Elementary Reaction Steps in Heterogeneous Catalysis NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an intemational board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DAT A BASE" with user-friendly retrieval software in English, French and German (©WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series C: Mathematical and Physical Sciences - Vol. 398 Elementary Reaction Steps in Heterogeneous Catalysis edited by R. W. Joyner Leverhulme Centre for Innovative Catalysis, Department of Chemistry, University of Liverpool, Liverpool, United Kingdom and R. A. van Santen Schuit Institute of CatalYSiS, Eindhoven Technical University, Eindhoven, The Netherlands Springer Science +Business Media, B.V. Proceedings of the NATO Advanced Research Workshop on Elementary Reaction Steps in Heterogeneous Catalysis Bedoin, Vaucluse, France November 1-7,1992 Library of Congress Cataloging-in-Publication Data NATO Advanced Research Workshop on Elementary Reaction Steps In Heterogeneous CatalysIs (1992 Bedoln, France) Elementary reaction steps In heterogeneous catalysIs proceedings of the NATO Advanced Research Workshop on Elementary Reaction Steps In Heterogeneous CatalysIs, Bedoln, Vaucluse, France, November 1-7, 1992 I edited by R.W. Joyner and R.A. van Santen. p. cm. -- (NATO ASI series. Series C, Mathematical and physical sCiences; no. 398) Inc 1udes Index. ISBN 978-94-010-4741-8 ISBN 978-94-011-1693-0 (eBook) DOI 10.1007/978-94-011-1693-0 1. Heterogeneous catalysls--Congresses. 2. Chemical reaction, Conditions and laws of--Congresses. I. Joyner, R. W. II. Santen, R. A. van (Rutger A.) III. Title. IV. Series. Q0505.N3644 1992 541.3' 95--dc20 93-17085 ISBN 978-94-010-4741-8 Printed on acid-free paper All Rights Reserved © 1993 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1993 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. CONTENTS Preface ix Introduction: Elementary Reaction Steps in Heterogeneous Catalysis .................................................................................................................. R.W. Joyner and R.A. van Santen Session 1: Catalytic Reactivity Surface Science as a Basis for Understanding Heterogeneous Catalysis ................................................................................................................... 3 G.A. Somorjai Organometallic Chemistry as a Basis for Understanding Heterogeneous Catalysis ............................................ ............................ ................. 39 J.M. Basset, S.L. Scott, A. Choplin, M. Leconte, F. Quignard, C. Santini and A. Theolier The Organic Chemical Approach to Heterogeneous Catalysis ................................ 51 J.J. Rooney Electrochemical Activation of Catalysed Reactions ................................................. 73 C.G. Vayenas Selective Oxidation Pathways at Oxide Surfaces: The Transformation of Alkanes on Vanadyl Pyrophosphate ............. ....................... 93 G. Centi Theory of Bronsted Acidity in Zeolites ............................................ ........ ................. 113 R.A. van Santen, G.J. Kramer and W.P.J.H. Jacobs Discussion Summary: Session 1 .............. .......................................... ........................ 133 Rapporteur P.B. Wells Session 2: Swface Science Studies in Catalysis Surface Reactivity of Oxides .................................................................................... 137 E. Bordes Adsorption and Reactions of CO, NO, H2 and Oz on Group VIII Metal Surfaces ........................................................................................ 155 B.E. Nieuwenhuys vi Model Catalyst Studies of Titania Supported Rhodium ............................................ 179 J. Evans, B.E. Hayden, J.F.W. Mosselmans and AJ. Murray The Dynamics of Alkane Adsorption on Metals. .... .... ...... .... ...... ...... ...... ...... ...... ...... 197 G.W. Coulston and G.L. Haller The Study of Dynamics at Catalytic Surfaces with Nuclear Magnetic Resonance Spectroscopy ........................................................................... 221 T.M. Duncan Discussion Summary: Session 2 ............................................................................... 243 Rapporteur H.P.C.E. Kuipers Session 3: In-situ Methods in Catalysis Applications of Synchrotron Radiation in Catalysis ............................................... 249 R.W. Joyner Infrared Spectroscopy as a Probe of Surface Acidity .............................................. 267 H. Knozinger The Effects of Coadsorbates on the Behaviour of Surface Species and Sites in Catalysis by Means of EXAFS and FTIR ................................. 287 Y.Iwasawa How Can Scanning Tunneling Microscopy, Coupled with Theory, Help Us Understand Some Elementary Steps in Catalysis ....................................... 305 P. Sautet, J.C. Dunphy and M.B. Salmeron Discussion Summary: Session 3 ................................................................................ 313 Rapporteur V. Ponec Session 4: The Contribution of Theory to Catalytic Understanding Quantum Chemistry of Chemisorption at Metal and Oxide Surfaces: A Cluster Model Approach ........................................................................ 317 G. Pacchioni and P.S. Bagus Reaction Dynamics at Surfaces .... .... .......... .... .......... .... .... ...... .... .... .... ...... ........ .... ...... 341 S. Holloway Chemical Reactivity as a Function of Coverage ........................................................ 359 V.P. Zhdanov Solvent Effects on the Diels-Alder Reaction of Methyl Vinyl Ketone and Cyclopentadiene from Computer Simulations ........................................ 377 W.L. Jorgensen, D. Lim and J.F. Blake vii Molecular Modeling and Molecular Graphics of Sorbates in Molecular Sieves ..... ............................................................................................... 389 D.P. Vercauteren, L. Leherte, DJ. Vanderveken, I.A. Horsley, C.M. Freeman and E.G. Derouane Discussion Summary: Session 4 ................................................................................. 403 Rapporteur E. Shustorovich Session 5: Chemical Kinetics alld Chemical Engineering Reaction Modelling on the Basis of the Published Potential Energy Diagram ................................................... ...................... ................................ 407 K.C. Waugh Transient Kinetics in Catalysis by Metals .................................................................. 423 A. Frennet Reaction Kinetics and Industrial Catalysis ................................................................. 441 I. Rostrup-Nielsen Discussion Summary: Session 5 ................................................................................. 461 Rapporteur I.C. Vedrine Summary Lectures Toward Next Century's Industrial Catalysis ............................................................. 465 J.J. Lerou and L.E. Manzer Elementary Reaction Steps in Heterogeneous Catalysis: A Workshop Overview ............................................................................................... 473 G.L. Haller and G.W. Coulston List of Contributors .................................................................................................... 485 Index ........................................................................................................................... 489 Preface This book comprises the proceedings of a NATO sponsored Advanced Research Workshop held from 1st November to 6th November 1992 in the delightful Chateau de Florans, Bedoin, Vaucluse, France and entitled 'Elementary Reaction Steps in Heterogeneous Catalysis.' The organisers are grateful to the Science Committee of NATO for their support of this meeting. This is believed to be the first wide ranging NATO ARW in the field of heterogeneous catalysis for 20 years, following a previous venture organised in Sardinia by Basolo and Burwell, of Northwestern University, Illinois, USA [1]. This volume collects the lecture presentations and reports on the lively Panel discussions.