Molecular Sieves - Science and Technology - Vol. 6 - Characterization II / 00-front-matter

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Molecular Sieves

Science and Technology

Editors: H. G. Karge · J. Weitkamp

Molecular Sieves

Editors: H. G. Karge · J. Weitkamp

Recently Published and Forthcoming Volumes

Characterization II	Structures and Structure Determination
Editors: Karge, H. G., Weitkamp J.	Editors: Karge, H. G., Weitkamp J.
Vol. 5, 2006	Vol. 2, 1999
Characterization I	Synthesis
Editors: Karge, H. G., Weitkamp J.	Editors: Karge, H. G., Weitkamp J.
Vol. 4, 2004	Vol. 1, 1998
Post-Synthesis Modification I
Editors: Karge, H. G., Weitkamp J.
Vol. 3, 2003

Characterization II

Editors: Hellmut G. Karge · Jens Weitkamp

With contributions by

R. Aiello · F. Bauer · J.-L. Bonardet · J. Fraissard R. Fricke · A. Gédéon · G. Giordano · H. G. Karge A. Katovic · I. Kiricsi · Z. Kónya · H. Kosslick

J. B.Nagy · G. Pál-Borbély · S. Sealy · M.-A. Springuel-Huet F. Testa · Y. Traa · J. Weitkamp

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Molecular Sieves – Science and Technology will be devoted to all kinds of microporous crystalline solids with emphasis on zeolites. Classical alumosilicate zeolites as well as microporous silica will typically be covered; titaniumsilicate, alumophosphates, gallophosphates, silicoalumophosphates, and metalloalumophosphates are also within the scope of the series. It will address such important items as hydrothermal synthesis, structures and structure determination, post-synthesis modifications such as ion exchange or dealumination, characterization by all kinds of chemical and physico-chemical methods including spectroscopic techniques, acidity and basicity, hydrophilic vs. hydrophobic surface properties, theory and modelling, sorption and diffusion, host-guest interactions, zeolites as detergent builders, as catalysts in petroleum refining and petrochemical processes, and in the manufacture of organic intermediates, separation and purification processes, zeolites in environmental protection.

As a rule, contributions are specially commissioned. The editors and publishers will, however, always be pleased to receive suggestions and supplementary information. Papers for Molecular Sieves are accepted in English. In references Molecular Sieves is abbreviated Mol Sieves and is cited as a journal.

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Library of Congress Control Number: 2006923496

ISSN 1436-8269

ISBN-10 3-540-30457-6 Springer Berlin Heidelberg New York

ISBN-13 978-3-540-30457-9 Springer Berlin Heidelberg New York

DOI 10.1007/b58179

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Editors

Dr. Hellmut G. Karge

Fritz Haber Institute

of the Max Planck Society

Faradayweg 4–6

14195 Berlin

Germany

Professor Dr.-Ing. Jens Weitkamp

Institute of Technical Chemistry

University of Stuttgart

70550 Stuttgart

Germany

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Preface

In the preface to Vol. 4, it was stressed that characterization of molecular sieves is an indispensable prerequisite for the evaluation of results in the synthesis, modification, and application of these microporous and mesoporous materials. Thus, Vol. 2 grouped together contributions to structure analysis of molecular sieves, whereas Vol. 4 was particularly devoted to characterization by spectroscopic techniques. Logically, Vol. 5 is intended to complement the preceding volume in that it covers a variety of non-spectroscopic techniques for the characterization of zeolites and related materials. Thereby, some of the contributions are specifically focused on methods of characterization such as chemical analysis, thermal analysis, pore-size characterization using molecular probes or 129Xe NMR, which are, of course, illustrated by a wealth of applications. Two other chapters deal specifically with the characterization of important molecular sieve systems, viz. coke on zeolites and isomorphously substituted molecular sieves.

The first chapter, co-authored by R. Fricke and H. Kosslick, provides, in an exhaustive manner, methods of chemical analysis of (microporous) aluminosilicates, aluminophosphates and related molecular sieves. These analytical methods are exemplified by a large number of cases and, very importantly, the chemical procedures and treatments are meticulously described. To the best of our knowledge, no comparable compendium of chemical analysis of zeolites and related substances has ever been available before.

In her contribution, G. Pál-Borbély shows the great potential of thermal analysis for the characterization of molecular sieves and processes occurring with them as far as they are accompanied by changes in weight and/or heat effects. Such processes are, for example, dehydration, dehydroxylation, deammoniation, phase transition, structure collapse, decomposition of occluded complexes, and oxidation or reduction of framework constituents. In this context, applications of thermogravimetry (TG), derivative thermogravimetry (DTG), differential thermoanalysis (DTA), differential scanning calorimetry (DSC), and also more recent developments such as tapered element oscillating microbalance (TEOM) measurements are discussed.

With respect to the understanding and possible applications of structured microporous and mesoporous materials, the knowledge of their pore sizes is of paramount importance. There are several approaches to determining pore

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Preface

sizes, for example, via scattering techniques, electron microscopy or 129Xe NMR (see also the fourth chapter). In this volume, however, Y. Traa, S. Sealy and J. Weitkamp describe and critically discuss the characterization of pore sizes using probe molecules, i.e., by techniques based on either adsorption or catalytic test reactions. The intense investigation of the relationship between a catalytic test reaction, viz. shape-selective hydrocracking of C10 cycloalkanes, and the effective pore width of zeolites finally led to the introduction of the spaciousness index (SI), which, since then, has found widespread acceptance. A versatile method of characterizing molecular sieves was developed with the help of 129 Xe NMR. One of the pioneers of this remarkable characterization technique, J. Fraissard, has contrubuted the fourth chapter of this volume. Here, he explains the fundamentals of the method and demonstrates its capability of studying the porosity of zeolites, the effect of cation exchange, the distribution of adsorbed phases, the behavior of zeolite-supported metals, phenomena of Xe diffusion, and special features of other microporous (pillared clays, heteropolyoxometalate salts, activated carbons) and mesoporous solids (M41S and SBA materials).

Catalyst deactivation as a consequence of the undesired deposition of carbonaceous materials plays an important role in many catalytic processes on microand mesoporous solids. Coke formation on zeolites and the effect of several features of coke deposition, such as shape selectivity, acidity of the catalyst, location, mechanism and kinetics of coke build-up, activity of and selectivation by coke are dealt with in the fifth chapter written by F. Bauer and H.G. Karge. However, the focus of this contribution is laid on the characterization of coke formed on zeolites by spectroscopic and non-spectroscopic techniques and the relationship derived therefrom between the nature of the coke and the conditions of its formation.

The last chapter is devoted to the characterization of very interesting derivatives of the common molecular sieves, i.e., the isomorphously substituted molecular sieves. The notorious main problem here is whether or not the hetero-element (such as B, Ga, Fe, Ti, V, Zn, Co) is unambiguously incorporated into the framework of the porous material. The authors, J. B.Nagy, R. Aiello, G. Giordano, A. Katovic, F. Testa, Z. Kónya, and I. Kiricsi provide a large body of experimental results of successful isomorphous substitution and a great number of cases where the position of the isomorphously introduced hetero-element (before and after additional treatment) can be identified by sophisticated physico-chemical investigations.

Most likely, the important art of characterizing microand mesoporous structured materials will turn out to have not been exhaustively covered by Vols. 4 and 5. Thus, it could well be that additional characterization techniques will be dealt with in a future volume of this book series.

April 2006	Hellmut G. Karge
	Jens Weitkamp

Contents

Chemical Analysis of Aluminosilicates,
Aluminophosphates and Related Molecular Sieves
H. Kosslick · R. Fricke . . . . . . . . . . . . . . . . . . . . . . . . . . .	1
Thermal Analysis of Zeolites
G. Pál-Borbély . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .	67
Characterization of the Pore Size of Molecular Sieves
Using Molecular Probes
Y. Traa · S. Sealy · J. Weitkamp . . . . . . . . . . . . . . . . . . . . . . .	103
NMR of Physisorbed 129Xe Used as a Probe
to Investigate Molecular Sieves
J.-L. Bonardet · A. Gédéon · M.-A. Springuel-Huet · J. Fraissard . . . . .	155
Characterization of Coke on Zeolites
F. Bauer · H. G. Karge . . . . . . . . . . . . . . . . . . . . . . . . . . . .	249
Isomorphous Substitution in Zeolites
J. B.Nagy · R. Aiello · G. Giordano · A. Katovic · F. Testa ·
Z. Kónya · I. Kiricsi . . . . . . . . . . . . . . . . . . . . . . . . . . . . .	365
Author Index Volumes 1–5 . . . . . . . . . . . . . . . . . . . . . . . . .	479
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .	483

Contents of Volume 4

Characterization I

Editors: Hellmut G. Karge, Jens Weitkamp

ISBN: 3-540-64335-4

Vibrational Spectroscopy

H. G. Karge · E. Geidel

NMR Spectroscopy

M. Hunger · E. Brunner

ESR Spectroscopy

H. Brunner, R. A · Schoonheydt · B. M. Weckhuysen

UV/VIS Spectroscopy

H. Förster

EXAFS, XANES and Related Techniques

P. Behrens

XPS and Auger Electron Spectroscopy

W. Grünert · R. Schlögl

Mössbauer Spectroscopy

L. Rees