Nonequilibrium Processes in Catalysis PDF
Preview Nonequilibrium Processes in Catalysis
Nonequilibrium Processes in Catalysis Oleg V. Krylov, Prof., DSc. Laboratory of Heterogeneous Catalysis Institute of Chemical Physics Moscow, Russia Boris R. Shub, Prof., D.Sc. Laboratory of Nonequilibrium Processes in Catalysis Institute of Chemical Physics Moscow, Russia Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business First published 1994 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Reissued 2018 by CRC Press © 1994 by CRC Press, Inc. CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.cop- yright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Krylov, O. V. (Oleg Valentinovich) [Neravnovesnye protsessy v katalize. English] Nonequilibrium processes in catalysis / Oleg V. Krylov, Boris R. Shub. p. cm. Includes bibliographical references and index. ISBN 0-8493-4478-6 1. Catalysis. 2. Nonequilibrium thermodynamics. I. Shub, B. R. (Boris Ruvimovich) II. Title. QD505.K7913 1993 541.3’95--dc20 93-9504 A Library of Congress record exists under LC control number: 93009504 Publisher’s Note The publisher has gone to great lengths to ensure the quality of this reprint but points out that some imperfections in the original copies may be apparent. Disclaimer The publisher has made every effort to trace copyright holders and welcomes correspondence from those they have been unable to contact. ISBN 13: 978-1-315-89592-5 (hbk) ISBN 13: 978-1-351-07502-2 (ebk) Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com FOREWORD This book treats elementary surface processes and heterogeneous catalysis from the unique perspective of the authors. The Institute of Chemical Physics in Moscow has long been the center for research of gas-surface interactions and catalysis on oxide surfaces. The chapters reflect the knowledge gained by studies in both fields of research. During the past twenty years, development of modem surface science techniques has permitted investigation of surfaces on the molecular level. The information gained through studies of energy transfer between incident gas molecules and the surface, using molecular beam-surface scattering, has pro- vided a new view of elementary surface reaction processes that are also often important in heterogeneous catalytic reactions. Surface science approaches to the understanding of catalysis have been gaining prominence worldwide. This book provides this important surface science view of catalysis from the perspective of nonequilibrium, irreversible processes. G. A. Somorjai Berkeley, California PREFACE The study of nonequilibrium processes in catalysis gives us an insight into the mechanism of catalytic transformations. For any catalytic reaction the following stages are necessary: the energy gain that is needed for the activation, the chemical conversion itself, and ultimately, the loss of excess energy by reaction products. The processes of activation and deactivation of solids are also of importance. In the 1970s experimental and theoretical activity in this field began under our supervision at the Institute of Chemical Physics in Moscow. First results have been generalized in our collected volume, Problems in Kinetics and Catalysis, Volume 17, Nonstationary and Nonequilibrium Processes in Het- erogeneous Catalysis, edited by 0.V . Krylov and M. D. Shibanova, Nauka, Moscow, 1978 (in Russian). Since that time, an increasing number of new methods have made their appearance in catalytic research. An extensive growth of publications in the last few years requires a new overview of this subject. This book is devoted to experimental works and modem methods of investigating nonequilibrium processes in catalysis. The latter include the energy exchange between active species and a solid, and the appearance of nonequilibrium ("dissipative") structures in the solid itself. The thermo- dynamics of irreversible processes is applied to analyze possible catalyst transformations. The surface migration of adsorbed particles and its role in catalytic trans- formations, as well as chemoenergetic stimulation (i.e., the acceleration of a chemical reaction on account of excitation of intermediate reagents, being outputs of another reaction), are also considered in this book. We have sup- plemented the English edition with references up to 1992. The works per- formed at the Institute of Chemical Physics are covered in greatest detail. Because the subject under consideration is, undoubtedly, at the origin of its development and there is no consensus on many questions, some results have not yet received an adequate explanation. We hope that this book will be of interest to both academic and industrial scientists specializing in the field of adsorption and catalysis. We are indebted for any critical remarks from our readers. The authors are grateful to A. D. Berman, Ju. M. Gershenzon, V. F. Kiselev, S. A. Kovalevsky, M. A. Kozhushner, V. G. Kustarev, A. S. Prost- nev, Ju. N. Rufov, M. E. Ryskin, and A. V. Skljarov for many stimulating discussions on different problems presented in this book. 0. V. Krylov B. R. Shub Moscow, Russia THE AUTHORS Oleg V. Krylov, D.Sc., is a professor and principal researcher at the Laboratory of Heterogeneous Catalysis, Institute of Chemical Physics, Rus- sian Academy of Science, Moscow, Russia. Professor Krylov graduated in 1947 from the Ivanovo Institute of Chem- ical Engineering, Ivanovo, Russia, and received his Ph.D. degree in 1951 from the Institute of Physical Chemistry, Moscow and his D.Sc. degree in 1964 from the Institute of Chemical Physics, Moscow. Professor Krylov is a member of several scientific organizations: Inter- national Academy of Creative Endeavours, International Committee of the World Congresses on Catalytic Oxidation, Council of the International Con- gress on Catalysis, Presidium of the Council on Catalysis of Russia, and serves on the editorial boards of several scientific journals. Professor Krylov has presented over 30 invited lectures at international meetings, over 50 invited lectures at national meetings, and many guest lectures at universities and institutes. Professor Krylov has published more than 400 scientific papers and sev- eral books, many of them published in English. Among these titles are: 0. V. Krylov, Catalysis by Nonmetals. Rules for Catalyst Selection, Academic Press, 1970; V. F. Kiselev and 0. V. Krylov, Adsorption Processes on Semicon- ductor and Dielectric Su$aces I, Springer, 1984; V. F. Kiselev and 0. V. Krylov, Electronic Phenomena in Adsorption and Catalysis on Semiconduc- tors and Dielectrics, Springer, 1987; and V. F. Kiselev and 0. V. Krylov, Adsorption and Catalysis on Transition Metals and Their Oxides, Springer, 1989. His current major scientific interests are heterogeneous catalysis, ki- netics of heterogeneous processes, ecology, chemistry of natural gas, and petroleum refining. Boris R. Shub, DSc., Professor, is Head of the Laboratory of Non- equilibrium Processes in Catalysis at the Institute of Chemical Physics, Rus- sian Academy of Sciences, Moscow, Russia. Professor Shub graduated from the Moscow Institute of Fine Chemical Technology, Moscow, Russia, in 1962 and received his Ph.D. degree from the Institute of Chemical Physics, Moscow, in 1969 and D.Sc. degree from the lnstitute of Chemical Physics, Moscow, in 1983. Professor Shub is a member of several scientific bodies including the Scientific Council for Chemical Kinetics and Structure, and the Scientific Council for Catalysis. Professor Shub has presented over 10 invited lectures at international meetings, over 20 invited lectures at national meetings, and some guest lec- tures at universities and institutes. Professor Shub has won the S. Z. Roginsky Prize, and has published more than 100 scientific papers. His current scientific interests include physics and chemistry of heterogeneous processes and catalysis, dynamics of ele- mentary processes and surface spectroscopy, ecology, and aircraft thermal protection. TABLE OF CONTENTS Chapter 1. Introduction ................................................. 1 Chapter 2 . Research Methods ........................................... 9 2.1. Beam Methods ...................................... 10 2.1.1. Molecular Beams ........................... 10 2.1.2. Ion Beams .................................. 14 2.2. Laser Methods ....................................... 18 2.2.1. Identification of Gas-Phase Particles .................................... 18 2.2.2. Surface Investigations ...................... 23 2.3. Excited Molecule Deactivation Studied by Flow Methods ....................................... 24 Chapter 3 . Heterogeneous Deactivation of Excited Molecules ........- 29 3.1 . Heterogeneous Deactivation of Vibrationally Excited Molecules ..................... 29 3.1.1. Historical Review .......................... 29 3.1.2. Deactivation on Metal Surface ............. 36 3.1.3. Deactivation on Semiconductor Surface ..................................... 42 3.1.4. Deactivation on NaCl and TeflonB Surfaces .................................... 45 3.1.5. D, Deactivation on Molecular CO, Crystal Surface ............................. 46 3.2. Heterogeneous Deactivation of Electronically Excited Particles ...................... 55 3.2.1. Ar(3P,., ) Quenching on Quartz ............. 56 3.2.2. N, (A3Z:) Quenching on Quartz and Nickel .................................. 62 3.2.3. Quenching of Singlet Oxygen .............. 69 3.2.4. O,('A, ) Quenching on Pt Surface in the Course of Catalytic CO Oxidation: SDOSO Method ................ 79 3.3. Kinetic Mechanisms of Heterogeneous Deactivation of Excited Particles .................... 82 Chapter 4 . Interaction of Molecular Beams With Surface .............. 91 4.1. Dynamic Scattering of Molecular Beams and Desorbed Molecules ............................ 91 4.1. l . Monoenergetic Atomic Beams .............. 91 4.1.2. Monoenergetic Molecular Beams: Translational Energy Change (V,- T Exchange) During Scattering and Adsorption ............................. 92
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