ADVANCES I N CATALYSIS VOLUME 23 Advisory Board G. K. BORESKOV Novosibirsk, U.S.S.R. P. H. EMMETT Baltimore, Maryland M. BOUDART Stanford, California J. HORIUTI Sapporo, J a p a n G. NATTA E. K. RIDEAL Milan, Ztaly London, England H. S. TAYLOR Princeton, New Jersey M. CALVIN Berkeley, California W. JOST Gottingen, Germany P. W. SELWOOD Santa Barbara, California ADVANCES IN CATALYSIS VOLUME 23 Edited by D. D. ELEY The University iV ottingham, England HERMAN PINES Northwestern University Euanston, Illinois PAULB. WEISZ Mobil Research and Development Corporation Princeton, New Jersey 1973 ACADEMIC PRESS NEW YORK AND LONDON COPYRIGHT 0 1973, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED. N O PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WI T H O U T PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. 111 Fifth Avenue, New York, New York 10003 Unired Kingdom Edifion published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 Oval Road. London N W l LIBRARY OF CONGRESS CATALOG CARDNUMBER:49-7755 PRINTED IN TH E UNITED STATES O F AMERICA Contents CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . PREFACE ................................................................ vii ix Metal Catalyzed Skeletal Reactions of Hydrocarbons J. R. ANDERSON I. 11. 111. IV. V. VI. Introduction.. . . . . Catalyst Structure ....,........... 1 .......................... ......... 2 16 ....................... Isomerization and Dehydrocyclization 25 Hydrogenolysis on Metals. . . . . . , . . . . . . . . . . . . . . . _ . . . . . . . . . . . _ . . _ .62 Reactions over Chromium Oxide Catal 81 References. . . , , . . . . . , . . . . , . , . , , , , . . . . . . . . . . . . . . . . . . . . . . . . . 84 Specificity in Catalytic Hydrogenolysis by Metals J. H. SINFELT I. 11. 111. IV. V. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 General Discussion on Hydrogenolysis Reactions. . . . . . . . . . . . . . . . . . . . . . . 92 Comparison of Metals as Hydrogenolysis Catalysts. . . . . . . . . . . . . . . . . . . . . 97 Contrast between Ethane Hydrogenolysis and Other Reactions, . . . . . . . . . 106 116 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Chemisorption of Benzene R. B. MOYESAND P. B. WELLS I. 11. 111. IV. V. Introduction, . . . ....................... Chemisorption , , . . , , , , . , . , , , , , , , , . , , , . , , , . . . . . . . . . . . . . . . . . . . . . . . . . . 121 122 133 . . . . . . . . . . . . . . . . . 148 Some Aspects of Benzene Hydrogenation. . , . . 152 ......._........... Conclusions. . . . . . . . . . . . . . . . . . . . . . 154 References. . . The Electronic Theory of Photocatalytic Reactions on Semiconductors TH.WOLKENSTEIN Introduction, . , . . . . . . . , . , . , , , , , . , , . , . , . , . . , . . . . , . , . . . . . . . . . . . . . . . . . 157 I. The Mechanism of the Influence of Illumination on the Adsorption and Catalytic Properties of a Surface. . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 V vi I1. 111. IV . V. VI . CONTENTS The Photoadsorptive Effect .