 3 l-P- 13 FAU cracking catalyst 11-P-23 FAU, crystallisation monitoring 02-P-37 FAU, Cs 29-P-20 FAU, Cs, Pt catalyst 23-0-05 FAU, Cu 12-P-09 17-P-14 27-P-13 FAU, Cu, oxidation catalyst 30-P-23 FAU, Cu, reforming catalyst 24-P-23 FAU, dealumination 1l-P-21 13-P-07 FAU, diffusion 19-P-07 FAU, diffusion, CH4-CF4, modelling 16-O-05 FAU drug carrier 32-0-05 FAU, effect of H20 on xylene adsorption 16-O-03 FAU, electric field gradient 14-P-27 FAU, Fe 27-P-13 30-P-I 1 FAU, Fe, HDS catalyst 12-P- 17 FAU, film synthesis 20-P-16 FAU, fluorination 11-P-I 7 FAU-Ga 10-P-06 FAU, H form 12-P-06 25-P-15 FAU, host 02-P-14 11-O-01 14-P-12 14-P-29 14-P-37 21-P-10 21-P-II 2 l-P- 13 22-P-07 23-P- 19 24-P-29 30-P-08 FAU, hydration 15-0-04 FAU hydration catalyst 23-P- 19 FAU hydrotreatment catalyst 26-P-08 FAU isomerisation catalyst 11-P-23 14-P-36 25-P-08 26-O-01 28-P-13 FAU, K, adsorbent 16-O-03 FAU, K-LSX, orthorhombic 09-O-01 FAU, La 13-P-13 FAU, La hydrogenation catalyst 26-0-03 FAU, La, proton sites 09-0-04 FAU, lattice vibrations 12-P-07 14-P-31 FAU, Li,Na, 23Na NMR 13-P-12 FAU, Li,Na, pyrrole adsorption 12-P-12 FAU/LTA mixture, from fly ash 18-P-10 FAU/LTL composites 07-P- 10 FAU membranes 20-0-02 FAU, mesopore imaging 14-0-01 FAU, mesoporous 1l-P-08 FAU, Mn 21-P-11 21-P-13 FAU, modelling 15-P-25 FAU, nanocrystals 02-P- 14 FAU, nanotubes formation on 22-P-08 FAU, Na 10-P-05 12-P-08 13-O-03 30-P-07

FAU, Ni 24-P-24 27-P- 13 FAU, Ni oligomerisation catalyst 24-P-17 24-P-24 FAU, Ni,W hydrocracking catalyst 1l-P-08 FAU, NiMo hydrotreatment catalyst 26-P-15 FAU, nitroxide EPR 14-P-07 FAU oxidation catalyst 27-P-13 FAU, P-treated 11-P-23 FAU, Pd/K,Na23-P-23 FAU, Pd, Heck catalyst 23-0-02 FAU, photocatalyst 30-P-20 FAU, phthalocyanine epoxidation catalyst 14-P-12 FAU, polymer degradation catalyst 30-P-17 26-P-20 FAU, porosity 16-0-04 FAU, proton tunnelling 17-P-08 FAU, Pt FAU, Pt aromatisation catalyst 15-P-09 FAU, Pt bifunctional catalyst 30-0-05 27-0-05 FAU, Pt-Pd hydrogenation catalysts 02-P-07 03-P-11 FAU, reagent 09-P-lO FAU, In-exchanged FAU, Ru bipyridyl photocatalyst 28-0-03 17-P-16 FAU, supercritical adsorption 16-0-02 FAU (111) surface simulation 02-0-03 FAU synthesis 03-P-15 FAU synthesis, microwaves 03-0-05 FAU synthesis, role of K and Na 13-P-16 FAU, toluene adsorption NMR 25-0-04 FAU, transalkylation catalyst 13-P-15 FAU, unit cell constant 29-P-23 FA U zincophosphate 17-P-14 FAU, Zn 26-0-01 FCC gasoline quality 26-0-05 FCC heavy gasoline, reforming Fe-AIPO4, s e e FAPO Fe-BEA 04-P-07 10-O-04 30-P-06 30-P-11 30-P-27 Fe in CIT-5, characterisation 16-P-09 FeCls, CVD 11-O-05 Fe,Co double layered hydroxides 30-P-26 Fe, coordination in FAPO-11 14-P-22 Fe distribution in MFI 13-O-02 Fe effect on citotoxicity 32-0-02 Fe-ERI, oxidation catalyst 27-P- 13 Fe-ETS-10 27-P-15 Fe, extra-lattice 30-0-02 Fe-FAU 30-P-11 Fe-FAU, HDS catalyst 12-P-17 Fe-FAU, oxidation catalyst 27-P- 13 Fe-FER 10-O-04 Fe-FER oxidation catalyst 29-P-25 Fe(III) impurities, zeolite Y 14-P- 15 Fe-LTL 07-P- 10 24-P- 11 Fe-MCM-22 14-P-21 Fe-MCM-41 06-P-28 07-P- 14 Fe-MCM-41 oxidation catalyst 29-P-25 Fe-MCM-41, redox behaviour 07-0-03 Fe-MEL oxidation catalyst 29-P-25

411

Fe-MFI

04-P-07 11-O-05 23-P-24 30-0-02 30-P-11 30-P-27 Fe in MFI, characterisation 12-O-02 16-P-09 Fe-MFI, deNOx catalyst 12-O-02 30-P-14 Fe-MFI oxidation catalyst 29-P-25 31-O-03 Fe-MFI, oxihalogenation catalyst 23-P-24 Fe-MFI, sulfide host 29-P-05 Fe-MFI synthesis 04-0-03 Fe-MFI synthesis, fluoride 04-P- 17 Fe-MOR 04-P-15 13-P-32 30-P-11 30-P-27 Fe-MOR, oxidation catalyst 27-P-13 Fe-MTW oxidation catalyst 29-P-25 Fe-MTW, synthesis 04-0-03 Fe203 nanoparticles in MCM-41 07-P-13 Fe, oxidation state in FAPO-11 14-P-22 Fe oxo binuclear species 11-O-05 Fe-phen complexes, encapsulated 02-P- 14 Fe Raney/MFI composite 30-P-29 Fe-SAPO-34 30-P-27 Fe sites, FAPO 14-P-39 Fe-TON 04-0-04 Fe-TON, synthesis 04-0-03 Fenton H202 chemistry 31-O-03 FER, acidity 13-P- 17 FER, adsorbent 17-P-06 FER, Ag 14-0-03 FER, AI distribution 13-P- 19 FER, Co 30-P-35 FER, Cu 14-0-03 FER, dealumination 13-P- 17 FER, Fe 10-0-04 FER, Fe oxidation catalyst 29-P-25 FER, isomerisation catalyst 24-P-21 26-O-01 26-P-09 FER synthesis 03-P-09 Ferrocene/MCM-41 07-P- 13 Ferromagnetic zeolites 22-P- 10 Fertilizers, zeoponic delivery 31-O-02 Fibers, health effect 32-0-02 Fibers, mesoporous silica PL-1 06-0-02 22-P-20 Fibers, MFI 2 l-P-06 Fibers, MFI, by bulk-material dissolution 02-P-26 Film, MFI/ceramic 20-P-09 Film, FAU 20-P-16 Film, LTA 20-P- 10 20-P- 15 20-P- 16 Film, LTA/glass 20-0-01 Film, MFI 20-0-04 Film, MFI on AI 20-P- 17 Film, MFI on cordierite 20-P- 13 Film, MFI on gold 20-P- 14 Film, zeolite, all-silica 20-P-11 Film, zeolite, anti-corrosion 22-0-04 Filtration media 21 -P-07 Filtration, MSU-X application 08-O-01 Fine chemicals 23-K-01 23-P-21 23-P-22 23-P-29 24-0-04 Fischer-Tropsch synthesis 24-P- 11

Fisheries, deammoniation 3 l-P- 12 Flexibility, zeolite lattice 13-P-22 Flue gas adsorption 18-P- 10 Flue gas, screening 18-0-01 Fuorescence 22-P-06 Fluorescence, dyes in mesoporous silica 22-P-20 Fluorescence, laser induced 13-P- 13 Fluoride anion effect 06-P-26 06-P-28 Fluoride in CoAPO synthesis 04-P-09 04-P- 17 Fluoride in MCM-41 synthesis 06-P-28 Fluoride in MFI synthesis 02-P-26 Fluoride in MOR synthesis 02-P-39 Fluoride, location in IFR 22-O-01 Fluorination of zeolite Y 1 l-P- 17 Fluorogallophosphate 11-O-03 16-P- 15 Fluorogermanates, layered 09-P- 12 Fly ash, source of silica 18-P- 10 Formation fields, M4 ls 06-P-25 FOS-5, synthesis and structure 09-0-03 Fractal, silica aggregates 14-P-25 Fragrance synthesis 23-P-22 Framework enumeration, zeolites 16-P- 13 Framework polarity 32-0-05 Framework substitution 04-P-07 Framework vibration, TS- 1 14-P-34 Framework vibrations, zeolites 12-P- 10 Freezing in confined systems 17-0-01 Frequency response 19-0-02 19-P-07 Friedel-Crafts alkylation 25-0-02 25-P-12 29-0-03 FSM from saponite 06-P- 15 FSM- 16 17-P-05 22-0-05 FSM- 16, AI, host 29-P-29 FTIR, BEA dealumination, realumination 11-P-22 FTIR, 2D correlation 12-O-01 FTIR, HPA 13-P-05 FTIR skeletal vibrations 13-P- 15 FTIR spectroscopy 09-0-04 1 I-P-21 12-O-03 12-O-04 12-P-06 12-P-09 12-P-13 12-P-15 12-P-16 13-O-02 13-O-04 13-P-09 13-P- 17 13-P-21 13-P-25 14-O-05 14-P-20 14-P-23 14-P-30 14-P-34 14-P-40 15-O-05 15-P-13 17-P- 11 22-P-21 26-P-22 27-0-05 29-P- 19 29-P-20 30-P-16 30-P-31 32-P-07 FTIR spectroscopy, in-situ 12-P- 14 23-P-23 FTIR-UV Vis 14-P- 12 Fuel cell catalyst 07-P-20 Fukui functions 15-P-06 Fukui function overlap method 15-P- 19 Fumed silica 02-P-35 Function groups 17-P-06 Functionalized mesoporous silica 07-0-02 Furan adsorption 12-P-08 Furfuryl alcohol, hydroxyethylation 23-P-06

412

G

H

Ga-BEA 03-P-10 Ga-CON 1 l-P- 16 Ga-DON 1 l-P- 16 Ga-FAU 10-P-06 Ga-MCM-22, activation 11-P-27 Ga-MCM-41 07-P- 14 Ga-MCM-58 29-P-19 Ga-MFI 03-P-10 Ga-MFI, activation 11-P-27 Ga-MTW 03-P-10 Gallophosphates 1 l-P- 12 Gallophosphates, activation 16-P- 15 Gallophosphates, phase change 11-O-03 Gallosilicate 05-P-07 GaPO-42 (LTA), stability 1l-P-12 Gas purification 18-P- 10 Gas sensors 2 l-P- 10 22-P- 11 Gas separation, CO2/C2 18-0-03 Gas separation, kinetic 18-0-03 Gases, structured 10-0-03 Gasoline pool PL-4 Gasoline quality, FCC 26-O-01 Gel composition 02-P-20 Gel composition, effect on synthesis 02-P-21 GeO2, FOS-5 structure 09-0-03 Germanates, fluoro, layered 09-P- 12 GIS beryllophosphate 05-P-06 GIS from fly ash 18-P-10 GIS manganese phosphate 05-P-11 Glass, controlled porosity 17-P- 12 Glass, porous, Beckmann catalyst 27-P-16 Glass support for LTA layer 20-0-01 Glass, volcanic, zeolitisation 0 I-P- 13 Glycerol carbonate 23-P-32 Glycidol synthesis 23-P-32 Glycol solvent 05-P-11 GME beryllophosphate 05-P-06 Gold 11-O-01 Gold support 20-P- 14 GON (see GUS-I) Grafted MCM-41 29-P-28 grafting 21-O-02 Grafting, aluminium 29-0-04 Grafting, mesoporous silicas 18-P-06 29-P-09 Grafting, one-step or two-step 29-P-31 Grains, porous catalysts 28-P- 12 Gravimetry, Ar/N2 adsorption 17-P- 15 Grazing incidence X-ray diffraction 20-0-04 Green chemistry 16-P-09 Grignard reagents 29-P-09 Growth surface, SSZ-24, AFM 02-0-05 Guanidine, supported catalysts 29-P- 10 GUS- 1 (GON) 02-P-27

IH 2D NMR 13-P-19 ~H-MAS NMR, acid sites 1 l-P-07 ~H MAS spin echo NMR 14-P- 10 IH-NMR 08-0-04 09-P-I 1 11-P-28 13-P-14 IH-NMR imaging 19-K-01 tH NMR, MFI synthesis 02-P-40 lH-27AIdipolar coupling NMR 13-P-23 IH(E7AI) TRAPDOR NMR 08-0-04 IH-29Si dipolar coupling NMR 13-P-23 2H-NMR 13-P-14 H2 adsorption, LSX 12-0-04 H-, Ce-, Fe-, Mo-, Cr-ZSM-5 23-P-24 H202 20-P-14 21-P-07 Hz02 conversion 27-P-11 H202, Fenton chemistry 31-O-03 H202, oxidation agent 27-0-01 27-P-09 27-P- 15 29-P-18 H~O2, in oxihalogenation 23-P-24 H202, photocatalytic synthesis 27-P-14 H3PO3 reactions 05-P-15 H2S effect 26-P-07 HAFS analysis 30-P-24 Haloaromatics olefination 23-0-02 Halogenide, K, in oxihalogenation 23-P-24 Hartree-Fock method 15-P-08 15-P-09 HDN (hydrodenitrogenation) 26-P-14 HDS catalysts 26-P-08 26-P-12 HDS, benzothiophene 26-P-07 HDS, dibenzothiophene 12-P-17 18-P-14 HDS, dimethyldisulfide HDS, thiophene 26-P- 17 26-P-22 Health, animals 32-P-06 32-P-I0 32-P- 11 Health, human 32-O-01 32-0-02 32-P-09 32-P-12 Heat storage 2 I-P-09 31-O-04 02-P-08 Heating rate Heavy metals 3 l-P-05 10-P-07 Heavy metal-exchanged zeolites 23-0-02 Heck olefination on Pd-zeolites 13-0-02 Heptane 26-P-18 n-Heptane 24-P-06 n-Heptane cracking 26-P-11 n-Heptane hydroconversion 18-P-10 Herschelite (CHA) from fly ash 13 -O-02 Heteroatom distribution 25-P-16 Heteropoly acid, alkylation catalyst 23-P-19 Heteropoly acids, encapsulated 13-P-05 Heteropoly acid microporous salts 09-P-09 HEU (see clinoptilolite) 01-P-10 Heulandite-type zeolites, Bulgaria 08-P-13 n-Hexadecane cracking 24-0-03 n-Hexadecane hydroconversion 26-P-21 n-Hexadecane hydroisomerisation 26-P-21 n-Hexadecane isomerisation 1 l-P-17 Hexafluoroethane reagent

413

Hexamethylbenzene, guest

14-P-29

1,6-Hexamethylenediamine, template

02-P-22 02-P-42 Hexamethyldisiloxane in pore modification 1l-P-09 n-Hexane aromatisation 15-P-09 28-0-02 n-Hexane conversion, silylated MFI 11-O-02 n-Hexane cracking 26-0-01 29-P-26 16-P-16 Hexane diamine template 19-K-01 n-Hexane diffusion, NMR imaging 19-P-08 n-Hexane diffusivity, MOR n-Hexane isomerisation 19-P-08 14-P-36 26-P-19 06-P-23 n-Hexane hydroisomerisation 24-P-24 Hexene formation 29-P-24 1-Hexene isomerisation 10-O-03 HgX2 encapsulated 25-0-02 4-Hydroxybutan-2-one reagent 17-P-07 High-silica zeolites 18-P-15 High-silica zeolite adsorbent 10-P-07 High temperature treatment 03-P-I2 High-throughput strategies 27-P-10 Histidine complexes, immobilized 02-P-25 HLS silica 25-P-11 HMS alkylation catalysts 06-P- 11 HMS, amine extraction 29-P-08 HMS catalysts 29-P-08 HMS, Co 28-P-07 HMS, Cr photocatalysts 29-P-08 HMS, Cu 29-P-31 HMS grafting HMS, Ti 23-P- 14 29-P-08 14-P-20 HMS, V 26-P-22 HMS, Zr, support 21-P-12 Hollow zeolite spheres 20-P-13 Honeycomb, cordierite 21 -O-03 Honeycomb, MCM-41 29-P-27 Honeycomb, MCM-48 14-P-16 Host-guest interaction HPA, s e e heteropoly acids 18-P-06 HPLC, mesoporous silicas for 14-P-19 HRSEM PL-5 14-P-19 HRTEM 01-P-15 HRTEM, Ag-clinoptilolite 32-0-03 Human byle 29-P-28 Hybrid acid catalyst 29-0-02 Hybrid MCM-41 08-P-10 Hybrid mesoporous acids 29-P-31 Hybrid organic-inorganic materials 22-0-02 Hybrid solids 13-P-20 15-P-17 Hydration, AIPO4 15-0-04 Hydration, FAU 23-P-19 Hydration, alpha-pinene 20-P-14 Hydrazine 17-P-07 19-0-02 Hydrocarbon adsorption 24-P-31 Hydrocarbons, C4, aromatisation 30-0-03 Hydrocarbons, chloro-, in SCR-NOx 11-O-02 Hydrocarbon conversion, silylated MFI Hydrocarbon diffusion, by 129XeNMR 19-P-09

Hydrocarbon pool, MTO Hydrocarbon removal Hydrocarbon removal, exhaust gases Hydroconversion, alkanes Hydroconversion, benzene Hydroconversion, cyclopentane Hydroconversion, n-decane Hydroconversion, n-heptane Hydroconversion methylcyclopentane Hydrocracking 1I-P-08 13-O-02 26-P-15 Hydrocracking, n-hexadecane Hydrodechlorination Hydrodecyclisation, aromatics Hydrodesulfurisation Hydrogel milling Hydrogen acceptor Hydrogen adsorption Hydrogen in refining Hydrogen transfer in ketone reduction Hydrogenation 26-P-08 26-P-13 Hydrogenation, acetonitrile Hydrogenation, asymmetric Hydrogenation, benzene Hydrogenation, CO Hydrogenation, CO2 Hydrogenation, crotonaldehyde Hydrogenation, cyclohexene Hydrogenation, cynnamaidehyde Hydrogenation, fatty oils Hydrogenation, liquid phase Hydrogenation, olefins Hydrogenation, rings Hydrogenation, toluene Hydrogenolysis, cyclohexene Hydroisomerisation, C5/C6 Hydroisomerisation, n-decane Hydroisomerisation, n-dodecane Hydroisomerisation, hexadecane 24-0-03 Hydroisomerisation, long-chain n-alkanes Hydrolysis, terminal epoxide Hydrophobic MCM-41 Hydrophobic zeolites Hydrophobic zeolite in epoxidation Hydrophobicity, BEA Hydrophobicity, MCM-41 Hydrophobicity, MCM-48 Hydrophobicity, mesoporous silica Hydrophobisation, clinoptilolite Hydrophobisation, mesoporous silica Hydroquinone Hydrotalcite, basic catalyst Hydrothermal natural zeolites Hydrothermal stability, MTS Hydrothermal transformation Hydrothermal transformation, clinoptilolite Hydrothermal treatment Hydrotreatment 26-P-08 26-P-12

24-P-18 3 l-P-07 30-P-32 16-0-01 26-P-15 26-P-16 29-P-19 26-P-11 11-O-01

26-P-18 24-0-03 23-P-16 26-P-13 18-P-14 02-P-09 25-0-05 17-P-10 PL-4 23-P-33 29-P-15 23-P-28 23-P-25 27-0-04 24-P-11 24-P-26 29-P-15 26-P-17 07-P-16 23-P-20 29-P-13 29-P-22 26-P-10 27-0-05 29-P-29 20-P- 18 26-P-06 08-P-13 26-P-21 26-P-23 23-P-10 17-P-13 19-P-06

11-P-29 28-P-14 29-0-02 06-P-06 06-P-27 32-0-04 29-P-09 27-P-17 23-0-05 0 l-P-06 06-P-07 02-P-36 32-P-07 11-P-25 26-P- 17

414

Hydrotreatment, mesoporous catalyst 26-P-14 Hydroxyalkylation of aromatics Hydroxyalkylation of furfuryl alcohol Hydroxyethylation with H-zeolites Hydroxyl groups, BEA Hydroxyl groups, silicalite Hydroxylation, aromatics Hydroxylation, phenol 07-P-07 Hydroxyls, bridging, NMR Hydroxysilane Hypothetical framework 07-P-21 Hypothetical framework, MCR- 16

IFR IFR, synthesis Imaging, ~H-NMR Immobilisation in FAU Immobilized base Immobilized enantioselective catalyst Immobilized Salen Co complexes Impact craters Impregnation 03-P-11 In exchange In-MFI ln-X ln-zeolites, deNOx catalysts Indium silicates, microporous Insertion compounds in porosil In-situ diffuse reflectance In-situ DRIFTS ln-situ IR spectroscopy 12-O-01 In-situ LTA synthesis ln-situ NMR In-situ ultrasound monitoring Interatomic potential technique Intercalation compounds Intercalation, MOR/magadiite Interfacial resistance, membrane Interference microscopy Internal reflection Iodide removal Ion dynamics Ionic conduction, lithium silicate Ionisation, polyaromatics IR spectroscopy, s e e FTIR Iran, natrolite Iran, natural zeolites Iridium zeolites, hydrogenation catalyst Isobutane alkylation Isobutane diffusion Isobutane in silicalite lsobutanol oxidation

26-P-22 23-P-21 23-P-06 23-P-06 28-P- 11 15-O-05 21 -P-07 27-P-17 14-P-10 29-P-08 16-P-13 16-P-07

22-0-01 03-0-04 19-K-01 24-P-29 23-0-04 23-P-11 23-P-10 0 l-P-06 10-P-05 09-P- 10 30-P- 15 09-P-10 10-O-01 05-P- 16 10-O-03 04-P-11 30-P-27 23-P-23 18-P-09 02-P- 18 02-P-37 16-O-02 22-P- 16 02-P-36 19-O-05 19-0-04 21-O-04 18-0-05 14-P-06 09-0-05 14-P- 18 0 l-P-08 3 l-P-06 26-0-04 24-P-20 19-0-04 16-P- 12 27-P- 13

Isobutene synthesis 24-0-01 Isobutyric aldehyde, formation 27-P- 13 Isodewaxing 26-P-23 Isodimorphism of templates 0 I-P- 11 Iso-eugenol 23-P-26 Isomerisation 13-0-02 26-P- 18 Isomerisation, 1-acetyl-2-metoxynaphthalene 25-P-08 Isomerisation, alkanes 26-0-02 Isomerisation, n-butane 24-P- 16 29-P- 17 Isomerisation, butenes 24-P-21 Isomerisation, n-butene, skeletal 14-P-22 Isomerisation, C6 hydrocarbons 26-P- 19 Isomerisation catalyst, treated USY 11-P-23 lsomerisation, cresols 28-P- 13 lsomerisation, cyclohexene 24-P-22 Isomerisation, 2,2-dimethylbutane 28-0-05 Isomerisation, p-eugenol 23-P-26 Isomerisation, n-hexane 14-P-36 19-P-08 26-O-01 Isomerisation, 1-hexene 29-P-24 Isomerisation, light paraffins 06-P-23 Isomerisation, long-chain n-alkanes 26-P-23 Isomerisation, olefins 26-P-09 Isomerisation, toluene, modelling 15-P-20 lsomerisation, xylenes 12-P- 14 28-P-06 Isomerisation, xylenes, modelling 15-P-20 Isomerisation, xylene, NMR 12-0-01 lsomorphous substitution, B 11 -P- 16 13-P- 11 Isomorphous substitution, A! 1 I-P-16 lsomorphous substitution, AIPO4 30-P-31 lsomorphous substitution, AIPO4-31 14-P- 13 lsomorphous substitution, Co 04-P-II 04-P-13 04-P-18 Isomorphous substitution, Cr 04-P-08 lsomorphous substitution, Fe 04-0-03 04-0-04 04-P-17 Isomorphous substitution, Fe/MCM-41 07-0-03 Isomorphous substitution, Ga 1 I-P-16 11-P-27 Isomorphous substitution, MCM-41 29-P- 18 Isomorphous substitution, MFI 13-O-02 Isomorphous substitution, Nb 0 l-P- 14 Isomorphous substitution, Ta 01 -P- 14 Isomorphous substitution, V 14-P-33 24-P-07 Isomorphous substitution, Zn 04-P- 14 Isomorphous substitution, Zr 04-P- 16 Isopropanol adsorption 18-P- 15 Isopropanol dehydration 29-P-06 Isopropylation 25-P-09 25-P-16 Isopropylation, biphenyl 16-P-08 29-P-11 Isopropylation, naphthalene 25-P-06 lsopropylnaphthalene 25-P- 16 Isosteric heats of adsorption 17-P- 14 Isotherm of adsorption 17-P- 15 Isotopic labelling, MTO 24-P- 18 Isotopic traces technique 23-P- 15 IST- 1 02-P-33 IST-2 02-P-33

415

ISV (see ITQ-7) ITQ-2 acidity ITQ-2, fine chemistry catalyst ITQ-4 (IFR) ITQ-6, fine chemistry catalyst ITQ-7, alkylation catalyst

13-0-04 23-P-21 22-0-01 23-P-21 24-P-20

Jet-loop reactor Jordanian CHA-PHI tuff

28-P- 16 31-O-01

K

39KNMR K exchange K cation in synthesis K-FAU K-FAU, adsorbent K+ location, LSX K-LTL, catalyst K-M (see MER) K, Sr-KFI, synthesis Kanemite-derived mesoporous silica Ketones, unsatutated Keywords Kinetic modelling, NO-N20 interaction KIT-I Knight shift Knoevenagel condensation 04-0-02 23-0-04 23-P-29 Kr adsorption, AEL KSW-2, HRTEM KZ-2 (TON), synthesis

La exchange La in AIPO4, deNOx catalyst La-FAU 09-0-04 La-FAU ring opening catalyst La-MCM-4 l, stability La promoters, deNOx Lactame Lake fresh water zeolitization Lamellar aluminophosphate Large crystals activation Large crystals, MFI Large pore Ni(II) phosphate VSB-1 Large pore vanadosilicates Large pore zeolites PL-3 17-P-07 Large pore zeolite catalysts 25-P-06 25-P-10 26-P-15 26-P-16

09-0-01 1l-P- 18 03-0-05 09-0-01 16-0-03 09-0-01 23-P-30 02-P-21 PL-1 23-P-33 PL- 1 16-P-20 25-P-16 14-P-37 29-P-23 17-O-03 PL- 1 04-0-04

1 l-P-19

30-P-31 13-P-13 26-0-03 06-P-19 30-P-25 23-P-21 01-P-10 02-P- 11 14-P-38 02-P-15 22-0-03 04-0-05 24-P-06 28-P-13

Laser ablation 14-P-29 Laser dyes, mesoporous silica 22-P-20 Laser-induced fluorescence 13-P-13 Lattice dynamical calculations 16-P-19 Lattice energy calculation 07-P-21 Lattice model, adsorption 16-P-10 Lattice vibrations 12-P-07 14-P-31 16-P-18 Lattice vibrations, natrolite 16-P-19 Laumontite, cation exchange 31-P-12 Layer-by-layer shaping method 2 l-P-06 Layered compounds 02-P- 11 Layered Cu molybdate 09-P-07 Layered double hydroxide, Fe,Co 30-P-26 Layered germanates 09-P-12 Layered silicate 02-P-25 02-P-36 Layered zeolite menbranes 20-0-02 LCO, reforming 26-0-05 Leaching, MFI 07-P-24 Lead removal 3 I-P-06 Lewis acid 14-P-21 29-0-03 Lewis acid sites 13-P-08 13-P-17 Lewis acidity 13-P-19 Lewis basic sites 15-P-22 7Li'MAS NMR 09-0-05 7Li NMR, FAU adsorbent 12-P-12 Li exchange 01-0-04 Li,Na-FAU, 23Na NMR 13-P-12 Li,Na-FAU, pyrrole adsorption 12-P-12 Li-LSX 12-O-04 Li-LTA, H2 adsorbent 17-P-10 Li-Phillipsite 01-O-04 Li silicate RUB-29 09-0-05 Linde F (see EDI) Linkers, covalent, LTA/glass 20-O-01 Liquid crystals, confined 21-P-14 Liquid phase sulfoxidation 27-P-09 Low silica zeolites, synthesis 05-P-07 LSX (low-silica X, FAU), JTo NMR 14-0-02 LSX, alkali-exchanged 14-0-02 LSX, K 09-0-01 LSX, La 09-0-04 12-0-04 LSX, Li 12-0-04 LSX, Na LTA adsorbent 18-O-03 18-P-07 17-P-15 LTA adsorbent, Ar/N2 17-P-16 LTA, adsorption, supercritical 14-0-04 LTA, Ag 18-P-09 LTA, capillary column 23-P-32 LTA, catalyst 14-P-06 LTA, cation relaxation 02-P-37 LTA, crystallisation monitoring 19-P-07 LTA, diffusion 15-P-08 LTA, encapsulation modelling 18-P-10 LTA/FAU mixture, from fly ash 20-0-01 LTA, film, glass supported LTA, film 20-P-10 20-P-16 1 l-P-12 LTA, GaPO

416

LTA, Hz adsorbent 17-P- 10 LTA host 14-0-04 2 l-P- 18 22-P- 17 LTA, host, sulfides 22-P- 19 LTA, Li 17-P- 10 LTA, membranes 20-0-02 LTA, Na 10-P-05 30-P-07 LTA, nanotubes formation on 22-P-08 LTA reagent 03-P-11 LTA, synthesis 02-P-18 02-P-29 02-P-32 LTA, synthesis, in-situ 18-P-09 LTA, synthesis, role of K and Na 03-0-05 LTA, ~70 NMR 14-0-02 LTA, P occlusion 18-P- 13 LTA, polystyrene beads 2 I-P- 12 LTA, reagent 02-P-07 LTL host, Pbl2 clusters 22-P-18 LTL synthesis 02-P- 19 LTL synthesis, alkaline earth effect 02-P-17 LTL, acid site NMR 13-P-23 LTL/FAU composites 07-P- 10 LTL, Fe 07-P-10 24-P-11 LTL, formation of nanotubes on 22-P-08 LTL, K, catalyst 23-P-30 LTL, lattice vibrations 12-P-07 LTL, morphology 02-P- 17 LTL, Pd, Heck catalyst 23-0-02 LTL, Pt aromatisation catalyst 15-P-09 LTL, Pt/K catalyst 1 l-P-07 Luminescence spectroscopy 22-P-09 27-P-11 Luminescence, Ag-LTA 14-0-04 Luminescence, PbljLTL 22-P- 18 LZ-210 (FAU) 18-O-05

M M41 s synthesis 07-P-24 M41 s, XRD 06-P-05 Macrocycles, aza05-0-03 Macrocycle synthesis 28-0-04 Macroporosity, BEA 2 l-P- 15 Magadiite-intercalated MCM-22 05-P- 14 Magadiite in MOR synthesis 02-P-36 Magadiite, pillared 23-P- 18 Magnetic properties 2 l-P- 18 22-P- 10 Magnetic semiconductors, diluted 21-O-03 Magnetic susceptibility 11-O-05 Magnetism, Rb clusters in LTA 21-P-I 8 Magnetite, guest 22-P- 10 Manganese complexes in FAU 2 l-P-13 Manganese phosphate, Al-substituted 05-P-11 Manometry, high-resolution 17-P- 15 MAPSO-31, Pt catalyst 26-P-06 MAPSO-56 (Co,Mn,Zr) 05-P- 18 Market, gasoline PL-4 Market, zeolite PL-4

MAS-5 06-P-07 MAS NMR (see individual nuclei) MAS NMR, high temperature 14-P- 17 Mass spectrometry 14-P-29 MAZ-EMT overgrowth 02-P-06 MBIK (methyl isobutyl ketone) synthesis 23-0-05 MCM-22, see MWW MCM-36, basicity 10-0-02 MCM-41 06-P-07 08-P-06 17-P-17 25-P-13 27-P-09 MCM-41, adsorbent 17-0-01 MCM-41 adsorbent, VOC removal 18-P- 12 MCM-41, adsorption 17-P- 12 MCM-41, fine chemistry catalyst 23-P-21 MCM-41, ZTAI-NMR 06-P- 17 MCM-41 alumination 23-P-33 25-P-12 MCM-41, aluminosilicate 06-P-08 MCM-41 Beckmann catalyst 23-0-03 MCM-41 bifunctional catalyst 26-P- 18 MCM-41 catalysts 28-0-04 MCM-41, Ce 07-P-23 MCM-41, Cu 07-0-04 MCM-41, deuterated 23-P- 15 MCM-41, Fe 06-P-28 07-0-03 07-P- 13 07-P-14 MCM-41, Fe oxidation catalyst 29-P-25 MCM-41, functionalized, synthesis 07-0-02 MCM-41, Ga 07-P- 14 MCM-41, grafting 17-P- 13 29-P-28 29-P-31 MCM-41, honeycomb 21-O-03 MCM-41, host 07-P- 19 21-O-05 21-P-14 22-P-09 22-P-21 22-P-08 MCM-41 hydrogenation catalyst 23-P-28 MCM-41 hydrophobisation 29-0-02 29-P-09 MCM-41 hydrotreatment catalyst 26-P-14 26-P-17 MCM-41 in HPLC 18-P-06 MCM-41 isomerisation catalyst 24-P-22 MCM-41, Mn, DeNOx catalyst 30-P- 12 MCM-41, Nb 07-0-04 24-P-12 MCM-41, Ni, hydrodechlorination catalyst 23-P-16 MCM-41, Ni,Zr 23-P-28 MCM-41, noble metals 29-P-22 MCM-41, porosity by positron annihilation 12-P-I 1 MCM-41, Pt chiral hydrogenation catalyst 23-P-25 MCM-41, Pt hydroisomerisation catalyst 26-P-21 MCM-41, reagent 07-P- 10 MCM-41 silylation 29-0-02 MCM-41, size control 06-P-09 MCM-41, spheres 06-P- 13 MCM-41, stability, effect of AI 06-P- 19 MCM-41, stability, effect of Ce 06-P- 19 MCM-41, stability, effect of La 06-P-19 MCM-41 support 24-0-05 26-P-07 26-P-12 27-P-10 29-P-22 MCM-41 support, chiral catalyst 23-P-10 23-P-11 MCM-41, synthesis 06-O-01 06-P-14 06-P-26 07-P-24 MCM-41, synthesis, aging effect 06-P-21

417

MCM-41, synthesis, microwave 03-P- 15 MCM-41, synthesis, secondary 06-P- 10 MCM-41, Ti 07-P- 14 22-P-06 24-P- 12 29-P-30 29-P-18 MCM-41, Ti, oxidation catalyst 29-P-21 MCM-41, transition metals 29-P-18 MCM-41, V, oxidation catalyst 08-P-14 MCM-41, wall properties 06-P-28 MCM-41, washing effect 06-P-05 MCM-41, XRD 29-P-24 MCM-41, Zr, isomerisation catalyst 29-P-18 MCM-41, Zr, oxidation catalyst 17-P-12 MCM-48, adsorption 29-0-04 MCM-48, alumination 23-0-03 MCM-48, Beckmann catalyst 06-P-12 MCM-48, Cr 29-P-27 MCM-48, honeycombs PL-5 MCM-48, HRTEM 06-P-06 MCM-48, hydrophobicity 29-P-27 MCM-48, morphology 06-P-06 MCM-48, stability 06-0-04 06-P-06 MCM-48, swelling 06-O-01 06-P-24 07-P-06 MCM-48, synthesis 29-P-30 MCM-48, Ti 06-P-06 07-P-06 MCM-48, V MCM-48, ~29XeNMR 06-P- 16 29-P-19 MCM-58 16-P-07 MCR- 16, hypothetical structure 29-P-25 MEL, Fe oxidation catalyst 14-P-08 MEL, Mo 14-P-20 MEL, V 17-0-01 Melting in confined systems 23-P-10 Membrane, asymmetric separation 20-P- 18 Membrane, BEA/alumina 20-P-12 Membrane, BEA/ceramic 20-P-18 Membrane, catalytic reactor 28-0-03 Membrane, FAU Membrane, MFI 03-P- 17 20-P-06 20-P- 17 Membrane, MFI/alumina 20-O-05 Membrane, MFI/ceramic 20-P- 12 Membrane, MOR 20-0-03 Membrane, MOR/alumina 20-P- 18 Membrane, VOC removal 20-P-12 Membrane, zeolites 20-0-02 20-P-07 Membrane, zeolite, modelling 16-O-05 Membrane, zeolite/polymer 19-0-05 Membrane, zeolitic, supported 20-0-03 Memory effect PL-2 Menthene condensation 23-P-29 MER from fly ash 18-P-10 Mercapto functionalisation 07-P- 17 Mesophases 08-P-12 Mesopores, FAU 1 l-P-08 14-0-01 Mesopores, MFI 03-0-02 1l-P-30 26-0-02 Mesoporosity SBA-15 08-0-03 08-0-04 Mesoporous alumina 07-P-08 07-P- 18 Mesoporous alumina, Cu, Zn 07-P- 16

Mesoporous aluminosilicate 06-P-07 06-P-08 06-P-22 Mesoporous anatase 22-P- 13 Mesoporous basic catalysts 29-P- 10 Mesoporous carbon PL- 1 07-0-01 07-P-22 29-P- 13 Mesoporous-microporous mixed structures 06-0-03 Mesoporous molecular sieve, keywords PL-1 Mesoporous molecular sieves 17-O-01 17-P-05 29-P-30 Mesoporous silica (see also specific names, e.g. FSM-16, HMS, KIT-l, KSW-2, LMV-1, M41s, MAS-5, MCM-41, MCM-48, MSU-X, MTS, SBA-n) PL-1 06-P-07 06-P-20 07-P-24 08-P-05 08-P-06 08-P-07 17-P-17 25-P-13 27-P-09 29-P-30 Mesoporous silica, acidity 29-0-03 Mesoporous silica, activation 29-P- 16 Mesoporous silica, 27AI_NMR 06-P- 17 Mesoporous silica adsorbent 17-0-01 17-P-05 17-P-12 18-P-12 23-P-17 28-P-10 Mesoporous silica adsorbent, VOC removal 18-P-12 Mesoporous silicas, adsorption 17-P- 12 Mesoporous silica alumination 23-P-33 25-P-12 29-0-04 Mesoporous silica alkylation catalyst 25-P-11 Mesoporous silica, Beckmann catalyst 23-0-03 Mesoporous silica, bifunctional catalyst 26-P-18 Mesoporous silica, Ce 07-P-23 Mesoporous silica, Co 08-0-02 29-P-08 Mesoporous silica, Cr 06-P- 12 Mesoporous silica, Cr photocatalysts 28-P-07 Mesoporous silica, cracking catalyst 08-P- 13 Mesoporous silica, Cu 07-0-04 29-P-08 Mesoporous silica, Fe 06-P-28 07-0-03 07-P-13 07-P-14 29-P-25 Mesoporous silica, Fe oxidation catalyst 29-P-25 Mesoporous silica fibers 06-0-02 22-P-20 Mesoporous silica, fine chemistry catalyst 23-P-21 Mesoporous silica, functionalized 07-0-02 07-P-17 08-P-08 08-P-I 0 29-P-16 Mesoporous silica, Ga 07-P- 14 Mesoporous silica, grafting 17-P-I 3 29-P-28 29-P-31 Mesoporous silica, honeycomb 21-O-03 29-P-27 Mesoporous silica, host 07-P- 19 21-O-05 21 -P- 14 22-P-09 22-P-21 22-P-08 29-P-17 22-P-20 29-P-29 Mesoporous silica, HPA support 25-P-16 Mesoporous silica in HPLC 08-O-01 18-P-06 Mesoporous silica, HRTEM PL-1 PL-5 Mesoporous silica, hybrid acids 08-P-10 Mesoporous silica, hydrodechlorination catalyst 23-P-16 Mesoporous silica hydrogenation catalyst 23-P-28 Mesoporous silica, hydrogenation catalyst, chiral 23-P-25

418

Mesoporous silica, hydroisomerisation catalyst 08-P- 13 26-P-21 Mesoporous silica, hydrophobicity 06-P-06 Mesoporous silica hydrophobisation 29-0-02 29-P-09 Mesoporous silica, hydrotreatment catalyst 26-P-14 26-P-22 Mesoporous silica, isomerisation catalyst 24-P-22 29-P-24 Mesoporous silica from kanemite PL-1 Mesoporous silica, Ni 08-0-02 Mesoporous silica, Mn, DeNOx catalyst 30-P-12 Mesoporous silica, Mo 14-P-26 Mesoporous silica, morphology 29-P-27 Mesoporous silica, Nb 07-0-04 24-P-12 Mesoporous silica, Ni 23-P- 16 Mesoporous silica, Ni,Zr 23-P-28 Mesoporous silica, noble metals 29-P-22 Mesoporous silica, oxidation catalyst 29-P- 18 Mesoporous silica, photocatalyst 24-P-07 24-P-12 Mesoporous silica, polymer degradation catalyst 24-P- 13 24-P-25 Mesoporous silica, porosity 08-0-03 Mesoporous silica, redox catalyst 23-P- 14 Mesoporous silica from saponite 06-P-15 Mesoporous silica spheres 06-0-02 06-P-13 Mesoporous silica spheres, SBA- 15 08-P-07 Mesoporous silicas, stability 06-O-01 Mesoporous silica silylation 29-0-02 Mesoporous silica, size control 06-P-09 Mesoporous silica, spheres 06-P-13 Mesoporous silica, stability 06-P-06 06-P- 19 08-P- 13 Mesoporous silica support 24-0-05 26-P-07 26-P-12 27-P-10 29-P-22 Mesoporous silica support, chiral catalyst 23-P- 10 23-P- 11 Mesoporous silica, swelling 06-0-04 06-P-06 Mesoporous silica, synthesis 06-0-01 06-P-14 06-P- 18 06-P-21 06-P-22 06-P-24 06-P-25 06-P-26 06-P-28 07-P-06 07-P-24 08-0-02 08-P-09 08-P-11 08-P-12 Mesoporous silica, synthesis, acidic pH 06-P-28 29-P-16 Mesoporous silica, synthesis, aging effect 06-P-21 Mesoporous silica, synthesis, microwave 03-P-15 Mesoporous silica synthesis, pH effect 06-P-20 Mesoporous silica, synthesis, secondary 06-P-10 Mesoporous silica, template extraction 06-P-11 Mesoporous silica, texture 08-P- 14 Mesoporous silica, Ti 07-P-14 22-P-06 23-P-14 24-P-12 29-P-08 29-P-18 29-P-30 Mesoporous silica, transformation 06-P- 18 Mesoporous silica, transition metals 29-P-21 Mesoporous silica, V 06-P-06 07-P-06 14-P-20 24-P-07 29-P-18 Mesoporous silica, XRD 06-P-05

Mesoporous silica, wall properties 08-P- 14 Mesoporous silica, washing effect 06-P-28 Mesoporous silica, 129XeNMR 06-P- 16 Mesoporous silica, Zr 26-P-22 29-P-18 29-P-24 Mesoporous single crystals 07-P-15 Mesoporous sulfides 1 I-P-11 Mesoporous titania 07-0-05 07-P-12 Mesoporous zirconia 07-P- 11 Mesoporous zirconia fuel cell catalyst 07-P-20 Mesostructural transformation 06-P-26 04-P-11 05-0-03 Metal aluminophosphates 32-P-07 Metal cations 04-0-01 Metal cation reduction 05-0-03 Metal cations in MeAPO synthesis 22-0-04 Metal corrosion prevention 24-0-05 24-P-08 Metallocene, supported catalyst 27-P-06 Metallosilicates, microporous 29-P-20 Methanol adsorption 11-P-25 Methanol amination 07-P- 19 29-P-20 Methanol conversion 10-P-05 Methanol dehydrogenation 24-P- 12 24-P-26 Methanol formation Methanol in alkylation 15-0-03 25-0-03 25-P- 13 Methanol to hydrocarbons 24-P-18 Methanol, reagent 25-0-01 Methanol, steam reforming 24-P-23 Methylamine in MFI synthesis 04-O-01 N-Methylation, aniline 25-P-11 Methylation, 4-methylbiphenyl 25-0-01 Methylation, toluene, model 15-0-03 4-methylbiphenyl, methylation 25-0-01 Methylcyclohexane cracking 26-P-11 Methylcyclopentane hydroconversion 1 I-O-01 Methylene silanes 2 I-P- 16 N-Methyl hexahydrojulodinium template 02-P-30 Methylnaphtalene alkylation 25-P- 13 Methyloxirane ring opening 23-P- 15 Methylpropyl ether 27-0-02 MFI 02-P-31 12-P-13 14-O-03 16-P-06 23-P-06 30-P-18 MFI, acid site NMR 13-P-23 MFI, acidity 13-P-08 13-P-25 MFI, acidity, modelling 15-0-01 MFI adsorbent 17-O-02 18-P-07 18-P-08 18-P-15 19-O-02 MFI, adsorption, biphenyl 14-P- 18 MFI, adsorption, bipyridine 14-P-24 MFI, adsorption, chloroalkenes 17-P- 11 MFI, adsorption modelling 16-P- 10 16-P- 12 MFI, Ag 14-O-03 15-P-10 30-0-03 30-P-28 MFI, Ag, deNOx catalyst 30-P-34 MFI, Ag, photocatalyst 30-P- 16 MFI, AI in activated 13-P- 18 MFI, A! distribution 13-P- 19 MFI, alkali leaching 07-P-24 1 l-P-30 MFI alkane conversion catalyst 15-P- 15

419

MFI alkylation catalyst 25-O-01 25-0-05 25-P-09 28-P-15 MFl/alumina membranes 20-0-05 MFI aromatisation catalyst 28-0-02 MFI, Beckmann catalyst 15-0-05 27-P- 16 MFI catalyst 24-P- 10 26-P- 10 MFI, Ce, oxihalogenation catalyst 23-P-24 MFI/ceramic composite membrane 20-P- 12 MFI, Co 10-P-08 04-P- 18 30-0-03 MFI, Co, deNOx catalyst 30-P-34 MFI, coke-selectivated 28-P-06 MFI on cordierite 30-P-33 MFI, crystal size control 02-P- 15 MFI cracking catalyst 28-P- 16 MFI, Cr, oxihalogenation catalyst 23-P-24 MFI, Cs 29-P-20 MFI, Cu 04-0-01 12-P- 15 14-O-03 15-P-13 30-0-03 30-P-09 30-P-33 MFI, Cu, aromatisation catalyst 24-P-30 MFI, Cu, deNOx catalyst 16-P-20 30-P- 14 MFI, Cu oxidation catalyst 27-P-12 MFI, Cu, synthesis 14-P-40 MFI, dealuminated, acidity 29-P-06 MFI dealumination 29-P-26 MFI, defects 14-P- 19 MFI, deNOx catalyst 30-P-13 30-P-25 MFI, deuterated 23-P- 15 MFI, diffusion 19-0-04 19-P-09 19-P- 10 MFI, diffusion, hydrocarbon 19-K-01 MFI, electronic material 14-P- 18 MFI, enhanced acidity 13-P- 10 MFI, Fe 04-P-07 11-O-05 12-O-02 16-P-09 30-P-11 30-P-27 31-O-03 MFI, Fe, deNOx catalyst 30-P-14 MFI, Fe oxidation catalyst 29-P-25 MFI, Fe, oxihalogenation catalyst 23-P-24 MFI, Fe, sulfide host 22-P-19 MFI, Fe, synthesis 04-0-03 MFI, Fe, synthesis, fluoride 04-P- 17 MFI fibers 2 l-P-06 MFI film 20-0-04 MFI film on AI support 20-P-17 MFI film on ceramic 20-P-09 MFI film on gold 20-P-14 MFI, Ga 03-P- 10 MFI, Ga, activation 11-P-27 MFI, growth rate 02-P-08 MFI, heteroatom location 13-O-02 MFI, hierarchically mesostructured 06-0-03 MFI host 13-P-06 14-P-29 15-P-26 2 l-P- 10 MFI, indium 30-P- 15 MFI, In deNOx catalyst 10-O-01 MFI isomerisation catalyst 12-O-01 25-P-08 26-0-01 MFI, large crystals activation 14-P-38 MFI, lattice vibrations 12-P-07 MFI, macropores 19-0-03

MFI membrane 03-P-17 19-O-05 20-0-02 20-P-06 MFI, mesoporous 03-0-02 1 l-P-30 26-0-02 MFI, Mo 14-P-08 30-K-01 MFI, Mo, oxihalogenation catalyst 23-P-24 MFI, modelling 15-P-06 15-P-25 MFI, nanoparticles agglomeration 03-P- 14 MFI, Na form 30-P-07 MFI, Na synthesis 02-P-09 MFI nanoslabs 02-0-04 MFI, nanotubes formation on 22-P-08 MFI, Ni 04-P-06 23-P-20 MFI, Ni deNOx catalyst 30-P-30 MFI nucleation 02-0-02 MFI, organozeolite 2 I-P- 16 MFI, oxihalogenation catalyst 23-P-24 MFI photocatalyst 15-P-07 30-K-01 30-P-20 MFI, polycrystalline film on cordierite 20-P-13 MFI, pore mouth plugging 11-O-02 MFI, pore mouthing 11-P-24 MFI porosity 26-P-20 MFI, Pt 17-P-08 23-P-20 MFI/Raney composite catalyst 30-P-29 MFI-resin composite 03-P-07 MFI, silylated 19-0-03 MFI, silylated, hydrocarbon conversion 11-O-02 MFI, silylation 10-P-09 11-O-02 MFI sites modelling 15-P-24 MFI, solid state synthesis 04-P-06 MFI, supercritical adsorption 17-P- 16 MFI spheres 03-P-07 21-P-06 MFI synthesis 02-O-01 02-P-31 02-P-41 MFI synthesis, bulk-material dissolution 02-P-26 MFI synthesis, clear solution 02-0-04 02-P-I 6 MFI, synthesis, microwave 03-P- 15 MFI synthesis, phosphate-affected 02-P-40 MFI, synthesis precursors 02-O-01 MFI, template removal 13-P- 10 MFI, thermal treatment 14-P-38 MFI, Ti (see TS-1) 14-P-20 MFI, V 24-P-27 MFI, Zn 24-P-30 24-P-31 MFI, Zn, aromatisation catalyst 28-0-02 MFI, Zn,Ni 24-P-31 MFI, Zn,Ni aromatisation catalyst 29-P-05 MFI, Zn, sulfide host 04-P-14 MFI, Zn, synthesis 02-P-17 Mg in alkaline synthesis 23-P-13 Michael condensation 19-P-08 Microbalance, oscillating 31-P-15 Microbial oxidation 01-P-15 Microbicide 13-P-07 Microcalorimetry Microcalorimetry, adsorption 17-0-02 17-0-03 17-P- 16 Microcalorimetry, Ar/N2 adsorption 17-P- 15 Microcalorimetry, chloroalkene adsorption 17-P-11 Microlaser, potential 21-O-04

420

Microporosity SBA- 15 08-O-03 08-0-04 Microporous-mesoporous mixed structures 06-0-03 Microscopy, atomic force, s e e AFM Microscopy, electron PL-5 Microscopy, interference 19-0-04 Microwave heating 20-P-38 Microwave heating, zeolites 1 l-P- 13 Microwave in catalysis 28-0-02 Microwave in synthesis 03-P- 15 MIL-34 AIPO4 05-P- 19 Milk yield, cows 32-P- 10 Miocene 01-O-02 Mn(x)Cd(l-x)S 21-O-03 MnAPO-31 14-P- 13 MnAPO-34 29-P- 14 MnAPO-43 05-P- 11 Mn-Bipyridyl, encapsulated 2 l-P- 11 Mn-FAU 21-P-11 21-P-13 Mn-MCM-41, deNOx catalyst 30-P- 12 Mn-zeolites, NOx storage 30-0-04 Mo-BEA 14-P-08 Mo incorporation in SBA-1 and-3 14-P-26 Mo-MEL 14-P-08 Mo-MFI 14-P-08 23-P-24 30-K-01 Mo-MFI, oxyhalogenation catalyst 23-P-24 Mo,Zr-MCM-41 26-P-22 Mobility, adsorbed molecules 16-O-03 Modelling, adsorption 12-0-03 16-P-06 18-P- 15 19-0-02 Modelling, adsorption in MOR 15-P- 12 Modelling, ab initio cluster 15-0-04 Modelling, alkylation of aromatics 16-P-08 Modelling, cation sites 15-P-23 Modelling, chloroform adsorption 16-P- 14 Modelling, desulfurisation 15-P-22 Modelling, DFT 15-P- 10 Modelling, dynamical processes 15-O-02 Modelling, embedded cluster 15-0-04 Modelling, galiophosphate activation 16-P- 15 Modelling, hypothetical framework 16-P-07 Modelling methylation reaction 15-O-03 Modelling, MOR catalysis 15-P-12 Modelling proton mobility 15-0-01 16-0-04 Modelling reactivity 15-P- 15 Modelling, reaction mechanism 15-0-05 15-P-20 Modelling structure changes 15-P- 17 Modelling, synthesis, TS- 1 16-P- 16 Modelling, synthesis, zeolites 02-P-22 15-P-06 Modelling, transition state, cluster 15-P- 16 Modelling, zeolite framework 15-P-14 15-P-25 16-P-13 Modification, MCM-41 surface 17-P- 13 Modified H-MFI, alkylation catalyst 25-0-05 Molecular confinement 14-P- 12 Molecular dynamics, adsorption 16-P- 14 Molecular dynamics simulations 15-P-28 16-O-03 16-P-06 16-P-17 16-P-18

Molecular dynamics, experimental 13-P-06 Molecular dynamics, external surface 16-0-02 Molecular modelling 16-0-01 Molecular modelling, multicomponent diffusion 16-O-05 Molecular orbital calculation, Ag-LTA 14-O-04 Molecular simulation, transition state 15-P- 19 Molecular traffic control 16-0-05 28-0-01 Molybdate, Cu, structure 09-P-07 Molybdenum sulfides, mesostructured 1 I-P-11 Monolayer, LTA crystal/glass 20-0-01 Monomer for polyesters, synthesis 25-P-07 Monooctylamine, synthesis 23-P-07 Monte Carlo docking 16-P- 16 Monte Carlo energy minimisation 07-P-21 16-P-I 1 Monte Carlo Simulation 16-O-01 16-O-03 16-P-12 Montmorillonite support 27-P- 10 Montmorillonite tuff 3 l-P-11 MORacidity 12-P-05 12-P-14 13-P-08 MOR, acid site 14-P- 10 MOR, acid site NMR 13-P-23 MOR adsorbent 18-P- 15 19-P-06 MOR, adsorption modelling 15-P- 12 MOR, AI distribution 13-P- 19 MOR, AI in activated 13-P- 18 MOR alkylation catalyst 16-P-08 24-P-06 25-P-07 25-P-09 MOR, alkylation catalyst, modelling 15-0-03 MOR/alumina membranes 20-P- 18 MOR, applications 3 I-P-08 3 l-P- 15 MOR, Armenia 0 l-P- 16 MOR catalyst 28-P- 15 MOR, cation location 09-P- 13 MOR, Ce 29-P- 11 MOR, Co 27-P- 13 MOR, composition 03-P- 19 MOR, Cu 11 -P-20 27-P- 13 MOR, dealuminated 12-P- 16 MOR, dealuminated 11-P-25 12-P-05 29-P-11 MOR, dehydration 09-P- 13 MOR dehydration catalyst 23-P-08 MOR, diffusivity 19-P-08 MOR, Fe 04-P-I 5 13-P-32 27-P-13 30-P-11 30-P-27 MOR, H form 27-0-04 MOR, high-silica 02-P-39 MOR, host 22-P-08 MOR, In deNOx catalyst 10-O-01 MOR isomerisation catalyst 26-0-01 28-P- 13 MOR from magadiite 02-P-36 MOR membranes 20-0-03 MOR, morphology 03-P- 19 MOR, Ni 27-P- 13 MOR, Ni deNOx catalyst 30-P-30 MOR, occurrences 01-O-02 MOR, oxidation catalyst 27-P-08 27-P- 13 MOR, Pd, Heck catalyst 23-0-02

421

MOR, Pd,Co,Ce 30-P-22 MOR photocatalyst 30-P-20 MOR porosity 26-P-20 MOR, Pt 26-P- 19 MOR ring opening catalyst 26-0-03 MOR, sigma transformation 16-P-07 MOR, synthesis 03-P- 19 MOR, structure modelling 16-P- 11 MOR, thermal stability 12-P-05 MOR, vibrational spectroscopy 16-P- 11 MOR, in zeolitic tuff 0 l-P-13 MOR, Zn 04-P-15 13-P-32 Morphology, effect on diffusion 19-O-04 Morphology, mesoporous silica PL- 1 06-P- 13 Morphology, MFI 02-P- 15 Morphology, MFI, internal 14-P-38 M0ssbauer spectroscopy 14-P-22 MPV (Meerwein-Ponndorf-Verley) reduction 23-P-33 08-P-06 MSU-S, synthesis from zeolite seeds 08-P-05 MSU-X 08-0-01 MSU-X in chromatography and filtration MTBE 28-P- 11 29-P-12 24-P-18 MTO, mechanism 24-P-28 MTO process 05-P-17 MTO on SAPO-47 05-P-18 MTO on SAPO-56 24-P-13 MTS polymer degradation catalysts 28-P-10 MTS, adsorbents 06-P-27 MTS, swelled 25-0-03 MTW alkylation catalyst 29-P-25 MTW, Fe oxidation catalyst 04-0-03 MTW, Fe, synthesis 03-P-10 MTW, Ga 26-P-16 MTW, Pt hydroconversion catalyst 02-P-27 MTW-related frameworks 11-O-03 Mu-2 by Mu-3 transformation 11-O-03 Mu-3 stability 16-O-05 Multicomponent diffusion, modelling 15-P-27 Multipole moment, substituted AIPO4 Multiquanta 2D 27A1MAS-NMR 13-P-18 Multiquanta MAS-NMR 13-0-03 13-P-24 27-O-01 MWW 13-0-04 MWW acidity 27-0-03 MWW, acid oxidation catalyst 28-P-15 MWW alkylation catalyst 10-0-02 MWW, basicity 23-P-27 MWW, Beckmann catalsyt 14-P-21 MWW, Co MWW, deNOx catalyst 30-P- 13 30-P-30 30-P-30 MWW, Ni 14-P-21 MWW, Fe 05-P-14 MWW, magadiite-intercalated MWW synthesis 02-P-34 02-P-42 03-P-13 27-O-01 MWW, Ti 14-P-21 MWW, trivalent distribution 32-0-04 Mycotoxin, adsorption

N 14N NMR, MFI synthesis 02-P-40 15N.NMR 13-P-22 N2 adsorption 17-P-05 N2 adsorption, AEL 17-O-03 12-P-09 N2 adsorption, IR 12-0-04 N2 adsorption, LSX 17-P-16 N2, supercritical adsorption, zeolites 17-P-15 N2/Ar adsorption, FAU 17-P-15 N2/Ar adsorption, LTA 18-P-13 N2/O2 selectivity of adsorption 30-0-02 N20 decomposition, Fe-MFI 30-P-13 NzO decomposition, MCM-22 27-0-03 N20 in oxidation 30-P-06 30-P-11 N20 reduction 30-P-14 N20 SCR with propene 16-P-20 N20-NO interaction 23Na 2D NMR 13-P-19 23Na MAS NMR 09-0-05 14-P-17 14-P-37 23Na MQ MAS NMR, Li,Na-FAU 13-P-12 23Na NMR, FAU adsorbent 12-P-12 23Na NMR, paramagnetic effect of 02 13-P-12 03-0-05 Na cations in synthesis 1 l-P-18 Na exchange 14-P-09 Na forms of zeolites, NO adsorption 12-P-12 Na,Li-FAU, pyrrole adsorption 12-0-04 Na-LSX 14-P-37 Na nanoparticles 14-P-37 Na-Rb alloy 13-P-16 Na-X, toluene adsorption NMR 16-O-03 Na-Y, adsorbent 22-P- 18 Nanoclusters, Pblz/LTL 2 l-K-01 Nanocomposite in zeolites Nanocrystailine FAU 02-0-03 02-P-14 Nanocrystalline MFI 02-0-04 28-P-08 22-P-13 Nanocrystals, anatase 02-P-12 Nanocrystals, offretite 06-P-27 Nanoemulsion template 03-P-14 Nanoparticles agglomerates, MFI 11-O-01 Nanoparticles, Au 07-P-13 Nanoparticles, Fe203 in MCM-41 21-P-10 Nanoparticles, SnO2 29-P-22 Nanoparticles, surfactant stabilized 29-P-17 Nanoparticles, ZrO2 in SBA-15 02-0-01 Nanoscopic precursor particles 02-0-04 Nanoslabs, silicalite- 1 22-0-05 Nanowires in FSM- 16 15-P-26 Nanowires, Se in MFI 26-P-23 Naphtha isomerisation 25-P-06 Naphthalene isopropylation Naphthalene alkylation 25-0-03 25-P- 13 25-P- 14 26-0-04 Naphthene ring opening 25-P-08 S-Naproxen synthesis

422

Natrolite 09-P-09 Natrolite, applications 3 l-P-06 Natrolite, ion exchange 0 l-P-08 Natrolite, lattice vibrations 16-P- 19 Natural zeolites, Antarctica 0 l-K-01 Natural zeolites applications PL-2 0 l-P- 16 22-P-10 22-P-15 30-P-10 31-O-01 31-P-06 31-P-08 31-P-12 31-P-14 31-P-15 32-O-01 32-0-04 32-P-06 32-P-09 32-P-10 32-P-12 Natural zeolites, Armenia 0 l-P-16 Natural zeolites, Bulgaria 0 l-P- 13 Natural zeolites, Croatia 3 l-P- 11 Natural zeolites formation 01-O-02 01-P-06 01-P-10 01-P-13 Natural zeolites, Croatia01 -P- 17 Natural zeolites, Iran 01-P-08 3 l-P-06 Natural zeolites and health 32-O-01 32-P-09 Natural zeolites, Jordan 31-O-01 Natural zeolites, occurrencies 0 l-K-01 Natural zeolites, properties 01-O-05 Natural zeolites, Romania 0 l-P-09 Natural zeolites, Russia 0 l-P- 12 Natural zeolites, Sardinia 01-O-02 Natural zeolites, South Africa 3 I-P-12 Natural zeolites, Ukraina 3 l-P-08 3 I-P- 10 Natural zeolites, Zambia 3 I-P-12 Nb, see also Niobate Nb-MCM-41 07-0-04 24-P-12 27-P-09 Nb-MFI 01 -P- 14 Nb-MFI, synthesis 04-P- 10 Nb nanoparticles 14-P-37 Neopentane diffusion 19-0-04 Neutron diffraction 09-0-04 09-0-05 Neutron diffraction, adsorbed phase 17-O-02 Neutron diffraction, AEL adsorbent 17-O-03 NH3, adsorption on zeolites 18-P- 10 NH3 TPD, see TPD Ni-aluminophosphate 09-P-08 Ni-bentonite 18-P- 14 Ni clusters in MFI 04-P-06 Ni-ERI, oxidation catalyst 27-P- 13 Ni-FAU 24-P-17 24-P-24 Ni-FAU, oxidation catalyst 27-P-13 Ni-MCM-22, deNOx catalyst 30-P-30 Ni-MCM-41 hydrodechlorination catalyst 23-P-16 Ni-mesoporous silica 08-0-02 Ni-MFI 04-P-06 23-P-20 Ni-MFI, deNOx catalyst 30-P-30 NiMo/H-BEA 26-P-15 NiMo/H-Y 26-P-15 NiMo hydrotreatment catalysts 26-P-08 NiMo hydrotreatment catalyst on MCM-41 NiMo/MCM-41 hydrotreatment catalyst 26-P-12 26-P-14 NiMo sulfide/large pore zeolites 26-P-15 NiMo/Zr-HMS hydrotreatment catalyst 26-P-22 Ni-MOR, deNOx catalyst 30-P-30

Ni-MOR, oxidation catalyst 27-P- 13 Ni phosphates 05-P-08 Ni phosphate, VSB- I 22-0-03 Ni Raney/MFI composite 30-P-29 Ni,W/Y hydrocracking catalysts 1 l-P-08 Ni,Zn/MFI aromatisation catalyst 24-P-31 28-0-02 Ni/Zr-MCM-41 23-P-28 Ni/ZrO2 fuel cell catalyst 07-P-20 Nine-member rings 09-P- 12 Niobate molecular sieves 05-O-01 Niobium ammonium complex in MFI synthesis 04-P-10 NIR spectroscopy 27-P-11 Nitrate cancrinite 02-P-07 Nitrate removal 3 l-P- 15 Nitration 29-P-28 Nitration, aromatics 13-P-22 Nitration, zeolites 04-0-02 Nitrene 24-0-04 Nitriles, source of template 03-0-03 p-Nitroaniline, adsorption 13-P-06 Nitrogen industry, wastewater 30-P-34 3 I-P- 10 Nitromethane reagent 23-P- 13 Nitromethane, ~3C NMR probe 23-P- 13 N-Nitrosamines degradation 30-P-07 30-P-08 N-Nitrosamine removal 18-P-07 Nitroxide, ditert-butyl 14-P-07 Nittoxide EPR label 32-0-02 Nitroxide EPR probe 14-P-07 Nitroxide radical adsorption 14-P-07 Nitroxyl radical probe 13-P-09 NMR (see individual nuclei) NMR cristallography, AIPOa-CJ2 09-0-02 NMR, in-situ 02-P- 18 NMR spectroscopy 27-P-11 NMR, MCM-48 07-P-06 NO adsorption 12-P-15 14-O-05 14-P-09 NO adsorption,Co-MFI 10-P-08 NO decomposition 07-0-04 12-P-15 14-O-03 30-P-33 NO decomposition, photocatalytic 28-P-07 30-P-24 NO-NzO interaction 16-P-20 NO reduction 30-P-15 30-P-27 30-P-28 30-P-34 NO reduction with propene 30-P-14 30-P-30 NO2 adsorption 14-0-05 NO2 decomposition 07-0-04 12-P-15 14-O-03 30-P-16 30-P-33 NOx decomposition, photocatalytic 28-P-07 30-P-24 NOx abatement, AIPO4 catalysts 30-P-31 NOx adsorption 10-0-04 10-P-08 12-P- 15 14-0-05 14-P-09 NOx decomposition 30-K-01 NOx reduction 30-P- 10 30-P-15 30-P-25 30-P-27 30-P-28 30-P-34 NOx reduction by CH4 10-O-01 30-P-22 30-P-35 NOx reduction by NH3 30-P-12 NOx reduction in propane 10-O-04

423

NOx reduction by propene 30-P-14 30-P-30 NOx reduction with hydrocarbons 30-0-03 12-O-02 NOx sorption, metal zeolites 30-0-04 NOx storage, metal zeolites 30-0-04 Noble metal zeolite 23-P-20 Noble metals/MCM-41 26-P-07 Nonasil, synthesis 02-P-41 Non-ionic surfactant 06-P-23 08-0-02 Nu-86 synthesis 02-P-20 NU-88, cracking catalyst 26-P-11 NU-88, hydroconversion catalyst 26-P-11 NU-88, pore topology 26-P-11 nuclear waste 05-0-01 Nucleation agent, zeolitic 2 l-P-09 Nucleation and growth 02-P- 16 Nucleation, FAU 02-0-03 Nucleation, LTA 02-P-32 Nucleation, zeolites 02-0-02 Nucleophilic Substitution 23-P-07

O 170 3Q MAS NMR 14-0-02 170 DOR NMR 09-0-02 14-0-02 14-0-02 ~70 NMR chemical shitt 17-0-01 02 adsorption 17-O-03 02 adsorption, AEL 27-P-16 02 as anti-coke agent 27-P-16 02 and Beckmann catalyst deactivation 27-P-16 02 and catalyst lifetime 18-P-13 O2/N2 selectivity of adsorption 02, paramagnetic effect on 23Na NMR 13-P-12 27-P- 11 02, singlet, molecular 21-P-16 O2 substitution by organics 17-P-16 02, supercritical adsorption, zeolites 11-P-27 03 in calcination 29-P-18 03, template removal, MCM-41 10-O-03 Occluded salts 22-P-17 Occluded salts, LTA 05-0-01 Octahedral molecular sieves Octahedral-tetrahedral frameworks 05-P-16 05-P-20 09-P-07 1 l-P- 15 27-P-15 Octane enhancers 28-P-11 Octane, iso-, synthesis 24-P-20 Octanol, amination 23-P-07 Offretite, colloidal 02-P- 12 Offretite isomerisation catalyst 28-P- 13 Offretite single crystals 03-P-08 OH groups, ferrierite 13-P- 17 Olefin adsorption 12-P-06 Olefin epoxidation 11-P-29 14-P- 12 15-P- 18 24-P- 14 27-0-02 Olefin hydrogenation 29-P-22 Olefin isomerisation 26-P-09 Olefin oxidation, ETS- 10 11-O-04

24-P-15 Olefin polymerisation Olefination of haloaromatics 23-0-02 01-0-02 Oligocene Oligomerisation, acetylene 24-P-15 Oligomerisation, ethylene 24-P-17 24-P-15 Oligomerisation, olefins Optical properties 21 -O-03 05-P-12 Optical properties, Ce-Eu silicates 22-P- 18 Optical properties, PbI//LTL 22-P-14 Optical sensors 22-P-17 Optical spectra 22-P-07 optical switching 22-0-01 Optics, non-linear 23-P-22 Orange blossom fragrance 17-O-03 Ordering, adsorbed phases, AEL 01-P-07 Ordering, Al, in dachiardite 13-O-01 Ordering, B and AI 22-0-01 Ordering, non-centrosymmetric 04-P-12 Organic acid templates 17-P-06 Organic adsorption, FER 21-P-16 Organic framework Organic functionalisation, mesoporous silica 29-P-31 14-P-30 Organic probe molecules 20-P-12 Organic removal, membrane Organic-modified clinoptilolite 22-P- 12 22-P-15 Organometallic complexes, encapsulated 07-P-10 14-P-16 Organophosphates, microporous 22-0-02 Organozeolites 2 l-P- 16 Oriented crystal growth 02-P-28 Oriented crystals, mordenite 20-0-03 OSB-1 (OSO) 05-0-05 OSB-2 05-0-05 Over-exchanged Cu-ZSM 5 30-P-21 Oxalate in Fe-zeolite synthesis 04-0-03 Oxidation, alkanes, selective 27-O-01 Oxidation, aromatics 2 I-P-07 Oxidation, benzene to phenol 27-0-03 Oxidation, biological 3 I-P- 15 Oxidation catalyst, Fe zeolites 07-P- 10 Oxidation catalyst, substituted MCM-41 29-P-18 Oxidation, CO 29-P- 14 30-P- 10 Oxidation, CVOC 30-P- 18 Oxidation, cyclohexane 02-P-14 07-P-10 27-P-15 Oxidation, cyclohexene 2 l-P- 13 Oxidation, isobutanol 27-P- 13 Oxidation, Fenton 31-O-03 Oxidation, hydrocarbons 27-P-06 Oxidation, methane, photocatalytic 24-P- 12 Oxidation by N20 27-0-03 Oxidation, olefins 11-O-04 Oxidation, phenol 04-0-01 Oxidation, phytotoxic chemicals 31-O-03 Oxidation, propane, photocatalytic 28-P-07 Oxidation, propane, selective 27-P- 12 Oxidation, propyl alcohols 27-P-08

424

Oxidation, selective 24-P- 14 27-0-02 Oxidation, styrene 29-P-21 Oxidation, thioethers 27-P-09 30-P-26 Oxidation, toluene 30-P-23 Oxidation, total 30-P-09 Oxidation, VOC 30-P- 18 Oxides, mixed 24-P-26 Oxidizing atmosphere, effect on activation 14-P-38 Oxyhalogenation, aromatics 23-P-24

31p NMR 09-0-02 09-P- 11 11-O-03 13-P-20 13-P-24 14-P-11 18-P-13 02-P-40 31p NMR, MFI synthesis 11-P-23 P-treated zeolites 08-P-12 Packing parameter 01-P-10 aleogene 13-P-22 para selectivity, toluene nitration 26-0-02 Paraffin isomerisation 06-P-25 Parallel synthesis 13-P-12 Paramagnetic effect of 02 on 23Na NMR 14-P-07 Paramagnetic radicals 28-P-08 Para-selectivity 29-P-12 Partially crystalline BEA 19-O-05 Particle effects, membranes 02-P-23 Particle size, BEA 10-P-09 Passivation, MFI 212pb radiotracer 3 l-P-06 22-P-18 PbI2 nanoclusters in LTL 11-O-01 Pd-Au/H-Y 23-P-26 Pd/BEA 30-P-22 Pd and Ce promoter 23-0-02 Pd/FAU, Heck catalyst 23-P-23 Pd/K,Na-X 27-P-08 Pd/LTA, oxidation catalyst 23-0-02 Pd/LTL, Heck catalyst 29-P-22 Pd/MCM-41 24-O-01 Pd/MeAPSO- 1 l 23-P-26 Pd/MOR 23-0-02 Pd/MOR, Heck catalyst 22-0-05 Pd nanowires 29-P-13 Pd, Pt on mesoporous carbon 24-O-01 Pd/SAPO- 11 27-0-05 Pd-Pt/Y hydrogenation catalysts 23-P-26 Pd/Y 26-P-20 n-Pentane conversion 19-0-04 Pentane, neo-, diffusion 30-P-09 Pentane, total oxidation 19-O-05 Permeability, composite membrane 20-P-07 Permeance, membranes 27-P-10 Peroxide decomposition, biomimetic PL-4 Petrochemistry evolution 1 l-P-10 pH, effect on alumination 31-P-11 pH effect on ion exchange

pH effect, MCM-41 synthesis pH indicators pH of synthesis Pharmacosiderite Phase change, zeolites Phase diagram Phase transformation, aluminium methylphosphonate

06-P-28 22-P-21 02-P-19 1 l-P-15 10-P-07 03-P- 18

21-P-17 Phase transformation, Mu-3 11-O-03 Phase transition, confined system 17-O-01 17-P-17 14-P-16 Phase transition, host-guest systems 2 l-P-09 Phase-change material Phenol alkylation 23-P-31 25-0-02 25-P-09 28-P-15 29-P-08 Phenol dehydroxylation Phenol hydroxylation 07-P-07 27-P-17 04-0-01 Phenol oxidation 20-P-12 Phenol removal, membrane 27-0-03 Phenol, synthesis Phenol-trimethylbenzene transalkylation 25-0-04 07-0-02 Phenyl-functionalized mesoporous silica 1-Phenyl- 1,2-propanedione hydrogenation 23-P-25 32-0-05 Pheromones 01 -O-05 PHI, cation exchange 01-O-04 PHI, Li 04-0-03 Phosphate in Fe-zeolite synthesis 02-P-40 Phosphate in MFI synthesis 22-0-03 Phosphate, Ni, VSB- 1 16-P-15 Phosphates, Ga, stability 32-0-03 Phospholipids 09-P-14 Phosphonate, AI methyl, polytypism 14-P-20 Phosphorescence spectra 31-P-14 Phosphorus removal 05-P-15 Phosphites, aluminium, microporous 30-P-16 Photocatalysis, NO2 decomposition Photocatalysis, transition metal oxides in zeolites 30-K-01 Photocatalytic decomposition, NO 28-P-07 30-P-24 Photocatalytic degradation 30-P-20 Photocatalytic oxidation of methane 24-P- 12 Photocatalytic oxidation of propane 28-P-07 Photocatalytic synthesis of H202 27-P- 14 Photochemical H20 decomposition 28-0-03 photochromic dye 22-P-07 Photoluminescence 14-P-20 14-P-35 21-O-03 21-O-05 29-P-30 Photolysis of alkyl ketones 15-P-07 Photonic devices 22-P-20 Photophysics 22-P-09 Photo redox system 24-P-07 Phtalocyanine 22-P-06 Phtalocyanine in FAU 14-P-12 Phytotoxics oxidation 31-O-03 Pigments, encapsulated 22-P- 19 Pillared clay 22-P- 16 Pillared clays, alkylation catalyst 25-P-13

425

Pillared magadiite Pillared bentonite Pillaring Alpha-Pinene derivatives Alpha-Pinene epoxidation Alpha-Pinene hydration Pinene oxide, rearrangement Piperidine, formation Plant growth enhancenent Plasma activation Plasma treatment, FAU Polarity effects Polluted river water Polyamine binders Polyaromatics adsorption Polyaromatics alkylation Polyaromatics ionisation Polyethylene binder Polyethylene conversion Polyethylene cracking Polyethylene degradation Polymer degradation Polymerisation, acetylene Polymerisation catalysts Polymerisation, ethylene Polymerisation, olefins Polymer-zeolite membrane 21-P-12 Polystyrene beads support Polytypism, BEA 02-P-24 Population balance Pore mouth catalysis Pore mouth plugging, MFI Pore mouthing, BEA Pore mouthing, MFI Pore size distribution, modified MCM-41 Pore size, effect on adsorption Pore size, effect on isomerisation Pore size expansion, see swelling Pore size, MCM-41 Pore structure, ERS- 10 Pore topology, NU-88 Porosils, host Porosils, synthesis Porosity, hierarchical Porous glass, Beckmann catalyst Positron annihilation Positron emission profiling Post-synthetic treatment 06-P-06 08-P-13 Powder diffraction 01-O-04 Pressure effect on natrolite Pressure effect on zeolite structure Pressure swing adsorption (see PSA) Probe, ~3C NMR, nitromethane Propane adsorption Propane formation Propane selective oxidation Propane, photocatalytic oxidation

23-P-18 22-P-16 09-P-08 23-P-14 23-P-14 23-P-19 23-P-14 23-P-08 31-O-02 1 l-P-14 1 l-P-17

18-P-07 31-P-15 20-0-01 14-P-18 25-O-01 14-P-18 22-P-15 24-P-13 30-P-17 24-P-25 30-P-17 24-P-15 24-P-08 24-0-05 24-P-15 19-O-05 21-P-15 0 l-K-01 02-P-29 26-0-02 11-O-02 1 l-P-09 11-P-24 17-P-13 17-P-07 25-P-08 12-P-11 29-0-01 26-P-11 10-O-03

02-P-41 21-P-07 27-P-16 12-P-11 19-P-10 1 l-P-16 09-P-09 16-P-19 09-P-09 23-P-13 18-0-04

24-0-02 27-P-12 28-P-07

Propane/propylene, separation 18-0-04 n-Propanol adsorption 18-P- 15 2-Propanol conversion 29-P-05 Propyl alcohols oxidation 27-P-08 Propylene adsorption 18-0-04 Propylene in alkylation 25-P- 14 Propylene in deNOx SCR 30-P-30 Propylene dimerisation 24-P-24 Propylene epoxidation 24-P- 14 27-0-02 Propylene oxide 24-P- 14 Propylene polymerisation 24-P-08 Propylene/propane, separation 18-0-04 Protein adsorption 23-P- 17 Proton mobility modelling 15-0-01 Proton positions, FAU 09-0-04 Proton transfer, modelling 15-0-02 Proton tunnelling, FAU 16-0-04 PSA, CO2 18-0-01 PSA separation, ethyl acetate 18-P-12 Pt,Au/H-Y 11-O-01 Pt-2,2'-bipyridyl complex 24-P-29 Pt catalysts 29-P- 19 Pt dispersion 26-P- 16 Pt/BEA 17-P-08 24-P- 16 Pt/BEA aromatisation catalyst 15-P-09 Pt/BEA hydrogenation catalyst 26-P- 13 Pt/BEA isomerisation catalyst 20-P- 18 Pt/Cs-BEA reforming catalyst 26-0-05 Pt/CsX basic catalyst 23-0-05 Pt-FAU 17-P-08 Pt-FAU aromatisation catalyst 15-P-09 Pt/FAU bifunctional catalyst 30-0-05 Pt/FAU catalyst, CH2C!2 conversion 30-0-05 Pt/K-LTL catalyst 1 l-P-07 Pt-LTL aromatisation catalyst 15-P-09 Pt/MAPSO-31 hydroisomerisation catalyst 26-P-06 Pt/MCM-41 chiral hydrogenation catalyst 23-P-25 26-P-21 Pt/MCM-41 hydroisomerisation catalyst Pt/MOR, diffusivity 19-P-08 28-0-05 26-P-19 Pt/MOR isomerisation catalyst 27-0-04 Pt/MOR hydrogenation catalyst 28-0-05 Pt-MOR hydroisomerisation catalyst Pt/MFI 17-P-08 23-P-20 26-P-16 Pt/MTW hydroconversion catalyst 14-P-36 Pt,Ni/USY isomerisation catalyst 29-P-13 Pt, Pd/mesoporous carbon 27-0-05 Pt-Pd/Y hydrogenation catalysts 22-0-05 Pt-Rh catalysts 26-0-03 (Pt,Rh,Pd,Ru,Ni)/HZSM-5 26-0-04 Pt zeolites, hydrogenation catalyst 29-P-15 Pt-Zn/zeolite X 03-P-08 Pyrocatechol in zeolite synthesis 2 l-P-08 Pyrolysis 12-P-12 Pyrrole adsorption, Li,Na-FAU

426

Q Quadrupolar interaction, ~B Quantum chemical calculations Quantum confinement Quantum confinement, Ag-LTA Quantum-chemical calculations Quinoline, fluorescence Quinone/BEA photocatalysts

13-P-11 14-0-03 21 -O-03 21 -O-05 14-0-04 15-O-05 13-P-13 27-P-14

R Radical sites 24-P-25 Radicals, adsorbed 24-P-07 Radicals, health effect 32-0-02 Radioanalytical methods 3 l-P-06 Radionuclides 3 l-P-05 32-P-12 Raman spectroscopy 14-P- 18 14-P-24 Raman spectroscopy, host-guest interactions 14-P-16 Raman spectroscopy, NIR 14-P-31 Raman spectroscopy, vanadium 14-P-33 Raman spectroscopy, zeolite lattice 12-P- 10 Raney metal/MFI composite 30-P-29 Rare earth exchange 1 l-P-19 Rare earth silicates 05-P- 12 Raspberry ketone 25-0-02 STRb NMR 14-P-37 Reaction dynamics, proton transfer 16-O-04 Reactivity enhancement 28-0-01 Reactivity index 15-P-06 Reactivity, silicalite 15-0-05 Rearrangement of pinene oxide 23-P- 14 Reconstructive transformation 02-P-25 REDOR MAS NMR 13-0-01 13-P-23 Redox behaviour, Fe in MCM-41 07-0-03 Redox behaviour, Ga-FAU 10-P-06 Redox ion exchange 09-P- 10 Redox mesoporous molecular sieves 23-P- 14 Reductibility, Cu/ZSM-5 27-P- 12 Reduction, Cu 2+in MFI 30-P-21 Reduction, Ga in FAU 10-P-06 Reduction, metal ions 04-0-01 Reduction, regioselective, ketones 23-P-33 Refining evolution PL-4 Reflection, internal 21-O-04 Reforming, FCC gasoline and LCO 26-0-05 Relaxation, lattice 16-P- 18 Relaxation processes, cations 14-P-06 Renewable feedstock 23-P-32 REPDOR triple resonance 13-O-01 Resin-silicate composite 03-P-07 Resonance Raman spectroscopy 14-P-34 RHO, dealumination 11-P-25 Rietveld analysis, molecules in zeolites 16-P-06

Rietveld refinement 09-0-01 01-O-04 05-P- 19 09-P- 11 Rietveld refinement, mesoporous silicas Ring opening, aromatics Ring opening, cyclohexane Ring opening, epoxides Ring opening, methyloxirane Ring opening, naphthenes 3-Rings Rings, penetrability Roboting synthesis Romania, clinoptilolite occurrences Ru bipyridyl complexes/FAU RUB-29 lithium silicate Rubidium clusters in LTA Russia, clinoptilolite tuff

Salen complex anchoring Salen complexes, Co, on MCM-41 Salen complex, Yi (IV), chiral Salt occlusion, PbI2/LTL SANS, synthesis SAPO-5 SAPO-5, amination catalyst SAPO-56 SAPO-I 1 alkylation catalyst SAPO-I 1 dehydroisomerisation catalyst SAPO-11 synthesis SAPO-I 1 amination catalyst SAPO-31 alkylation catalyst SAPO-31 amination catalyst SAPO-31, synthesis SAPO-34 MTO catalyst SAPO-34, acidity SAPO-34, amination catalyst SAPO-34, Fe SAPO-34, host SAPO-37, acid site SAPO-37, thermal decomposition SAPO-41 alkylation catalyst SAPO-47, characterisation SAPO-47, synthesis Saponite, reagent Sardinia, zeolite occurrences Saturation, unsaturated rings SAXS, synthesis SBA-1, functionalized, synthesis SBA-1, Mo SBA- 1, synthesis SBA-2, functionalised SBA-3 in HPLC SBA-3 synthesis

09-P-14 08-P-14 26-P-13 26-0-03 23-P-10 23-P-15 26-0-04 O5-0-O5 15-P-14 03-K-01 0 l-P-09 28-0-03 09-0-O5 21-P-18 01-P-12

29-P-08 23-P-10 23-P- 11 22-P-18 02-0-01 13-P-14 23-P-07 05-P-18 23-P-31 24-O-01 02-P-13 23-P-07 23-P-31 23-P-07 04-P-09 24-P-28 24-P-26 23-P-07 30-P-27 24-P-26 14-P-10 14-P-11 23-P-31 05-P-17 05-P-17 06-P- 15 01-O-02 26-P-10 02-0-01 07-0-02 14-P-26 06-P- 18 07-P-17 18-P-06

06-P-28

427

SBA-3, Mo 14-P-26 SBA-3, synthesis 06-P- 18 SBA-6, HRTEM PL-5 SBA-15 08-P-07 SBA- 15, adsorbent 17-0-01 SBA- 15, AI, cracking catalyst 08-P- 13 SBA-I 5, AI, Pt hydroisomerisation catalyst 08-P- 13 SBA- 15, AI, template interaction 08-0-04 SBA-15 host 29-P-17 SBA- 15 in HPLC 18-P-06 SBA- 15 porosity 08-0-03 SBA-15, stability 08-P-13 SBA- 15, V, photocatalyst 24-P-07 SBA- 15, wall properties 08-P- 14 SBA- 15, Y, HRTEM PL- 1 Scaffolding 7-P- 11 Scolecite 09-P-09 Sea water 3 l-P- 16 Sea water, bentonite zeolitisation 03-P-06 Secondary synthesis, mesoporous silica 08-P-11 Sedimentary zeolites, properties 01-O-05 Sedimentary zeolites, volcano01-O-02 Seeding 02-P-08 02-P-19 02-P-20 02-P-31 Seeding, effect on synthesis 02-P-21 Seeding, film 20-P-09 20-P-16 Seeding, zeolite layers 20-0-02 Selectivation by coke 28-P-06 Selectivity, diffusion-controlled 28-0-01 Selenium, nanowires in MFI 15-P-26 SEM ETS- 10 27-P- 15 Semiconductor, MoS I l-P-11 Semiconductors, magnetic 21-O-03 Semi-empirical quantum-mechanical method 16-P-16 Semiochemicals 32-O-05 Sensor, calorimetric 22-P-11 Sensor, gas 2 l-P- 10 Sensor, optical 22-P- 14 Separation, cafeine 20-0-05 Separation, CO2 18-0-01 Separation, CO2/C2 hydrocarbons 18-O-03 Separation of mixtures 17-P- 16 Separation, membrane 19-0-05 Separation, membrane, asymmetric 23-P- 10 Separation, propane/propylene 18-0-04 Separation, xylenes 18-P-08 SF6-Xe diffusion in BOG, modelling 16-O-05 Shape selectivity 11-P-24 25-P-07 25-P-09 25-P- 14 28-P-08 28-P- 13 29-0-01 29-P- 11 Shape selectivity enhancement 10-P-09 Shape selectivity simulation 15-P-19 16-O-01 16-P-08 Shape selectivity, test reactions 26-P-11 Shape-selective alkylation 25-0-01 Ship-in-the-bottle complexes 07-P-10 14-P-12 21-K-01 21-P-11 22-P-07 22-P-09 24-P-29 27-P-10

295i 2D NMR 13-P- 19 29Si NMR 0 l-P-07 03-0-04 04-P- 18 09-0-01 1 I-P-07 l l-P-21 18-P-13 13-P-06 13-P-10 30-P-19 29Si NMR, MFI synthesis 02-P-40 29Si NMR, spectra prediction 15-P-25 Si/A1 distribution, clinoptilolite PL-2 Si/AI ratio, dealuminated Y 13-P- 15 Si/AI ratio, effect of alkalinity 03-P- 19 SiC nanoparticles 21-O-05 Sigma transformation 16-P-07 Silane, functionalisation by 29-P- 16 Silane, hydrophobisation by 06-P-06 Silane, methylene framework 2 I-P- 16 Silica adsorbents 18-0-04 Silica aggregates, fractal 14-P-25 Silica deposits 28-P-08 Silica fibers, zeolitisation 02-P-26 Silica MTS 06-P-27 Silica source 02-P-I 9 02-P-20 06-P- 15 Silica source, effect on synthesis 02-P-23 Silica source, effect on synthesis of MOR 03-P- 19 Silica spheres with Cu 07-P-07 Silica template 07-P-22 Silica BEA, pure 02-P-35 Silica, CaCI2 impregnated 31-O-04 Silica, HLS 02-P-25 Silica, reagent 02-P- 13 Silica-alumina, amorphous 27-0-05 silica-alumina, amorphous catalyst 28-P- 15 Silica-alumina, Beckmann catalyst 27-P- 16 Silicalite- 1 (see also MFI) 0 I-P- 14 Silicalite-1 adsorbent 17-0-02 19-0-02 Silicalite-1, adsorption modelling 16-P-10 16-P-12 Silicalite- 1, diffusion 19-P- 10 Silicalite- 1 film 20-0-04 Silicalite-1 membrane 03-P-17 19-O-05 20-0-02 Silicalite- 1 nanoslabs 02-0-04 Silicalite, supercritical adsorption 17-P- 16 Silica-rich mordenite 02-P-39 Silica-zirconia, mesoporous 07-P-09 Siliceous ferrierite 17-P-06 Silicon incorporation in SAPO 23-P-31 Silicon nanoparticles 21-O-05 Silylation, effect on diffusivity 19-0-03 Silylation, MCM-41 29-0-02 Silylation, mesoporous silica 18-P-06 29-P-31 Silylation, MFI 11-O-02 Silylation, Ti-BEA 11-P-29 Simulation, FAU (111) surface 16-0-02 Single crystal mesoporous 07-P-15 Single crystals, offretite 03-P-08 Single file diffusion 28-0-01 Single file diffusion in MOR 28-0-05 Single file diffusion, effect on catalysis 28-0-05 Singlet molecular oxygen 27-P-11 Sintering in membrane preparation 03-P-17

428

Smectite adsorbent 32-0-04 Smectite, reagent 06-P- 15 Sn NMR 05-P-13 21-P-10 SnO2 in Zeolites 05-P-13 Sn silicates 19-P-06 SO2 adsorption, effect of water 18-P-10 SO2 adsorption on zeolites 30-P-25 SO2, effect on DeNOx activity 29-P-25 SO2 oxidation 08-P-10 SO3H- anchored on mesoporous silica 09-P- 11 SOD AIPO4-20 02-P-28 SOD-CAN composite 02-P-28 SOD-CHA composite 15-P-08 SOD, encaspsulation, modelling 18-P-10 SOD from fly ash SOD, 170 NMR 14-0-02 22-P- 19 SOD, sulfide host 02-P-29 SOD synthesis 02-P-25 SOD synthesis, solid state 02-P-25 SOD, TMA 07-P-21 Sodalite building blocks 16-P-17 Sodalite cage 31-O-01 Soil amendment 14-P-25 Sol-gel, silica 29-P-12 Solid acid catalysts, partially crystalline 10-P-06 Solid state cation exchange 17-P-17 Solidification, confined phase 10-P-08 Solid-state cation exchange Solid-state reactions by microwave heating 1 I-P-13 18-P-07 Solvent effects 07-P-12 Solvent extraction, mesoporous Ti02 SOMS (Sandia octahedral molecular sieves) 05-O-01 06-P-14 Sonochemistry in synthesis 29-0-01 Spaciousness index 03-P-07 Sphares, silicalite 06-P-13 Spheres, mesoporous silica 2 l-P-06 Spheres, MFI, hollow 21-P-12 Spheres, zeolite, hollow 14-P-10 Spin echo double resonance 10-P-07 Spinel ceramic from zeolites 22-P-07 Spiropyrane in zeolite Y Sr exchange 05-0-01 1 l-P-18 Sr2+ removal 05-O-01 02-P-21 Sr, K-KFI, synthesis 1 l-P-16 SSZ-33 (-CON) 02-P-30 SSZ-35, synthesis 26-0-05 SSZ-42 03-0-03 SSZ-53 03-0-03 SSZ-55 05-0-03 STA-6 (SAS) 05-0-03 STA-7 (SAV) 05-0-03 STA-8 31-P-13 Stabilisation in cement matrix 13-P-20 Stability of AIPO4 vs. hydration 01-O-03 Stability, clinoptilolite 29-0-02 Stability, functionalized MCM-41 06-P-06 Stability, MCM-48

Stability, mesoporous alumina 06-P-23 Stability, mesoporous silica 06-O-01 06-P-06 06-P-07 08-P-06 08-P-14 Stability, SBA-15 08-P-13 Stability, substituted MCM-41 06-P- 19 Stability, thermal, FAU 1 I-P-13 Stability, thermal, SAPO-37 14-P-11 Statistical mechanics treatment, adsorption 16-P-10 Steam dealumination 1 I-P-08 13-P-07 28-P-08 Steam reforming 24-P-23 Steamcracker feed, synthetic 26-P-10 STF (see SSZ-35) Stirring, effect on synthesis 02-P-19 Storage, chromium 31-P-13 Storage, heat 2 l-P-09 31-O-04 17-P-10 Storage, Hz Storage, NOx 30-0-04 Strawberry crop enhancement 31-O-01 Structural modelling 08-P- 14 15-P-25 09-0-02 Structure analysis by NMR data Structure determination 01-O-04 05-0-02 05-0-05 05-P-06 05-P-10 05-P-11 05-P-16 05-P-20 09-0-04 09-P-08 09-P-09 1 l-P-12 09-0-03 Structure, FOS-5 Structure, packing parameter 08-P-12 Structure prediction 07-P-21 Structure, rare earth silicates 05-P-12 PL-5 Structure resolution, HRTEM 08-0-03 Structure, SBA- 15 16-P-07 Structure, sigma transformation 11-O-03 Structure transformation, Mu-3 Structure-directing agent (see template) 29-P-08 Styrene epoxidation 29-P-21 Styrene oxidation 1 l-P-11 Sulfides, mesoporous 22-P-19 Sulfide pigments 29-P-28 Sulfonation 08-P-lO Sulfonic acids, supported 27-P-09 Sulfoxidation, thioethers 26-P-06 Sulfur effect on catalysis 18-P-14 Sulfur guard PL-4 Sulfur in refining 27-0-05 Sulfur resistance 27-0-04 Sulfur tolerance 29-P-25 Sulfuric acid synthesis 2 l-P-09 Supercooling avoidance 17-P-16 Supercritical adsorption, zeolites 20-0-05 Supercritical CO2 extraction 07-P-09 Supercritical ethanol synthesis 17-P-05 Supercritical fluid, adsorption 30-P-12 Support effect in DeNOx SCR 29-P-13 Supported metals 29-P-16 Surface modification by silanes 1 l-P-17 Surface modification, FAU 29-P-09 Surface modification, mesoporous silica 14-P-08 Surface properties, Mo-zeolites 32-0-02 Surface reactivity

429

Surface species, ethylene conversion 24-P- 10 Surface structure, FAU (111 ) 16-0-02 Surface topography, SSZ-24 02-0-05 Surfactant extraction 06-P-11 Surfactant on clinoptilolite PL-2 Surfactant removal, mesoporous TiO2 07-P- 12 Surfactant, adsorbed adsorbent 06-P-27 32-0-04 Surfactant, cationic 06-P-09 Surfactant, deca(oxyethylene)oleyl ether 08-0-02 Surfactant, mixed 08-P- 12 Surfactant, non-ionic 08-0-03 08-P-05 08-P-11 08-P-12 06-P-18 Surfactants, triblock copolymers 08-P-07 Surfactant-silica interaction 08-P-05 SUZ-4, isomerisation catalyst 24-P-21 Swelled mesoporous silica 06-P-27 Swelling agents 06-P-27 17-P-05 Swelling agent, amine 06-0-04 Swelling, MCM-48 06-P-06 Sylilation, MFI 10-P-09 Synchrotron diffraction 01-O-03 09-P-09 09-P- 13 20-0-04 Synthesis, acidic, mesoporous silica 29-P-16 Synthesis, aging effect 02-P-19 02-P-21 02-P-29 Synthesis, AIPO4, additives 02-P-33 Synthesis, AIPO4, intermediates 02-P-11 Synthesis AIPO4-31, substituted 04-P-09 Synthesis, AI-SBA- 15 08-0-04 Synthesis, AI source, effect of 02-P- 19 Synthesis, alternate silica and surfactant 08-P-09 Synthesis, anatase nanocrystals 22-P- 13 Synthesis, asymmetric, terminal epoxides 23-P-10 Synthesis, BEA 02-P-23 Synthesis, BEA, all-silica 02-P-35 Synthesis, BEA, Cr, AI 04-P-08 Synthesis, cancrinite 03-P- 11 Synthesis, cation effect 03-0-05 Synthesis, clear solution 02-0-02 02-P-29 20-P-16 Synthesis, combinatorial methods 03-K-01 03-P-12 03-P-13 03-P-16 03-P-18 06-P-25 Synthesis, Co-MFI 04-P- 18 Synthesis, cosurfactants 06-P- 18 Synthesis, CrAPO-5 04-P- 12 Synthesis, dry-gel conversion 03-P- 10 Synthesis, ETS-4 04-P- 16 Synthesis, FAU 02-0-03 Synthesis, FAU film 20-P-16 Synthesis, Fe-MFI 04-0-03 Synthesis, Fe-MFI, fluoride 04-P-17 Synthesis, Fe-MOR 04-P- 15 Synthesis, Fe-MTW 04-0-03 Synthesis, FER 03-P-09 Synthesis, Fe-TON 04-0-03 Synthesis, fluoride medium 05-0-02 05-P-08 Synthesis, FOS-5 09-0-03 Synthesis by gel impregnation 04-P-07 Synthesis gel, thermal treatment 02-P-32

Synthesis, GUS- 1 02-P-27 Synthesis, IFR 03-0-04 Synthesis, K,Na-EDI 03-0-05 Synthesis, K,Na-FAU 03-0-05 Synthesis, K,Na-LTA 03-0-05 Synthesis, KFI 02-P-21 Synthesis, LTA 02-P-29 02-P-32 Synthesis, LTA film 20-P- 16 Synthesis, LTA, in-situ 18-P-09 Synthesis, LTL, alkaline earth effect 02-P-17 Synthesis, layer-by-layer 2 I-P- 12 Synthesis, layered germanates 09-P- 12 Synthesis, M41 s 07-P-24 Synthesis, MCM-22 02-P-34 03-P- 13 Synthesis, MCM-41 06-0-01 07-P-24 Synthesis, MCM-41, aging, effect of 06-P-21 Synthesis, MCM-41, aluminosilicate 06-P-08 Synthesis, MCM-41, Ce 07-P-23 Synthesis, MCM-41, Fe 06-P-28 Synthesis, MCM-41, substituted 06-P- 19 29-P-21 Synthesis, MCM-41, time of 06-P-21 Synthesis, MCM-41, Zr 29-P-24 Synthesis, MCM-48 06-O-01 06-P-06 06-P-24 Synthesis, MeAPO 05-0-03 Synthesis mechanism 02-P- 18 Synthesis, mesoporous alumina 07-P-08 07-P-I 8 Synthesis, mesoporous silica 06-P-07 06-P-09 06-P- 15 06-P-I 8 06-P-26 08-P-I 1 08-P-12 17-P-05 Synthesis, mesoporous silica, pH effect 06-P-20 Synthesis, mesoporous silica, functionalized 07-0-02 08-P-08 Synthesis, mesoporous silica, temperature effect 06-P-26 Synthesis, mesoporous zirconia 7-P-11 Synthesis with methylamine 04-O-01 Synthesis, MFI 02-O-01 02-P-09 02-P-15 Synthesis, MFI, bulk-material dissolution 02-P-26 Synthesis, MFI in carbon matrix 03-0-02 Synthesis, MFI on cordierite 30-P-33 Synthesis, MFI, Nb 04-P- 10 Synthesis, MFI, phosphate-affected 02-P-40 Synthesis, MFI, solid state 04-P-06 Synthesis, MFI, supported 20-P- 17 Synthesis, MFI, Zn 04-P- 14 Synthesis, microwave 0 l-P- 14 02-0-02 02-P-08 03-P- 15 Synthesis, MIL-34 05-P- 19 Synthesis, models 02-P-24 Synthesis, MOR 02-P-39 03-P-19 Synthesis, MOR from magadiite 02-P-36 Synthesis, MOR, Zn 04-P- 15 Synthesis, MSU-X, two-step 08-P-05 Synthesis, MWW 02-P-42 Synthesis, nanocrystalline FA U 02-P- 14 , Synthesis, non-aqueous media 05-P-08 05-P-11 Synthesis, organozeolite 2 I-P- 16

430

Synthesis, oxide mesostructures 07-0-05 Synthesis, parallel 03-P- 12 Synthesis parameters 02-0-02 02-P-08 02-P-20 Synthesis, particulate precursors 02-O-01 Synthesis, pH effect 06-P-28 Synthesis, phosphates, substituted 05-P-11 Synthesis, phosphates, Ti 05-0-02 Synthesis, phosphates, W 05-P-20 Synthesis, porosils 02-P-41 Synthesis, rare earth silicates 05-P- 12 Synthesis, SAPO- 11 02-P- 13 Synthesis, SBA-15 08-0-04 08-P-07 Synthesis, seeding, effect of 02-P-21 Synthesis, silica source, effect of 02-P-19 Synthesis, silicalite on resin 03-P-07 Synthesis, silicalite, clear solution 02-P-16 Synthesis, single crystals 03-P-08 Synthesis, SOD, solid state 02-P-25 Synthesis, sol-gel 0 I-P- 14 07-P-07 Synthesis, solvothermal 05-P-09 Synthesis, SSZ-35 02-P-30 Synthesis, stannosilicates 05-P- 13 Synthesis, static 02-P-34 Synthesis, stirring, effect of 02-P- 19 Synthesis, zeolites, supported 2 l-P- 12 Synthesis, temperature dependence 02-P-34 03-P-12 Synthesis, TON 02-P-22 02-P- 10 04-0-04 Synthesis, two-stage 02-0-03 02-P-34 Synthesis, ultrasound 06-P- 14 Synthesis, vanadosilicates 04-0-05 Synthesis, variable-temperature 20-P-07 Synthesis, zeolites from bentonite 03-P-06 Synthesis, zeolites from fly ash 18-P- 10 Synthesis, zeolites from MCM-41 07-P- 10 Synthesis, zeolites, modelling 02-P-22 15-P-06 Synthesis, zeolites, substituted 05-P-I 1 Synthesis, ZSM-34 02-P-22

Ta-MFI Tantalum-pillared magadiite Tartrate complexes Tb[(CIBOEP)4P](acac) encapsulation TBHP in epoxidation TEM TEM, 3 D TEM Pt,Ni-USY TEM, overgrowth TEM-EDX Temperature effect on ion exchange Temperature effect on MCM-41 synthesis Temperature effect, FAU surface Temperature effect on synthesis

01-P-14 23-P-18 29-P-08 22-P-09 29-P-30 23-0-05 14-0-01 14-P-36 02-P-06 26-P-15 1 l-P-18

06-P-26 16-0-02 02-P-21

Template (for mesoporous materials s e e also surfactant) 02-P-20 Template, alkali cations 03-P-18 Templates, AIPO4 synthesis 02-P-33 Template, amine 03-0-03 05-0-02 07-0-05 Template, butylamine 05-P- 17 Template, chiral 05-0-04 Template, colloidal 07-P-22 Template, concentration effect 02-P-41 Template cyclobutylamine 05-P- 19 Template, DABCO-based 02-P-27 Template degradation 02-P-22 11-P-27 20-P-38 Template degradation, MFI 14-P-38 Template, diethylenetriamine 02-P-41 Template, dodecylamine 29-P-08 Template, ethylenediamine 05-P-08 09-P-08 Template, ex nitriles 03-0-03 Template extraction 06-P-11 Template, hexamethylenediamine 02-P-22 02-P-42 16-P-16 Template, N-methyl hexahydrojulodinium 02-P-30 Template modelling 16-P- 16 Templates, multiple 04-P- 12 Template, nanoemulsion 06-P-27 Template, nitrate 02-P-07 Template, non-ionic surfactant 08-0-03 Template ordering 22-0-01 Template, organic acids 04-P- 12 Template, organic, choice 16-P-07 Template removal, gallophosphates 16-P- 15 Template removal, MCM-41 29-P- 18 Template removal, ZSM-5 13-P- 10 Template, silica 07-P-22 Template, tetrahydrofuran 03-P-09 template-trivalent interaction 13-O-01 TEOS, CVD on MFI 10-P-09 Terpene valorisation 23-P-29 Tert-butylation of biphenyl 25-P-07 Tetraalkylammonium degradation 20-P-38 2,4-di-Tetrabutylphenol, reagent 25-P- 12 Tetrachloethylene adsorption, MFI 17-O-02 Tetrafluoromethane reagent 1 l-P- 17 Tetrahydrofuran adsorption 12-P-08 Tetrahydrofuran template 03-P-09 Tetrapropylammonium cation 14-P-29 Texture SBA- 15 08-0-03 TG/DTA-MASS fluorinated FAU 1 l-P- 17 TGA 12-P-16 20-P-15 Therapy, adjuvants 32-P-09 Thermal activation, clinoptilolite 3 l-P-09 Thermal analysis, ETS-4 04-P- 16 Thermal behavior, clinoptilolite 11-P-26 Thermal desorption 17-P-09 Thermal stability, FAU 1 l-P-13 Thermal stability, MOR 12-P-05 Thermal stability, zeolites 10-P-07 Thermal treatment, MFI 14-P-38

431

Thermochemical storage of heat Thioether sulfoxidation Thiol-functionalized SBA-2 Thiophene cracking, modelling Thiophene HDS 26-P-17 Ti (IV) Salen complex, chiral Ti in AIPO4-31 Ti-BEA 27-P-11 Ti-BEA, epoxidation catalyst Ti-BEA, silylated Ti-ETS-10 11-O-04 Ti, framework, octahedral Ti-HMS 23-P-14 Ti-HMS deNOx catalyst Ti-HMS, local structure Ti-MCM-41 07-P-14 24-P-12 Ti-MCM-41 oxidation catalyst Ti-MCM-48 Ti-MFI (see TS-1) Ti-MWW TiO2, in MCM-41 TiO2, mesoporous 07-0-05 Ti-peroxo species Ti phosphates, synthesis Ti-zeolites Ti sites in TS- 1 14-P- 14 Tiling theory TI-X, exchange with In TMA-SOD Toluene adsorption Toluene, adsorption NMR, Na-X Toluene conversion, silylated MFI Toluene disproportionation 10-P-09 11-P-24 24-P-06 Toluene hydrogenation Toluene isomerisation, modelling Toluene methylation model Toluene-Na-X interaction Toluene nitration Toluene oxidation Toluene total oxidation TON catalyst TON, Fe TON, Fe, synthesis TON synthesis 02-P-22 Toxicity, clinoptilolite Toxicity, mineral dust TPD (temperature-programmed desorption) 12-P-08 13-P-10 13-P-21 26-P-22 TPD diazines/FAU TPD NH3 12-P-17 13-P-10 29-P-14 TPD-MS TPR 07-0-04 10-O-01 10-P-06 Trace elements in crop growth Transalkylation 25-0-03 Transalkylation, phenol/trimethylbenzene Transalkylation, trimethylbenzene/toluene

31-O-04 27-P-09 07-P- 17 15-P-22 26-P-22 23-P-11 14-P- 13 27-P-17 11-P-29 11-P-29 27-P-15 1 I-P- 15 29-P-08 30-P-24 30-P-24 29-P-30 29-P- 18 29-P-30 27-O-01 22-P-06 07-P-12 15-P- 18 05-0-02 27-P- 17 14-P-30 16-P- 13 09-P-10 02-P-25 18-P- 15 13-P- 16 11-O-02 29-P-26 27-0-05 15-P-20 15-O-03 13-P- 16 13-P-22 30-P-23 30-P-26 26-P- 10 04-0-04 04-0-03 04-0-04 32-P- 12 32-0-02 10-O-01 29-P-19 12-O-03 30-P-18 12-P-16 30-P-23 31-O-01 29-0-01 25-0-04 25-P-10

Transformation, hydrothermal Transformation, mesostructural Transient uptake measurement Transition energies in UV-visible Transition metal cations 04-P-11 15-P-I 1 15-P-23 Transition metal cation-modified silica Transition metal-exchanged MCM-22 Transition metal halides in porosils Transition metal incorporation Transition metal incorporation, mesoporous

02-P-36 06-P-26 19-P-08 14-O-03

27-P-08 24-P-07 30-P- 13 10-O-03 06-P- 12 silica 08-0-02 Transition metals in MCM-41 29-P-21 Transition metal mixed oxides 07-P-15 Transition metal oxide mesostructures 07-0-05 Transition metal oxides in zeolites, local structure 30-K-01 Transition metal oxides, supported catalysts 22-P-08 Transition metal-zeolite models 15-P- 13 Transition state modelling 15-P- 16 15-P- 19 Transition state selectivity 23-P-20 Tribloc copolymer surfactants 08-0-03 08-P-07 08-P-12 21-O-03 1,2,4-trichlorobenzene 23-P- 16 Trichloroethylene adsorption 18-P- 15 Trichloroethylene adsorption, MFI 17-0-02 Triethylmethylammonium in MFI 16-P-06 1,3,5-Triisopropylbenzene conversion, silylated MFI 11-O-02 1,3,5-Trisopropyibenzene cracking 29-P-07 trimetallic catalysts 30-P-22 Trimethylamine, template 09-0-03 Trimethyl benzene, swelling agent 06-P-27 1,2,4-Trimethylbenzene conversion, silylated MFI 11-O-02 Trimethylbenzene transalkylation 25-P- 10 Trimethylbenzene-phenol transalkylation 25-0-04 Trimethylpentane synthesis 24-P-20 Trimethylsilylcyanation, asymmetric 23-P-11 Tris (acetylacetonato)Cr 04-P-08 Trivalent distribution in MCM-22 14-P-21 Trivalent distribution in MFI 13-0-02 Trivalent-template interaction 13-O-01 TS-1 01-P-14 ll-P-15 27-P-11 27-P-17 TS- 1 catalyst 15-P- 18 TS-1 catalyst, effect of AI 27-0-02 TS-1, crystal morphology 06-P-25 TS- 1, framework vibrations 14-P-34 TS- 1, supported catalyst 24-P- 14 TS- 1 synthesis 14-P- 14 TS- 1 synthesis, modelling 16-P- 16 TS- 1, Ti sites 14-P- 14 14-P-30 TS- 1, water adsorption 14-P-34 Tschernichite (BEA) 0 l-K-01 Tuff, CHA, PHI-rich 31-O-01

432

Tuff, clinoptilolite-rich 0 l-P-09 22-P-12 22-P-15 31-P-11 32-P-10 Tuff, FAU-rich Tuff, montmorillonite-rich Tuff, zeolite-rich 0 I-P- 13 Tungsten carbide/FSM- 16 Tungstophosphate, Co Tunneling, proton, FAU Two-step synthesis, MSU-X

01 -P- 12 32-P-11 3 I-P-13 3 I-P-11 32-0-04 29-P-29 05-P-20 16-O-04 08-P-05

Vibrational spectroscopy, MOR 16-P-11 VOC removal 18-P-15 30-0-05 VOC removal, MCM-41 adsorbent 18-P-12 VOC deep oxidation 30-P-I 8 30-P-23 Volcano-sedimentary succession 01-O-02 Volumetric method, static 17-P-08 VPI-5 adsorbent 17-P-17 VPI-5 story PL-3 VSB-1 catalytic properties 22-0-03

W Ukraina, natural zeolites 3 l-P-08 Ultramarine, encapsulated Ultrasound monitoring, crystallisation Ultrasounds in synthesis Unit cell constant, FAU Unsaturated alcohol Unsaturated aldehydes Unsaturated ketone reduction USY (see also FAU) USY hydrotreatment catalyst USY alkylation catalyst USY polymer degradation catalyst USY, Pt,Ni isomerisation catalyst USY, treated, isomerisation catalyst USY, treated, cracking catalyst UTD-1 (DON) UTD- 1 host UV Raman spectroscopy 12-P-07 UV-Visible spectroscopy 04-P-I 1 04-P-18 10-P-08 1l-P-20 13-0-02 14-P-14 14-P-18 14-P-26 14-P-35 22-P-21 30-P-31 Vis-UV spectroscopy UV-Visible spectroscopy, models UV-Visible-NIR

3 I-P- 10 22-P- 19 02-P-37 06-P- 14 13-P-15 23-P-33 23-P-33 23-P-33 26-P-08 25-P-09 30-P-17 14-P-36 11-P-23 11-P-23 1l-P-16 10-0-03 14-P-33 lI-P-15 14-P-20 32-P-07 14-O-03 14-P-30

V V-HMS 14-P-20 V-MCM-41 oxidation catalyst 29-P- 18 V-MCM-48 06-P-06 07-P-06 V-SBA- 15, photocatalyst 24-P-07 V-Silicalites 14-P-20 Vanadium organophosphates 22-0-02 Vanadosilicate, large pore 04-0-05 Vanadosilicates, synthesis 04-0-05 Vanadyl/BEA, spectroscopic study 14-P-35 VAPO 14-P-33 VAPO-5 14-P-33 VAPO-11, synthesis 03-P-16 VAPO-41, synthesis 03-P-16 VAPSO-5 14-P-33

W,Ni/FAU hydrocracking catalyst W-based hydrotreatment catalyst Wall properties, mesoporous silica Wall structure, mesoporous silica Wall structure, SBA- 15 Washing, effect on MCM-41 Waste streams, nuclear industry Wastewater treatment 3 l-P-14 Wastewater, agroindustrial Wastewater, Cr removal Wastewater, nitrogen industry Wastewater, Pb removal Wastewater, petroleum refineries Water adsorption models Water adsorption, TS- 1 Water adsorption, AIMepO Water clusters in FAU Water desorption from LTA Water desorption, modified MCM-41 Water diffusion, simulation Water, drinking, deammoniation Water effect on adsorption 16-O-03 19-P-06 Water, effect on NOx storage Water rolling Water storage Water treatment, fisheries WS2 HDS catalyst

1 l-P-08

26-P-08 08-P-14 06-P-05 08-0-03 06-P-28 05-O-01 31-P-15 31-0-03 31-P-13 31-P-10 3 I-P-06 30-P-20 16-O-03 14-P-34 09-P- 14 15-0-04 17-P-09 17-P-13 15-P-28 3 I-P-09 32-P-08 30-0-04 15-P-28 31-O-04 31 -P- 12 26-P- 17

X XAFS measurement 14-P-20 14-P-26 XAFS, Fe ZSM-5 XANES 14-P-08 129Xe-NMR, chemical shift 129Xe NMR in diffusion studies 129Xe NMR, MCM-48 131Xe-NMR, chemical shift Xe-SF6 diffusion in BOG, modelling XPS 04-P-18 09-P-10 26-P-14 XPS, Co XPS, Cu in MFI

28-P-07 12-O-02 14-P-39 14-P-27 19-P-09 06-P- 16 14-P-27 16-O-05 30-P-26 04-P- 18 30-P-21

433

X-ray diffraction X-ray diffraction, Ag-clinoptilolite X-ray diffraction, chloroalkene adsorption X-ray diffraction, grazing incidence X-ray diffraction, mesoporous silica X-ray diffraction, temperature resolved X-ray powder refinement X-ray scattering, mesoporous silica Xylene adsorption models m-Xylene conversion 12-P-14 Xylene isomerisation Xylene isomerisation, modelling Xylene isomerisation, NMR Xylene production Xylene separation Xylene separation, affected by water

05-0-04 01-P-15 17-P-11 20-0-04 06-P-05 09-P-13 09-P-07 06-P-05 16-O-03 26-P-20 28-P-06 15-P-20 12-0-01 25-P-10 18-P-08 16-O-03

Z Zearalenone, adsorption Zeolite A, s e e LTA Zeolite adsorbents, from fly ash Zeolite Beta, s e e BEA Zeolite F (EDI) synthesis, role of K and Na Zeolite modification Zeolite P (GIS) Zeolite X, s e e FAU Zeolite Y, s e e FAU Zeolitisation, bentonite in sea water Zeolitisation, diatoms Zeolitisation of volcanic glass Zeolitisation, volcano-sedimentary Zeoponic fertilizer delivery ZK-21, Ca form (LTA) ZK-21, Na,TMA (LTA) ZK-5, rare earth ZK-5, synthesis Zn-alumina, mesoporous ZnAPO-31 ZnAPO-37 Zn-FAU 10-P-05 Zn-LTA Zn-MFI Zn-MFI, sulfide host Zn-MFI, synthesis Zn-MOR 04-P-15 Zn,Ni-MFI, aromatisation catalyst 24-P-30 24-P-31 Zn phosphates Zn phosphate catalysts Zn spinel from zeolites ZnO clusters ZnO-CuO-ZrO2 Zn-Pt/zeolite X Zn-zeolites, oxidation catalyst

32-0-04 18-P- 10 03-0-05 3 l-P-08 3 I-P-05

03-P-06 2 l-P-07 0 I-P-I 3 01-O-02 31-O-02 18-P-13 18-P-13 I l-P-19 02-P-21 07-P- 16 14-P- 13 29-P-23 17-P-14 10-P-05 24-P-27 29-P-05 04-P- 14 13-P-32 28-0-02 05-0-04 29-P-23 10-P-07 10-P-05 24-P-26 29-P- 15 27-P-08

Zorite Zr/AI-MCM-41 Zr/AI-MCM-41, synthesis Zr-ETS-4 Zr-HMS, hydrotreatment catalyst Zr-HMS, support Zr-MCM-41 as Ni support Zr-MCM-41 oxidation catalyst ZrO2-CuO-ZnO ZrO2 derivatives ZrO2 nanoparticles in SBA-15 ZrO2 mesoporous 07-P-090 ZrO2/Na-Y ZrO2, Ni fuel cell catalyst ZrO2/SO42" ZSM-5, s e e MFI ZSM-12, s e e MTW ZSM-20 (FAU-EMT intergrowth) ZSM-22, s e e TON ZSM-25, synthesis ZSM-34 (ERI/OFF), synthesis ZSM-35 (FER) catalyst ZSM-48, synthesis

1 l-P-15

16-P-19 29-P-24 04-P- 16 26-P-22 26-P-22 23-P-28 29-P-18 24-P-26 07-P-09 29-P-17 7-P-I 1 07-P-20 30-P-08 07-P-20 29-P-07

13-P-21 02-P-10 02-P-22 26-P-10 02-P-41

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STUDIES IN SURFACE SClENCEAND CATALYSIS Advisory Editors: B. Delmon, Universitd Catholique de Louvain, Louvain-la-Neuve, Belgium J.T.Yates, University of Pittsburgh, Pittsburgh, PA, U.S.A. Volume 1

Volume 2

Volume 3

Volume 4

Volume 5

Volume 6 Volume 7 Volume 8 Volume 9 Volume 10 Volume 11

Volume 12 Volume 13 Volume 14 Volume 15

Preparation of Catalysts I.Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings of the First International Symposium, Brussels, October 14-17,1975 edited by B. Delmon, RA. Jacobs and G. Poncelet The Control of the Reactivity of Solids. A Critical Survey of the Factors that Influence the Reactivity of Solids, with Special Emphasis on the Control of the Chemical Processes in Relation to Practical Applications by V.V. Boldyrev, M. Bulens and B. Delmon Preparation of Catalysts II. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedingsofthe Second International Symposium, Louvain-la-Neuve, September 4-7, 1978 edited by B. Delmon, R Grange, R Jacobs and G. Poncelet Growth and Properties of Metal Clusters. Applications to Catalysis and the Photographic Process. Proceedings of the 32nd International Meeting of the Soci6td de Chimie Physique, Villeurbanne, September 24-28,1979 edited by J. Bourdon Catalysis by Zeolites. Proceedings of an International Symposium, Ecully (Lyon), September 9-11,1980 edited by B. Imelik, C. Neccache,Y. BenTaadt, J.C.Veddne, G. Coududer and H. Praliaud Catalyst Deactivation. Proceedings of an International Symposium, Antwerp, October 13-15,1980 edited by B. Delmon and G.E Froment New Hodzons in Catalysis. Proceedings of the 7th International Congress on Catalysis,Tokyo, June 30-July4, 1980. PartsA and B edited by 1".Seiyama and K.Tanabe Catalysis by Supported Complexes by Yu.I.Yermakov, B.N. Kuznetsov andV.A. Zakharov Physics of Solid Surfaces. Proceedings of a Symposium, Bechy~e, September 29-October 3,1980 edited by M. L6zni~,ka Adsorption at the Gas-Solid and Liquid-Solid Interface. Proceedings of an International Symposium, Aix-en-Provence, September 21-23,1981 edited by J. Rouquerol and K.S.W. Sing Metal-Support and Metal-Additive Effects in Catalysis. Proceedings of an International Symposium, Ecully (Lyon), September 14-16,1982 edited by B. Imelik, C. Naccache, G. Coududer, H. Preliaud, R Medaudeau, R Gallezot, G.A. Martin and J.C.Veddne Metal Microstructures in Zeolites. Preparation - Properties-Applications. Proceedings of aWorkshop, Bremen, September 22-24, 1982 edited by RA. Jacobs, N.I. Jaeger, R Jid= and G. Schulz-Ekloff Adsorption on Metal Surfaces. An Integrated Approach edited by J. B6nard Vibrations at Surfaces. Proceedings of theThird International Conference, Asilomar, CA, September 1-4,1982 edited by C.R. Brundle and H. Morawitz Heterogeneous Catalytic Reactions Involving Molecular Oxygen by G.I. Golodets

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Volume 32 Volume 33 Volume 34 Volume 35

Preparation of Catalysts Ul. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings oftheThird International Symposium, Louvain-la-Neuve, September 6-9, 1982 edited by G. Poncelet, R Grange and RA. Jacobs Spillover of Adsorbed Species. Proceedings of an International Symposium, Lyon-Villeurbanne, September 12-16,1983 edited by G.M. Pajonk, S.J.Teichner and J.E. Germain Structure and Reactivity of Modified Zeolites. Proceedings of an International Conference, Prague, July 9-13,1984 edited by RA. Jacobs, N.I. Jaeger, R Ji~,V.B. Kazansky and G. Schulz-Ekloff Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium on Catalysis, Quebec, RQ., September 30-October 3,1984 edited by S. Kaliaguine andA. Mahay Catalysis by Acids and Bases. Proceedings of an International Symposium, Villeurbanne (Lyon), September 25-27,1984 edited by B. Imelik, C. Naccache, G. Coud.uder,Y. BenTaadt and J.C.Veddne Adsorption and Catalysis on Oxide Surfaces. Proceedings of a Symposium, Uxbridge, June 28-29,1984 edited by M. Che and G.C. Bond Unsteady Processes in Catalytic Reactors by Yu.Sh. Matros Physics of Solid Surfaces 1984 edited by J. Koukal Zeolites: Synthesis, Structure,Technology and Application. Proceedings of an International Symposium, Portoroi-Portorose, September 3-8,1984 edited by B. Dr~aj, S. Ho(:evar and S. Pejovnik Catalytic Polymerization of Olefins. Proceedings of the International Symposium on Future Aspects of Olefin Polymerization,Tokyo, July 4-6,1985 edited by T. Keii and K. Soga Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference, Bowness-on-Windermere, September 15-19,1985 edited by D.A. King, N.V. Richardson and S. Holloway Catalytic Hydrogenation edited by L. Cerven~ New Developments in Zeolite Science andTechnology. Proceedings of the 7th International Zeolite Conference,Tokyo, August 17-22,1986 edited by Y. Murakami, A. lijima and J.W.Ward Metal Clusters in Catalysis edited by B.C. Gates, L. Guczi and H. Kn6zinger Catalysis andAutomotive Pollution Control. Proceedings of the First International Symposium, Brussels, September 8-11,1986 edited by A. Crucq andA. Frennet Preparation of Catalysts IV. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings of the Fourth International Symposium, Louvain-laNeuve, September 1-4,1986 edited by B. Delmon, R Grange, RA. Jacobs and G. Poncelet Thin Metal Films and Gas Chemisorption edited by RWissmann Synthesis of High-silicaAluminosilicate Zeolites edited by RA. Jacobs and J.A. Martens Catalyst Deactivation 1987. Proceedings of the 4th International Symposium, Antwerp, September 29-October 1,1987 edited by B. Delmon and G.E Froment Keynotes in Energy-Related Catalysis edited by S. Kaliaguine

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Methane Conversion. Proceedings of a Symposium on the Production of Fuels and Chemicals from Natural Gas,Auckland, April 27-30, 1987 edited by D.M. Bibby, C.D. Chang, R.E Howe and S.Yurchak Innovation in Zeolite Materials Science. Proceedings of an International Symposium, Nieuwpoort, September 13-17,1987 edited by RJ. Grobet, W.J. Mortier, E.EVansant and G. Schulz-Ekloff Catalysis 1987.Proceedings ofthe 10th North American Meeting ofthe Catalysis Society, San Diego, CA, May 17-22,1987 edited by J.W.Ward Characterization of Porous Solids. Proceedings of the IUPAC Symposium (COPS I), Bad Soden a.Ts.,Apri126-29,1987 edited by K.K. Unger, J. Rouquerol, K.S.W. Sing and H. Kral Physics of Solid Surfaces 1987. Proceedings of the Fourth Symposium on Surface Physics, Bechyne Castle, September 7-11,1987 edited by J. Koukal Heterogeneous Catalysis and Fine Chemicals. Proceedings of an International Symposium, Poitiers, March 15-17,1988 edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier and G. P6rot Laboratory Studies of Heterogeneous Catalytic Processes by E.G. Chdstoffel, revised and edited by Z. Pa61 Catalytic Processes under Unsteady-State Conditions by Yu. Sh. Matros Successful Design of Catalysts. Future Requirements and Development. Proceedings 0ftheWorldwide Catalysis Seminars, July, 1988, on the Occasion of the 30th Anniversary of the Catalysis Society of Japan edited by T. Inui Transition Metal Oxides. Surface Chemistry and Catalysis by H.H. Kung Zeolites as Catalysts, Sorbents and Detergent Builders. Applications and Innovations. Proceedings of an International Symposium,W~irzburg, September 4--8,1988 edited by H.G. Karge and J.Weitkamp Photochemistry on Solid Surfaces edited by M.Anpo andT. Matsuura Structure and Reactivity of Surfaces. Proceedings of a European Conference, Trieste, September 13-16,1988 edited by C. Morterra,A. Zecchina and G. Costa Zeolites: Facts, Figures, Future. Proceedings of the 8th International Zeolite Conference, Amsterdam, July 10-14,1989. Parts A and B edited by P.A.Jacobs and R.A. van Santen Hydrotreating Catalysts. Preparation, Characterization and Performance. Proceedings of the Annual International AIChE Meeting,Washington, DC, November 27-December 2,1988 edited by M.L. Occelli and R.G.Anthony New Solid Acids and Bases.Their Catalytic Properties by K.Tanabe, M. Misono,Y. Ono and H. Hattori RecentAdvances in Zeolite Science. Proceedings of the 1989 Meeting of the British Zeolite Association, Cambridge, April 17-19,1989 edited by J. Klinowsky and RJ. Barrie Catalyst in Petroleum Refining 1989. Proceedings of the First International Conference on Catalysts in Petroleum Refining, Kuwait, March 5-8,1989 edited by D.L.Tdmm,S.Akashah, M.Absi-Halabi andA. Bishara Future Opportunities in Catalytic and Separation Technology edited by M. Misono, Y. Moro-oka and S. Kimura

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New Developments in Selective Oxidation. Proceedings of an International Symposium, Rimini, Italy, September 18-22,1989 edited by G. Centi and I-.Tdfiro Volume 56 Olefin Polymerization Catalysts. Proceedings of the International Symposium on Recent Developments in Olefin Polymerization Catalysts,Tokyo, October 23-25,1989 edited by T. Keii and K. Soga Volume 57A SpectroscopicAnalysis of Heterogeneous Catalysts. Part A: Methods of SurfaceAnalysis edited by J.L.G. Fiewo Volume 57B SpectroscopicAnalysis of Heterogeneous Catalysts. Part B: Chemisorption of Probe Molecules edited by J.L.G. Fierro Introduction to Zeolite Science and Practice Volume 58 edited by H. van Bekkum, E.M. Flanigen and J.C. Jansen Volume 59 Heterogeneous Catalysis and Fine C.hemicals II. Proceedings of the 2nd International Symposium, Poitiers, October 2-6,1990 edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, G. P6rot, R. Maurel and C. Montassier Volume 60 Chemistry of Microporous Crystals. Proceedings of the International Symposium on Chemistry of Microporous Crystals,Tokyo, June 26-29,1990 edited by T. Inui, S. Namba andT.Tatsumi Volume 61 Natural Gas Conversion. Proceedings of the Symposium on Natural Gas Conversion, Oslo, August 12-17,1990 edited by A. Holmen, K.-J. Jens and S. Kolboe Volume 62 Characterization of Porous Solidsll. Proceedings of the IUPAC Symposium (COPS II),Alicante, May 6-9,1990 edited by F.Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing and K.K. Unger Volume 63 Preparation of CatalystsV. Scientific Bases for the Preparation of Heterogeneous Catalysts. Proceedings of the Fifth International Symposium, Louvain-la-Neuve, September 3-6,1990 edited by G. Poncelet, P.A.Jacobs, P.Grange and B. Delmon Volume 64 NewTrends in COActivation edited by L. Guczi Volume 65 Catalysis and Adsorption by Zeolites. Proceedings of ZEOCAT 90, Leipzig, August 20-23,1990 edited by G. ~hlmann, H. Pfeifer and R. Fdcke Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedings of the Fourth International Symposium on Dioxygen Activation and Homogeneous Catalytic Oxidation, Balatonf(ired, September 10-14,1990 edited by L.I. Sim~ndi Volume 67 Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis. Proceedings of the ACS Symposium on Structure-Activity Relationships in Heterogeneous Catalysis, Boston, MA, Apri122-27, 1990 edited by R.K. GrasseUi andA.W. Sleight Volume 68 Catalyst Deactivation 1991. Proceedings of the Fifth International Symposium, Evanston, IL, June 24-26,1991 edited by C.H. Bartholomew and J.B. Butt Volume 69 Zeolite Chemistry and Catalysis. Proceedings of an International Symposium, Prague, Czechoslovakia, September 8-13, 1991 edited by RA. Jacobs, N.I. Jaeger, L. Kubelkov6 and B.Wichtedov6 Volume 70 Poisoning and Promotion in Catalysis based on Surface Science Concepts and Experiments by M. Kiskinova

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Catalysis and Automotive Pollution Control II. Proceedings of the 2nd International Symposium (CAPoC 2), Brussels, Belgium, September 10-13,1990 edited by A. Crucq New Developments in Selective Oxidation by Heterogeneous Catalysis. Proceedings of the 3rd European Workshop Meeting on New Developments in Selective Oxidation by Heterogeneous Catalysis, Louvain-la-Neuve, Belgium, April 8-10,1991 edited by R Ruiz and B. Delmon Progress in Catalysis. Proceedings of the 12th Canadian Symposium on Catalysis, Banff, Alberta, Canada, May 25-28, 1992 edited by K.J. Smith and E.C.Sanford Angle-Resolved Photoemission.Theory and CurrentApplications edited by S.D. Kevan New Frontiers in Catalysis, PartsA-C. Proceedings of the 10th International Congress on Catalysis, Budapest, Hungary, 19-24 July, 1992 edited by L. Guczi, F.Solymosi a~d RT6t6nyi fluid Catalytic Cracking: Science andTechnology edited by J.S. Magee and M.M. Mitchell, Jr. NewAspects of Spillover Effect in Catalysis. For Development of HighlyActive Catalysts. Proceedings of theThird International Conference on Spillover, Kyoto, Japan,August 17-20,1993 edited by T. Inui, K. Fujimoto,T. Uchijima and M. Masai Heterogeneous Catalysis and Fine Chemicals III. Proceedings of the 3rd International Symposium, Poitiers, April 5 - 8,1993 edited by M. Guisnet, J. Barbier, J. Barrault, C. Bouchoule, D. Duprez, G. P6rot and C. Montassier Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and Industrial Catalysis edited by J.A. Moulijn, RW.N.M. van Leeuwen and R.A. van Santen Fundament=_!s of Adsorption. Proceedings of the Fourth International Conference on Fundamentals ofAdsorption, Kyoto, Japan, May 17-22,1992 edited by M. Suzuki Natural Gas Conversion ~.. Proceedings of theThird Natural Gas Conversion Symposium, Sydney, July 4-9,1993 edited by H.E. Curry-Hyde and R.F.Howe New Developments in Selective Oxidation II. Proceedings of the SecondWorld Congress and Fourth EuropeanWorkshop Meeting, Benalmddena, Spain, September 20-24,1993 edited by V. Cort6s Corber6n and S.Vic Bell6n Zeolites and Microporous Crystals. Proceedings of the International Symposium on Zeolites and Microporous Crystals, Nagoya, Japan,August 22-25,1993 edited byT. Hattod andT.Yashima Zeolites and Related Microporous Materials: State of theArt 1994. Proceedings of the 10th International Zeolite Conference, Garmisch-Partenkirchen, Germany, July 17-22,1994 edited by J.Weitkamp, H.G. Karge, H. Pfeifer andW. H61dedch Advanced Zeolite Science and Applications edited by J.C. Jansen, M. St6cker, H.G. Karge and J.Weitkamp Oscillating Heterogeneous Catalytic Systems by M.M. Slin'ko and N.I. Jaeger Characterization of Porous Solids Ul. Proceedings of the IUPAC Symposium (COPS III), Marseille, France, May 9-12,1993 edited by J.Rouquerol, F.Rodriguez-Reinoso, K.S.W. Sing and K.K. Unger

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Catalyst Deactivation 1994. Proceedings of the 6th International Symposium, Ostend, Belgium, October 3-5,1994 edited by B. Delmon and G.E Froment Catalyst Design forTailor-made Polyolefins. Proceedings of the International Symposium on Catalyst Design forTailor-made Polyolefins, Kanazawa, Japan, March 10-12,1994 edited by K. Soga and M.Terano Acid-Base Catalysis II. Proceedings of the International Symposium on Acid-Base Catalysis II, Sapporo, Japan, December 2-4,1993 edited by H. Hattori, M. Misono andY. Ono Preparation of CatalystsVI. Scientific Bases for the Preparation of Heterogeneous Catalysts. Proceedings of the Sixth International Symposium, Louvain-La-Neuve, September 5-8,1994 edited by G. Poncelet, J. Martens, B. Delmon, RA. Jacobs and R Grange Science andTechnology in Catalysis 1994. Proceedings of the SecondTokyo Conference on Advanced Catalytic Science andTechnology, Tokyo, August 21-26,1994 edited by Y. Izumi, H.Arai and M. Iwamoto Charactedzation and Chemical Modification of the Silica Surface by E.EVansant, RVan DerVoort and K.C.Vrancken Catalysis by Microporous Matedals. Proceedings of ZEOCAT'95, Szombathely, Hungary, July 9-13,1995 edited by H.K. Beyer, H.G.Karge, I. Kiricsi and J.B. Nagy Catalysis by Metals andAIIoys by V. Ponec and G.C. Bond Catalysis and Automotive Pollution Control III. Proceedings of theThird International Symposium (CAPoC3), Brussels, Belgium, April 20-22,1994 edited by A. Frennet and J.-M. Bastin Zeolites:A RefinedTool for Designing Catalytic Sites. Proceedings of the International Symposium, Qu6bec, Canada, October 15-20,1995 edited by L. Bonneviot and S. Kaliaguine Zeolite Science 1994: Recent Progress and Discussions. Supplementary Materials to the 10th International Zeolite Conference, Garmisch-Partenkirchen, Germany, July 17-22,1994 edited by H.G. Karge and J.Weitkamp Adsorption on New and Modified Inorganic Sorbents edited by A. Dqbrowski andV.A.Tertykh Catalysts in Petroleum Refining and Petrochemical Industdes 1995. Proceedings ofthe 2nd International Conference on Catalysts in Petroleum Refining and Petrochemical Industries, Kuwait, April 22-26,1995 edited by M.Absi-Halabi, J. Beshara, H. Qabazard andA. Stanislaus 11th International Congress on Catalysis - 40th Anniversary. Proceedings ofthe 11th ICC, Baltimore, MD, USA, June 30-July 5,1996 edited by J.W. Hightower, W.N. Delgass, E. Iglesia andA.T. Bell RecentAdvances and New Hodzons in Zeolite Science andTechnology edited by H. Chon, S.I.Woo and S.-E. Park Semiconductor Nanoclusters - Physical, Chemical, and CatalyticAspects edited by RV. Kamat and D. Meisel Equilibda and Dynamics of GasAdsorption on Heterogeneous Solid Surfaces edited by W. Rudzir~ski,W.A. Steele and G. Zgrablich Progress in Zeolite and Microporous Matedals Proceedings of the 11th International Zeolite Conference, Seoui, Korea, August 12-17,1996 edited by H. Chon, S.-K. Ihm andY.S. Uh

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Volume 119

Hydrotreatment and Hydrocracking of Oil Fractions Proceedings of the 1st International Symposium / 6th EuropeanWorkshop, Oostende, Belgium, February 17-19,1997 edited by G.F. Froment, B. Delmon and R Grange Natural Gas Conversion IV Proceedings of the 4th International Natural Gas Conversion Symposium, Kruger Park, South Africa, November 19-23,1995 edited by M. de Pontes, R.L. Espinoza, C.R Nicolaides, J.H. Scholtz and M.S. Scurrell Heterogeneous Catalysis and Fine Chemicals IV Proceedings of the 4th International Symposium on Heterogeneous Catalysis and Fine Chemicals, Basel, Switzerland, September 8-12,1996 edited by H.U. Blaser,A. Balker and R. Pdns Dynamics of Surfaces and Reaction Kinetics in Heterogeneous Catalysis. Proceedings of the International Symposium,Antwerp, Belgium, September 15-17,1997 edited by G.F. Froment and K.C.Waugh ThirdWorld Congress on Oxidation Catalysis. Proceedings of theThirdWorld Congress on Oxidation Catalysis, San Diego, CA, U.S.A., 21-26 September 1997 edited by R.K. Grasselli, S.T. Oyama, A.M. Gaffney and J.E. Lyons Catalyst Deactivation 1997. Proceedings of the 7th International Symposium, Cancun, Mexico, October 5-8,1997 edited by C.H. Bartholomew and G.A. Fuentes Spillover and Migration of Surface Species on Catalysts. Proceedings ofthe 4th International Conference on Spillover, Dalian, China, September 15-18,1997 edited by Can Li and Qin Xin RecentAdvances in Basic and Applied Aspects of Industrial Catalysis. Proceedings ofthe 13th National Symposium and Silver Jubilee Symposium of Catalysis of India, Dehradun, India, April 2-4,1997 edited by T.S.R. Prasada Rao and G. Murali Dhar Advances in Chemical Conversions for Mitigating Carbon Dioxide. Proceedings of the 4th International Conference on Carbon Dioxide Utilization, Kyoto, Japan, September 7-11,1997 edited by T. Inui, M.Anpo, K. Izui, S.Yanagida andT.Yamaguchi Methods for Monitoring and Diagnosing the Efficiency of Catalytic Converters. A patent-oriented survey by M. Sideris Catalysis and Automotive Pollution Control IV. Proceedings of the 4th International Symposium (CAPoC4), Brussels, Belgium, April 9-11,1997 edited by N. Kruse, A. Frennet and J.-M. Bastin Mesoporous Molecular Sieves 1998 Proceedings of the 1st International Symposium, Baltimore, MD, U.S.A., July 10-12,1998 edited by L.Bonneviot, E B61and,C. Danumah, S. Giasson and S. Kaliaguine Preparation of Catalysts VII Proceedings ofthe 7th International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts, Louvain-la-Neuve, Belgium, September 1-4,1998 edited by B. Delmon, RA. Jacobs, R. Maggi, J.A. Martens, R Grange and G. Poncelet Natural Gas ConversionV Proceedings of the 5th International Gas Conversion Symposium, Giardini-Naxos, Taormina, Italy, September 20-25,1998 edited by A. Parmaliana, D. Sanfilippo, E Frusted,A.Vaccad and F.Arena

442 Volume 120A Adsorption and its Applications in Industry and Environmental Protection. Vol I: Applications in Industry edited by A. D0browski Volume 120B Adsorption and its Applications in Industry and Environmental Protection. Vol I1:Applications in Environmental Protection edited byA. Dsbrowski Volume 121 Science andTechnology in Catalysis 1998 Proceedings of theThirdTokyo Conference in Advanced Catalytic Science and Technology,Tokyo, July 19-24,1998 edited by H. Hattori and K. Otsuka Volume 122 Reaction Kinetics and the Development of Catalytic Processes Proceedings ofthe International Symposium, Brugge, Belgium, April 19-21,1999 edited by G.E Froment and K.C.Waugh Volume 123 Catalysis: An Integrated Approach Second, Revised and Enlarged Edition edited by R.A. van Santen, RW.N.M. van Leeuwen, J.A. Moulijn and B.A.Averill Volume 124 Experiments in Catalytic Reaction Engineering by J.M. Berry Volume 125 Porous Materials in Environmentally Friendly Processes Proceedings ofthe 1st International FEZA Conference, Eger, Hungary, September 1-4,1999 edited by I. Kiricsi, G. P=tl-Borb61y,J.B. Nagy and H.G. Karge Volume 126 Catalyst Deactivation 1999 Proceedings of the 8th International Symposium, Brugge, Belgium, October 10-13,1999 edited by B. Delmon andG.E Froment Volume 127 Hydrotreatment and Hydrocracking of Oil Fractions Proceedings of the 2nd International Symposium/7th European Workshop, Antwerpen, Belgium, November 14-17,1999' edited by B. Delmon, G.E Froment and R Grange Volume 128 Characterisation of Porous SolidsV Proceedings of the 5th International Symposium on the Characterisation of Porous Solids (COPS-V), Heidelberg, Germany, May 30- June 2,1999 edited by K.K. Unger, G. Kreysa and J.R Baselt Volume 129 Nanoporous Materials II Proceedings of the 2nd Conference on Access in Nanoporous Materials, Banff, Alberta, Canada, May 25-30, 2000 edited byA. Sayari, M. Jaronier andT.J. Pinnavaia Volume 130 12th Intemational Congress on Catalysis Proceedings of the 12th ICC, Granada, Spain, July 9-14, 2000 edited byA. Corma, EV. Melo, S. Mendioroz and J.L.G. Fierro Volume 131 Catalytic Polymerization of Cycloolefins Ionic, Ziegler-Natta and Ring-Opening Metathesis Polymerization byV. Dragutan and R. Streck Volume 132 Proceedings of the Intemational Conference on Colloid and Surface Science, Tokyo, Japan, November 5-8, 2000 25th Anniversary ofthe Division of Colloid and Surface Chemistry, The Chemical Society of Japan edited byY. Iwasawa, N. Oyama and H. Kunieda Volume 133 Reaction Kinetics and the Development and Operation of Catalytic Processes Proceedings of the 3rd International Symposium, Oostende, Belgium, April 22-25, 2001 edited by G.E Froment and K.C.Waugh Volume 134 Fluid Catalytic CrackingV Materials and Technological Innovations edited by M.L. Occelli and R O'Connor

443 Volume 135

Zeolites and Mesoporous Materials at the Dawn of the 21st Century. Proceedings of the 13th International Zeolite Conference, Montpellier, France, 8-13 July 2001 edited by A. Galameau, E di Renzo, E Fajula and J.Vedrine

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