Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry 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 international board of publishers in conjunction with the NATO Scientific Affairs Division A LHe 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 IG Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo Series C: Mathematical and Physical Sciences -Vol. 320 Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry edited by C. Gutierrez Instituto de Qufmica Ffsica "Rocasolano", C.S.I.C., Madrid, Spain and C. Melendres Argonne National Laboratory, Argonne, Illinois, U.S.A. Springer Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute an Spectroc:opic and Diffraction Techniques in Interfaaal Electrochemistry Puerta de la Cruz, Tenerife, Spain July 3-15,1988 Ubrary of Congress Cataloglng-in~Publlcation Data NATO Advanced Stuay Institute on SpectroscoplC and Dlffractlon Technlques In InlerfaClz1 Electroche.,stry 11968 Puerto de la Cru2. Can,ry !sllnds) Spectroscop'C 'nd dlffr~CI'on tachnlques In Interflclal electroche",stry I edlted Oy C. Gut llrrez and C. Melendres. p. C • . -- (NATO ASI serles. Ser les C. Matheutlc,l and physlcal sClences ; o. fdfffhj320e)fISBN 978-94-011-3782-9 (eBook) -Proceedlngs of Ihe NATO Advanced Study Institute on SplctrO$coplC and Dlffractlen Technlques In !nterhclal EleCtrocheMlstry. Puerte de la Cruz, hnerlfr. Sp"n, 3-15 ..July 1988." Includes blbl,o!iraphlcal referlnces ana IndeK. ISBN 978-94-010-5684-7 ISBN 978-94-011-3782-9 (eBook) DOI 10.1007/978-94-011-3782-9 1. i:lectrochu,stry--Con!iresses. 2. Surface chellstry -Congresses. 3. Spectrul analysls--Cen!iresses. 4. Olffract ion- -Congresses. 1. Gut,errez. C. (Claudlo). 1942- Il. Melendres. C. (Cules). 1939- III. T,tle. IV. Tltle, InterfiClil e lectrocne .. ,stry. V. Ser les. 00551.N36 1988 541.3·7--oc20 90-5353 ISBN 978-94-010-5684-7 Printed on acid-free paper AII Rights Reserved © 1990 Springer Science+Busincss Media Dordrecht Origina11y published by Kluwer Academic Publishers in 1990 Softcover reprint of the hardcover 1 st edition 1990 No part 01 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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .v ii List of Participants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................i x List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .xv The Advancing Frontier in the Knowledge of the Structure of Interphases J. O'M. Bockris and A. Gonzalez Martin. ................................1 Some Recent Spectroscopic Approaches to the Solid-Solution Interface J. O'M. Bockris and M. Gamboa Aldeco ..................................5 5 Application to Electrocatalysis of EMIRS (Electrochemically Modulated Infrared Reflectance Spectroscopy) and Related Techniques B. Beden. ..................................................... 103 Photoacoustic Spectroscopy and the In-Situ Characterization of the Electrochemical Interface C. E. Vallet. ................................................... 133 Raman Spectroscopic Techniques in Interfacial Electrochemistry R K. Chang. ................................................... 155 Laser Raman Spectroscopy in Studies of Corrosion and Electrocatalysis C. A. Melendres. .................................................1 81 UV- Visible Reflectance Spectroscopy in Electrochemistry W. Plieth. ..................................................... 223 Study of Anodic Oxides by UV-Visible Potential-Modulated Reflectance Spectroscopy C. Gutierrez. ................................................... 261 vi Nonlinear Optical Techniques for Surface Studies Y. R. Shen. .................................................... 281 X-Ray Diffraction at the Electrode-Solution Interface J. Robinson .....................................................3 13 X-Ray Reflectivity and Surface Roughness B. M. Ocko .....................................................3 43 Surface Structural Investigations by Electron Diffraction Techniques D.M. Kolb, G. Lehmpfuhl and M. S. Zei ................................. 361 Auger Electron Spectroscopy and the Electrochemical Interface D. J. Aberdam. ................................................. 383 Photoelectron Spectroscopy (xpS and UPS) of Electrode Surfaces R. Katz ....................................................... 409 Rutherford Backscattering Spectroscopy of Electrode Surfaces R. Katz ....................................................... 439 Electrochemical Applications of Scanning Tunneling Microscopy A. J. Arvia. .................................................... 449 Subject index ................................................... .471 PREFACE Electrochemistry is one of the oldest branches of Physical Chemistry. Having its foundations in the work of Faraday, Arrhenius and others, it evolved from the study of transport in electrolyte solutions to that of electrode kinetics. Kinetic methods are inherently unable to identify unequivocally the species involved in a reaction. Therefore, beginning in the 70s many spectroscopic and diffraction techniques were applied to the study of the electrode-electrolyte interface, in order to identify intermediary reaction species, and even the spatial arrangement of atoms or molecules at the interface. In order to disseminate these techniques, a NATO Advanced Sutdy Institute was held at Puerto de la Cruz, Tenerife (Canary Islands, Spain) from July 2 to 15, 1988. The Institute consisted of tutorial type lecutures, poster sessions, and round-table discussions. It was attended by over 65 participants from NATO-member countries, and others from Argentina and Japan. In the present volume most of the lectures presented at the Institute have been collected. At least one chapter is devoted to each technique. Emphasis has been made on case studies, rather than theory, which can be found in textbooks and other publications. Our purpose in this book is to help the electrochemists uninitiated in spectroscopic methods to decide which techniques would be suitable for application to their particular problems. We thank all the lecturers who contributed to this volume, and even those UHPs (Unrepentant Habitual Procrastinators) who did not in spite of our urgings to do so. We greatly appreciate the many hours they spent in preparing their lectures and in after-hours discussions with the participants. We owe a great deal of gratitude to our local co-director, Prof. Arevalo, for his excellent organization of the local arrangements. It was our pleasure to have as company participants from so many lands. Finally, we thank the Scientific Affairs Division of NATO for their financial support. C. Gutierrez and C. A. Melendres vii LIST OF PARTICIPANTS ALBARELLI, Michael J. Baker Laboratory, Department of Chemistry, Cornell University, Ithaca, NY 14853, U.S.A. ANDERSON, Mark R. Department of Chemistry, University of Utah, Salt Lake City, UT 84112, U.S.A. ANDREU, Rafael. Depto. de QUimica Fisica, Fac. de Quimica, Universidad de Sevilla, 41012-Sevilla. Spain. BEREKET, Gozen. Dept. of Chemistry, Faculty of Arts and SCience, University of Anatolia, Turkey. CASADO GIMENEZ, Juan. Dept. of Physical Chemistry, Universidad Aut6noma de Barcelona, Bellaterra, Barcelona, Spain. CELDRAN, Raquel. Universidad Aut6noma de Madrid, F.3.cultad de Ciencias, Depto. Quimica, C-II, 28049 Madrid, Spain. CROUIGNEAU, Pierre. Laboratoire de Chimie I, UER Sciences, Universite de POitiers, 86022 Poitiers Cedex, France. DA SILVA, Rui. Faculdade de Engenharia, Universidade do Porto, 4000 Porto, Portugal EPPEL, Steve Department of Physics, Case Western Reserve University, Cleveland, OH 44106, U.S.A. ERBOLUKBAS, Aysen. Istanbul Universitesi Fen Fakultesi Fizik Bolumu, Vezneciler Istanbul, Turkey. ESKIKAYA, Tulay. Chemistry Dept., Istanbul Technical 82060 Istanbul, Turkey Uni~rersity, ix x FERNANDES, Joao. Instituto Superior Tecnico, Lab. Electroquimica, Universidade Tecnica de Lisboa, 1096 Lisboa Codex, Portugal. FERREIRA, Mario G.S. Depto. de Eng. Quimica, Instituto Superior Tecnica, Universidade Tecnica de Lisboa, 1096 Lisboa Codex, Portugal. FONSECA, Ines. Dept. of Chem., Faculty of Science of Lisbon, CECUL, R. da Escola Pol1teenica 58-1293 Lisboa Codex, Portugal. FONTANESI, Claudio. University of Modena, Dept. of Chemistry, Via Campi 183, 41100 Modena, Italy. GIORDANO, Cristina. INIFTA, Casilla de Correo 16, Sucursal 4, (1900) La Plata, Argentina. GOMEZ, Mercedes Depto. de Quimica, Facultad de Ciencias, C-II, Universidad Aut6noma de Madrid, 28049 Madrid, Spain. GOSLICH, Roland. Insttitut fUr Solarenergieforschung GmbH, Sokelant StraSe 5, D-3000 Hannover 1, West Germany. HANSEN, Galen J. Physics Dept., UMC 4415, Utah State University, I-ogan, UT 84322. USA. JAEGERMANN, Wolfram. Hahn-Meitner Institut, Glienicker Str. 100, D-1000 Berlin 39, West Germany. JEHOULET. Laboratoire des Surfaces et Interfaces, 13 rue de Toul, 59046 Lille Cedex, France. JIMENEZ FERRER, M. Isabel. Dpto. Fisiea Aplicada, Facultad de Ciencias, Ciudad Universitaria de Cantoblanco, 28049 Madrid. Spain. JUSTO, Maria Julia. L.N.E.T.!., Az. Lameiros, Est. Paco Lumiar, 1600 Lisboa, Portugal. KAUTEK, W.M. Laboratory for Chemical Surface Technologies, Federal Insitute for Materia.l;; Research, Unter den Eichen 87, D-1000 Berlin 45, West Germany xi KESSEL, Robert. Inst. of Physical Chemistry, Universitat Dusseldorf, D-4000 Dusseldorf, Universitatsstrasse I, Gebaude 26.32, West Germany. LARRAMONA, Gerardo Instituto de Quimica Fisica "Rocasolano", tSIC, Serrano, 119, 28006-Madrid, Spain. LA UERMANN, Iver. Institut fur Solarenergieforschung, SokelantstraBe 5, D-3000 Hannover I, West Germany. MAKKY, Wagih. Dept. of Electrical Engineering, University of Illinois, Chicago, IL 60680, U.S.A. MARASSI, Roberto. Dept. of Chemistry, University of Camerino, Via S. Agostino I, Italy. MARCO SANZ. Jose F. Instituto de Quimica Fisica "Rocasolano", CSIC, Serrano. 119, 28006-Madrid, Spain. MARTIN NEVSKAIA, Daniela. Dpto. Fisica Aplicada. Facultad de Ciencias, Ciudad Un1vers1tar1a de Cantoblanco, 28049 Madrid. Spain. McMAHON, John J. Dept. of Chemistry, Fordham University, Bronx, N.Y. 10458, U.S.A. MEISSNER, Dieter. Inst1tut fur Solarenergiesforschung, Sokelantstrasse 5, D-3000 Hannover 1, West Germany. MONTEIRO, Fernando J. Depto. de Engenharia Metalurgica, Universidade do Porto, Rua dos Bragas, 4099 Porto Codex, Portugal. MuLLER JEVENOIS, Carlos. Dpto. Quimica Fisica. Universidad de Barcelona, Marti i Franques I, 08028 Barcelona, Spain. OLLIER, Nathalie. Laboratoire d'Electrochimie Interfaciale (LEI), CNRS, 1, Place Aristide Briand, 92195 Meudon Principal Cedex, France. OZSAVASCI, Cenglz. Gazi Universitesi, Fen-Edebiyat Fakultesi, Kimya Boliimu, 06500 Teknikokullar, Ankara. Turkey.