Surface Reactions PDF
Preview Surface Reactions
Springer Series in Surface Sciences 34 Editor: Robert Gomer Springer Series in Surface Sciences Editors: G. ErtI, R. Gomer, and D.L. Mills Managing Editor: H.K.V. Lotsch 1 Physisorption Kinetics 19 Desorption Induced by Electronic Transitions By H.J. Kreuzer, Z.W. Gortel DIET IV Editors: G. Betz, P. Varga 2 The Structure of Surfaces Editors: M.A. Van Hove, S.Y. Tong 20 Scanning Tunneling Microscopy I General Principles and Applications to Clean Dynamical Phenomena at Surfaces, Interfaces and Adsorbate-Covered Surfaces and Superlattices Editors: H.-J. Giintherodt, R. Wiesendanger Editors: F. Nizzoli, K.-H. Rieder, R.F. Willis 21 Surface Pbonons 4 Desorption Induced by Electronic Transitions, Editors: W. Kress, F.W. de Welte DIET II Editors: W. Brenig, D. Menzel 22 Chemistry and Physics of Solid Surfaces VIII Editors: R. Vanselow, R. Howe 5 Chemistry and Physics of Solid Surfaces VI Editors: R. Vanselow, R. Howe 23 Sorface Analysis Methods in Materials Science 6 Low-Energy Electron Diffraction Editors: D.J. O'Connor, B.A. Sexton, Experiment, Theory and Surface R. SI. C. Smart Structure Determination 24 The Structure of Surfaces III By M.A. Van Hove, W.H. Weinberg, C.-M. Chan Editors: S.Y. Tong, M.A. Van Hove, 7 Electronic Phenomena in Adsorption and Catalysis K. Takayanagi, X.D. Xie By V.F. Kiselev, O.V. Krylov 25 NEXAFS Spectroscopy 8 Kinetics of Interface Reactions By J. Stohr Editors: M. Grunze, H.J. Kreuzer 26 Semiconductor Surfaces and Interfaces 9 Adsorption and Catalysis on Transition By W. Monch Metals and Their Oxides 27 Helium Atom Scattering from Sorfaces By V.F. Kiselev, O.V. Krylov Editor: E. Hulpke 10 Chemistry and Physics of Solid Surfaces VII 28 Scanning Tunneling Microscopy II Editors: R. Vanselow, R. Howe Further Applications and Related Scanning 11 The Structure of Surfaces II Techniques Editors: J.F. van der Veen, M.A. Van Hove Editors: R. Wiesendanger, H.-J. Giintherodt 12 Diffusion at Interfaces: Microscopic Concepts 29 Scanning Tunneling Microscopy III Editors: M. Grunze, H.J. Kreuzer, J.J. Weimer Theory of STM and Related Scanning Probe Methods 13 Desorption Induced by Electronic Transitions, Editors: R. Wiesendanger, H.-J. Giintherodt DIET III Editors: R.H. Stulen, M.L. Knotek 30 Concepts in Surface Physics 14 Solvay Conference on Surface Science By M.C. Desjonqmlres, D. Spanjaard Editor: F.W. de Wette 31 Desorption Induced by Electronic Transitions 15 Surfaces and Interfaces of Solids DIET V By H. Liith Editors: A.R. Bums, E.B. Stechel, D.R. Jennison 16 Atomic and Electronic Structure of Surfaces 32 Scanning Tunneling Microscopy and Related Theoretical Foundations Techniques By M. Lannoo, P. Friedel By Ch. Bai 17 Adhesion and Friction 33 Adsorption on Ordered Surfaces of Ionic Solids Editors: M. Grunze, H.J. Kreuzer Editors: H.J. Freund, E. Umbach 18 Auger Spectroscopy and Electronic Structure 34 Surface Reactions Editors: G. Cubiotti, G. Mondio, K. Wandelt Editor: R.J. Madix R.J. Madix (Ed.) Surface Reactions With Contributions by DJ. Auerbach B.E. Bent L.H. Dubois C.M. Friend R.M. Lambert R.J. Madix H.A. Michelsen C.B. Mullins R.G. Nuzzo R.M. Ormerod C.T. Rettner J.T. Roberts W.H. Weinberg With 150 Figures Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest Professor R.J. Madix Department of Chemical Engineering Stanford University Stanford, CA 94305-5025, USA Series Editors Professor Dr. Gerhard Ert! Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany Professor Robert Gomer, Ph.D. The James Franck Institute, The University of Chicago, 5640 Ellis Avenue, Chicago, IL 60637, USA Professor Douglas L. Mills, Ph.D. Department of Physics, University of California, Irvine, CA 92717, USA Managing Editor: Dr. Helmut K.Y. Lotsch Springer-Verlag, Tiergartenstrasse 17, D-69121 Heidelberg, Germany ISBN-13: 978-3-642-78748-5 e-ISBN-13: 978-3-642-78746-1 DOl: 10.1007/978-3-642-78746-1 Library of Congress Cataloging· in-Publication Data. Surface reactions/Robert J. Madix (ed.) p. cm. (Springer series in surface sciences; 34) Includes bibliographical references and index. 1. Surfaces (Physics) 2. Surface chemistry. I. Madix, Robert J., 1938- . II. Series. QC173. 4. S94S9638 1994 546'. 6---dc20 93-49867 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. © Springer-Verlag Berlin Heidelberg 1994 Softcover reprint of the hardcover 1s t edition 1994 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. SPIN: 10068806 54/3140/SPS - 5 4 3 2 1 0 - Printed on acid-free paper Preface In the past ten years the study of the mechanisms of chemical transformations on metal surfaces has advanced appreciably. Today complex reaction networks can be unraveled by combining several spectroscopies, derived principally from the practice of ultrahigh-vacuum surface physics. Of paramount importance in this field is the combination of mass spectrometric methods for the identification of reaction products with spectroscopies which help identify surface-bound reactive intermediates. This quasi-monograph highlights the progress in this field with studies which clearly exemplify such research and at the same time provide more general understanding of chemical reactivity at surfaces. This book was constructed to be a resource to all scientists interested in the chemical reactivity of metals, including those whose primary interest may lie in fields outside surface reactivity. The book is'intended to be an advanced case study text, not a "review" in the standard sense. Each chapter develops principles and illustrates the use of experimental methods. Consequently, more attention is given to experimentation than normally found in journal articles or review articles. My intent in organizing these chapters was to make this field accessible to professionals and graduate students in the fields of chemistry, material science, and physics. Even so, we hope that experts in the field of surface reactivity will also find these chapters informative. After the introduction (Chap. 1) the book consists of chapters on the mechanism of selective oxidation by silver (Chap. 2 by R.1. Madix and J.T. Roberts), desulfurization (Chap. 3 by CM. Friend), alkyne cyclization (Chap. 4 by R.M. Lambert and R.M. Ormerod), and organic rearrangements on alumi num (Chap. 5 by L.H. Dubois, B.E. Bent and R.G. Nuzzo). In each of these chapters illustrations of the use of isotopic labelling, temperature programmed reaction spectroscopy, photoelectron spectroscopies and vibrational spectro scopy in dissecting complex surface reaction processes are presented. Where possible, the relationships between the heterogeneous reactions studied and the counterparts in homogeneous chemistry are discussed. Whereas the first four chapters address the important issue of molecular rearrangements and the elementary bond-breaking and bond-forming reactions that occur, Chapters 6 and 7 are concerned with the dynamics and kinetics of activated adsorption. Chapter 7 (by H.A. Michelson, C.T. Rettner and D.J. Auerbach) concerns the activated adsorption of dihydrogen on copper - the surface analogue ofH + H2 in the gas phase-from both the state integrated and VI Preface state-to-state viewpoints. The book concludes with a discussion of the activated adsorption of alkanes (Chapter 7 by c.B. Mullins and W.H. Weinberg). It is my pleasure to thank all the contributors to this volume. I am also grateful to Springer-Verlag for their interest in publishing this book and to Professor Robert Gomer for inviting it. Finally, all of us owe thanks to the many scientists who have contributed significantly to the rapid growth of this field to those who laid the foundation for modern surface chemical physics and chemistry through the development of the many methods in use today. Stanford, April 1994 R.J. Madix Contents 1. Introduction R.J. Madix 1 References . . 3 2. The Problem of Heterogeneously Catalyzed Partial Oxidation: Model Studies on Single Crystal Surfaces R.J. Madix and J.T. Roberts (With 27 Figures) . . . . . . 5 2.1 Modes of Oxygen Chemisorption on Metal Surfaces 6 2.2 Reactions of Molecularly Chemisorbed Oxygen . 13 2.3 Reactions of Atomically Chemisorbed Oxygen. . . 16 2.3.1 Atomic Oxygen as a NUcleophile on Silver. . 17 2.3.2 Atomic Oxygen as a Bmnsted Base on Silver 19 2.3.3 Addition of Atomic Oxygen to Carbon-Carbon Double Bonds on Silver. . . . . . . 38 2.3.4 Generalization to Other Metals . . 43 2.4 Conclusion . 49 References . . . . . . . . . . . . . . . . . . . . . 50 3. Desulfurization Reactions Induced by Transition Metal Surfaces C.M. Friend (With 16 Figures) . . . . . . . . . . . . . . . . . 55 3.1 Background. . . . . . . . . . . . . . . . . . . . . . . . . . . 55 3.2 The Reactions of Thiols on Transition-Metal Surfaces . 58 3.2.1 Spectroscopic Identification and Characterization. 58 3.2.2 Structural Studies of Adsorbed Intermediates 66 3.2.3 Chemical Probes of the Mechanism . . . . . . . . . 72 3.2.4 Coverage Dependence of Reactivity . . . . . . . . . 76 3.3 Desulfurization of Cyclic Sulfur-Containing Molecules' . 76 3.4 Conclusions. . . . . . . . . . 85 References and Notes. . . . . . . . . . . . . . . . . . . . . 86 4. Tricyclisation and Heterocyclisation Reactions of Ethyne over Well-Defined Palladium Surfaces R. M. Lambert and R.M. Ormerod (With 26 Figures) . 89 4.1 Background. . . . . . . . . . . . . . . . . . . . . . . 89 VIII Contents 4.2 Mechanistic Studies of Ethyne Tricyclisation . . . . . . . . . 90 4.2.1 Molecular Beam Results, Temperature-Programmed Reaction and Isotope Labelling: Molecular Formula of the Reaction Intermediate . . . . . . . . . 90 4.2.2 Characterisation of the C4H4 Intermediate. . . . . . . 95 4.2.3 The Reactively Formed Benzene is Tilted: Effect of Surface Packing Density on the Conformation, Yield and Desorption Kinetics of Benzene Formation. . . . . . . . . . . . . . . . . . . 100 4.3 Studies at High Pressures . . . . . . . . . . . . . . . . . . . . 105 4.4 The Effects of Promoters, Poisons and Othel Coa dsorbed Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 4.5 The Structure and Bonding of Ethyne Chemisorbed on Transition Metal Surfaces . . . . . . . . . . . . . . 113 4.6 Why is Tricyclisation so Specific to Palladium and Why is the (111) Plane so Strongly Favoured? . 122 4.7 Other Cyclisation Reactions. 127 4.8 Conclusions. 131 References . . . . . . . . . . . . . . 131 5. Model Organic Rearrangements on Aluminum Surfaces L.H. Dubois, B.E. Bent, and RG. Nuzzo (With 21 Figures) 135 5.1 Background. . . . . . . . . . . . . . . 135 5.2 Carbon-Halogen Bond Cleavage . . . . . . . . . . . . . 138 5.2.1 Reactive Sticking Probability. . . . . . . . . . . . 138 5.2.2 High-Resolution EELS and TPRS Observations of C-X Bond Cleavage. . . . . . . . . 141 5.3 Integrated Desorption Mass Spectrometry 147 5.4 Alkyl Surface Chemistry . . . . . . . . 149 5.4.1 Iodoalkanes with p-Hydrogens. . . . 152 5.4.2 Dihaloalkanes. . . . . . . . . . . . . . . 160 5.4.3 Radical Participation in Aluminum Alkyl Chemistry. 172 5.5 Etching of Aluminum Surfaces with Alkyl Halides. 174 5.6 Model and Real Systems: A Comparison . . . . . 175 5.7 Aluminum Surfaces vs. Aluminum Compounds: A Summary. . . . 179 5.8 Conclusion. . . . 180 References and Notes 181 6. The Adsorption of Hydrogen at Copper Surfaces: A Model System for the Study of Activated Adsorption H.A. Michelsen, C.T. Rettner, and D.l. Auerbach (With 34 Figures). . . . . . 185 6.1 Introductory Remarks . . . . . . . . . .. . . . 185 Contents IX 6.2 A One-Dimensional Description: The Translational Degree of Freedom. . . . . . . . . . . . . . . . . . . . . . . . . . 190 6.2.1 The Activation Barrier. . . . . . . . . . . . . . . . 190 6.2.2 Early Adsorption Measurements with Molecular Beams. . . . . . . . . . . . . . . . . . . . . . . . . . 193 6.2.3 Early Desorption Measurements and Detailed Balance. 194 6.3 A Two-Dimensional Description: The Translational and Vibrational Degrees of Freedom 198 6.3.1 The 2-D Potential Energy Surface. . . . . . . . . . 198 6.3.2 Recent Adsorption Measurements with Molecular Beams. . . . . . . . . . . . . . . . . . . . . . . . . . . 201 6.3.3 Quantitative Treatment of Adsorption and Desorption Data. . . . . . . . . . . . . . . . . . . . . . . . . . . 208 a) Sticking Probability Models. . . . . . .. . . . . 209 b) Quantitative Comparison of Adsorption Data. 212 c) Desorption and the Role of Surface Motion 213 6.3.4 State-Resolved Scattering Measurements. 220 a) Reflection Probability Measurements 220 b) Inelastic Scattering Measurements: Vibrational Excitation . . . . . . . . . 221 6.3.5 State-Resolved Desorption Measurements: So(v,EJ via Detailed Balance . . . . . . . . . . . . . . . . . . . . . . 224 6.4 A Multidimensional Description: The Degrees of Freedom Including Translation, Vibration, Rotation, Molecular Orientation, and Impact Parameter. . . . . . . . . . 228 6.4.1 Theoretical Descriptions for More than Two Dimensions . . . . . . . . . . . . . . . . . . . 228 6.4.2 Activation Energy Measurements: The Effect of Rotation on Adsorption Rate. 229 6.4.3 State-Resolved Desorption Measurements: The Role of Rotation in Adsorption and Desorption. 229 6.4.4 Inelastic Scattering Measurements: The Influence of Rotation on Vibrational Excitation 233 6.5 Summary . 234 References. . . . . . . . . . . . . . . . . . . . . 235 7. Kinetics and Dynamics of Alkane Activation on Transition Metal Surfaces c.B. Mullins and W.H. Weinberg (With 26 Figures). 239 7.1 Background. . . . . . . . . . . . . . . . . . . . . . 239 7.2 Trapping-Mediated Dissociative Chemisorption. 249 7.2.1 Trapping Dynamics. . . . . . . . . . 250 7.2.2 Kinetics. . . . . . . . . . . . . . . . . 255 7.2.3 Microscopic Reaction Mechanism. 265 X Contents 7.3 Direct Dissociative Chemisorption. 267 7.3.1 Activation via Translational Energy. 268 7.3.2 Activation via Vibrational Energy. 271 7.3.3 Collision-Induced Activation . 273 References . 275 Subject Index . 279
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