Developments in electrochemistry science inspired by martin fleischmann ( PDFDrive com )

Developments in Electrochemistry Science Inspired by Martin Fleischmann Editors:  Derek Pletcher • Zhong-Qun Tian • David E Williams Developments in Electrochemistry Developments in Electrochemistry Science Inspired by Martin Fleischmann Editors DEREK PLETCHER Chemistry, University of Southampton, UK ZHONG-QUN TIAN State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, China DAVID E WILLIAMS School of Chemical Sciences, University of Auckland, New Zealand This edition first published 2014 © 2014 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988 All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic books Designations used by companies to distinguish their products are often claimed as trademarks All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners The publisher is not associated with any product or vendor mentioned in this book Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose It is sold on the understanding that the publisher is not engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom If professional advice or other expert assistance is required, the services of a competent professional should be sought The advice and strategies contained herein may not be suitable for every situation In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read No warranty may be created or extended by any promotional statements for this work Neither the publisher nor the author shall be liable for any damages arising herefrom Library of Congress Cataloging-in-Publication Data applied for A catalogue record for this book is available from the British Library ISBN: 9781118694435 Set in 10/12pt Times by Aptara Inc., New Delhi, India Contents List of Contributors Martin Fleischmann – The Scientist and the Person A Critical Review of the Methods Available for Quantitative Evaluation of Electrode Kinetics at Stationary Macrodisk Electrodes Alan M Bond, Elena A Mashkina and Alexandr N Simonov 2.1 DC Cyclic Voltammetry 2.1.1 Principles 2.1.2 Processing DC Cyclic Voltammetric Data 2.1.3 Semiintegration 2.2 AC Voltammetry 2.2.1 Advanced Methods of Theory–Experiment Comparison 2.3 Experimental Studies 2.3.1 Reduction of [Ru(NH3 )6 ]3+ in an Aqueous Medium 2.3.2 Oxidation of FeII (C5 H5 )2 in an Aprotic Solvent 2.3.3 Reduction of [Fe(CN)6 ]3− in an Aqueous Electrolyte 2.4 Conclusions and Outlook References Electrocrystallization: Modeling and Its Application Morteza Y Abyaneh 3.1 3.2 Modeling Electrocrystallization Processes Applications of Models 3.2.1 The Deposition of Lead Dioxide 3.2.2 The Electrocrystallization of Cobalt 3.3 Summary and Conclusions References Nucleation and Growth of New Phases on Electrode Surfaces Benjamin R Scharifker and Jorge Mostany 4.1 4.2 An Overview of Martin Fleischmann’s Contributions to Electrochemical Nucleation Studies Electrochemical Nucleation with Diffusion-Controlled Growth xiii 21 23 23 26 29 32 35 36 36 40 42 43 45 49 53 56 58 60 61 63 65 66 67 vi Contents 4.3 Mathematical Modeling of Nucleation and Growth Processes 4.4 The Nature of Active Sites 4.5 Induction Times and the Onset of Electrochemical Phase Formation Processes 4.6 Conclusion References 68 69 Organic Electrosynthesis Derek Pletcher 77 5.1 Indirect Electrolysis 5.2 Intermediates for Families of Reactions 5.3 Selective Fluorination 5.4 Two-Phase Electrolysis 5.5 Electrode Materials 5.6 Towards Pharmaceutical Products 5.7 Future Prospects References 79 80 84 85 87 88 90 91 Electrochemical Engineering and Cell Design Frank C Walsh and Derek Pletcher 95 6.1 Principles of Electrochemical Reactor Design 6.1.1 Cell Potential 6.1.2 The Rate of Chemical Change 6.2 Decisions During the Process of Cell Design 6.2.1 Strategic Decisions 6.2.2 Divided and Undivided Cells 6.2.3 Monopolar and Bipolar Electrical Connections to Electrodes 6.2.4 Scaling the Cell Current 6.2.5 Porous 3D Electrode Structures 6.2.6 Interelectrode Gap 6.3 The Influence of Electrochemical Engineering on the Chlor-Alkali Industry 6.4 Parallel Plate Cells 6.5 Redox Flow Batteries 6.6 Rotating Cylinder Electrode Cells 6.7 Conclusions References Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS): Early History, Principles, Methods, and Experiments Zhong-Qun Tian and Xue-Min Zhang 7.1 Early History of Electrochemical Surface-Enhanced Raman Spectroscopy 71 72 72 96 96 97 98 98 98 99 100 100 101 102 105 106 107 108 109 113 116 Contents 7.2 Principles and Methods of SERS 7.2.1 Electromagnetic Enhancement of SERS 7.2.2 Key Factors Influencing SERS 7.2.3 “Borrowing SERS Activity” Methods 7.2.4 Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy 7.3 Features of EC-SERS 7.3.1 Electrochemical Double Layer of EC-SERS Systems 7.3.2 Electrolyte Solutions and Solvent Dependency 7.4 EC-SERS Experiments 7.4.1 Measurement Procedures for EC-SERS 7.4.2 Experimental Set-Up for EC-SERS 7.4.3 Preparation of SERS Substrates Acknowledgments References Applications of Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS) Marco Musiani, Jun-Yang Liu and Zhong-Qun Tian vii 117 118 119 121 123 124 124 125 125 125 127 128 131 131 137 8.1 8.2 8.3 8.4 8.5 8.6 Pyridine Adsorption on Different Metal Surfaces Interfacial Water on Different Metals Coadsorption of Thiourea with Inorganic Anions Electroplating Additives Inhibition of Copper Corrosion Extension of SERS to the Corrosion of Fe and Its Alloys: Passivity 8.6.1 Fe-on-Ag 8.6.2 Ag-on-Fe 8.7 SERS of Corrosion Inhibitors on Bare Transition Metal Electrodes 8.8 Lithium Batteries 8.9 Intermediates of Electrocatalysis Acknowledgments References 138 141 143 146 147 149 150 150 150 152 154 156 156 In-Situ Scanning Probe Microscopies: Imaging and Beyond Bing-Wei Mao 163 9.1 164 164 166 167 167 167 170 Principle of In-Situ STM and In-Situ AFM 9.1.1 Principle of In-Situ STM 9.1.2 Principle of In-Situ AFM 9.2 In-Situ STM Characterization of Surface Electrochemical Processes 9.2.1 In-Situ STM Study of Electrode–Aqueous Solution Interfaces 9.2.2 In-Situ STM Study of Electrode–Ionic Liquid Interface 9.3 In-Situ AFM Probing of Electric Double Layer 9.4 Electrochemical STM Break-Junction for Surface Nanostructuring and Nanoelectronics and Molecular Electronics 9.5 Outlook References 173 176 177 viii 10 Contents In-Situ Infrared Spectroelectrochemical Studies of the Hydrogen Evolution Reaction Richard J Nichols 10.1 The H+ /H2 Couple 10.2 Single-Crystal Surfaces 10.3 Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy 10.4 Surface-Enhanced Raman Spectroscopy 10.5 Surface-Enhanced IR Absorption Spectroscopy 10.6 In-Situ Sum Frequency Generation Spectroscopy 10.7 Spectroscopy at Single-Crystal Surfaces 10.8 Overall Conclusions References 11 12 13 183 183 184 186 189 190 193 194 197 198 Electrochemical Noise: A Powerful General Tool Claude Gabrielli and David E Williams 201 11.1 11.2 Instrumentation Applications 11.2.1 Elementary Phenomena 11.2.2 Bioelectrochemistry 11.2.3 Electrocrystallization 11.2.4 Corrosion 11.2.5 Other Systems 11.3 Conclusions References 202 204 204 205 207 209 215 217 217 From Microelectrodes to Scanning Electrochemical Microscopy Salvatore Daniele and Guy Denuault 223 12.1 The Contribution of Microelectrodes to Electroanalytical Chemistry 12.1.1 Advantages of Microelectrodes in Electroanalysis 12.1.2 Microelectrodes and Electrode Materials 12.1.3 New Applications of Microelectrodes in Electroanalysis 12.2 Scanning Electrochemical Microscopy (SECM) 12.2.1 A Brief History of SECM 12.2.2 SECM with Other Techniques 12.2.3 Tip Geometries and the Need for Numerical Modeling 12.2.4 Applications of SECM 12.3 Conclusions References 224 224 226 227 230 230 231 233 234 235 235 Cold Fusion After A Quarter-Century: The Pd/D System Melvin H Miles and Michael C.H McKubre 245 13.1 13.2 247 247 The Reproducibility Issue Palladium–Deuterium Loading Electrochemical Impedance Spectroscopy 363 the parameters obtained from the PDM optimization is shown in Figure 19.6b As seen from this figure, there is a linear dependence of log(Iss ) on the applied potential, which is consistent with the PDM diagnostic criteria for p-type passive films The parameters obtained from the PDM optimization listed in Tables 19.2 and 19.3 were used to calculate, theoretically, the steady-state properties (thickness and passive current density) of the barrier layer using Equations (19.16) and (19.45) In order to calculate the experimental steadystate thickness, the well-known parallel plate capacitance formula was used [Equation (19.46)], assuming a value of the capacitance from the high-frequency (1 kHz) imaginary part of the experimental impedance data C= 𝜀𝜀 ̃ d (19.46) where 𝜀̃ is the dielectric constant (calibrated based on the obtained thickness, 𝜀̃ = 724), 𝜀0 = 8.85 × 10−14 (in F cm−1 ) is the vacuum permittivity, d is the thickness of the film (in cm), and C is the capacitance (in F cm−2 ) As can be seen, the thickness of the barrier layer increases with applied potential, as predicted by the PDM [26] A good agreement was obtained between the calculated and experimental thickness, except at the lowest potential, which is closest to the active-to-passive transition (Figure 19.2); it is also possible that the barrier layer had not fully developed at that potential This postulate is somewhat supported by the fact that instabilities were observed in the impedance measurements at that potential 19.4 Summary and Conclusions In this chapter, the application of the point defect model for analyzing impedance data for passive metal systems has been detailed The feasibility of deriving an impedance version of the PDM, and of optimizing the model upon experimental impedance data to extract values for important model parameters, has also been demonstrated These, in turn, were used to calculate the steady-state barrier layer thickness and passive current density as a function of voltage These studies have provided a scientific basis for estimating the lifetimes of copper canisters in crystalline rock repositories in Sweden for the disposal of HLNW Acknowledgments In these studies the authors gratefully acknowledge the support of Stralsăakerhetsmyndigheten (SSM) of Sweden References (1) Abrantes, L., Fleischmann, M and Peter, L (1988) On the diffusional impedance of microdisc electrodes Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 256, 229– 233 364 Developments in Electrochemistry (2) Fleischmann, M., Pons, S and Daschbach, J (1991) The ac impedance of spherical, cylindrical, disk, and ring microelectrodes Journal of Electroanalytical Chemistry, 317, 1–26 (3) Chao, C.Y., Lin, L.F and Macdonald, D.D (1981) A point defect model for anodic passive films I Film growth kinetics Journal of The Electrochemical Society, 128, 1187– 1194 (4) Lin, L.F., Chao, C.Y and Macdonald, D.D (1981) A point defect model for anodic passive films II Chemical breakdown and pit initiation Journal of The Electrochemical Society, 128, 1194–1198 (5) Chao, C.Y., Lin, L.F and Macdonald, D.D (1982) A point defect model for anodic passive films III Impedance response Journal of The Electrochemical Society, 129, 1874–1879 (6) Macdonald, D.D (1999) Passivity – the key to our metals-based civilization Pure and Applied Chemistry, 71, 951–978 (7) Macdonald, D.D (2006) On the existence of our metals-based civilization Journal of The Electrochemical Society, 153, B213 (8) Song, H and Macdonald, D.D (1991) Photoelectrochemical impedance spectroscopy I Validation of the transfer function by Kramers–Kronig transformation Journal of The Electrochemical Society, 138, 1408–1410 (9) Macdonald, D.D., Sikora, E., Balmas, M.W and Alkire, R.C (1996) The photo-inhibition of localized corrosion on stainless steel in neutral chloride solution Corrosion Science, 38, 97– 103 (10) Urquidi, M and Macdonald, D.D (1985) Solute–vacancy interaction model and the effect of minor alloying elements on the initiation of pitting corrosion Journal of The Electrochemical Society, 132, 555–558 (11) Zhang, L and Macdonald, D.D (1998) Segregation of alloying elements in passive systems – I XPS studies on the Ni–W system Electrochimica Acta, 43, 2661–2671 (12) Macdonald, D.D and Smedley, S.I (1990) An electrochemical impedance analysis of passive films on nickel(111) in phosphate buffer solutions Electrochimica Acta, 35, 1949–1956 (13) Macdonald, D.D and Urquidi-Macdonald, M (1985) Application of Kramers–Kronig transforms in the analysis of electrochemical systems I Polarization resistance Journal of The Electrochemical Society, 132, 2316–2319 (14) Urquidi-Macdonald, M., Real, S and Macdonald, D.D (1986) Application of Kramers–Kronig transforms in the analysis of electrochemical impedance data II Transformations in the complex plane Journal of The Electrochemical Society, 133, 2018–2024 (15) Ai, J., Chen, Y., Urquidi-Macdonald, M and Macdonald, D.D (2007) Electrochemical impedance spectroscopic study of passive zirconium Journal of The Electrochemical Society, 154, C52 (16) Macdonald, D.D and Sun, A (2006) An electrochemical impedance spectroscopic study of the passive state on Alloy-22 Electrochimica Acta, 51, 1767–1779 (17) Geringer, J., Taylor, M.L and Macdonald, D.D (2012) Predicting the steady state thickness of passive films with the point defect model in fretting corrosion experiments Proceedings, PRIME 2012; 222nd Electrochemical Society Meeting Pacific Rim Meeting on Electrochemical and Solid State Science, 7–12 October, Honolulu, Hawaii (18) DataFit, Oakdale Engineering www.oakdaleengr.com Accessed 11 February 2014 (19) Levenberg, K (1944) A method for the solution of certain problems in least squares Quarterly of Applied Mathematics, 2, 164 (20) Ellis 2: Complex curve fitting for one independent variable | IgorExchange (2012) Available at: http://www.igorexchange.com/project/gencurvefit (21) Băack, T and Schwefel, H.-P (1993) An overview of evolutionary algorithms for parameter optimization Evolutionary Computation, 1, 1–23 (22) King, F., Ahonen, L., Tax´en, C et al (2002) Copper corrosion under expected conditions in a deep geologic repository Swedish Nuclear Fuel Waste Management Company Report, SKB TR 01-23, 2001 Posiva Oy Rep POSIVA 2002-01 (23) King, F (2013) Container materials for the storage and disposal of nuclear waste Corrosion, 69, 986–1011 Electrochemical Impedance Spectroscopy 365 (24) King, F., Lilja, C and Văahăanen, M (2013) Progress in the understanding of the long-term corrosion behaviour of copper canisters Journal of Nuclear Materials, 438, 228–237 (25) Kosmulski, M (2010) Surface Charging and Points of Zero Charge, CRC Press-Taylor & Francis Group, Boca Raton, FL (26) Macdonald, D.D., Biaggio, S.R and Song, H (1992) Steady-state passive films interfacial kinetic effects and diagnostic criteria Journal of The Electrochemical Society, 139, 170– 177 Index References to tables are given in bold type References to figures are given in italic type AC voltammetry, 32–5 advantages over DC voltammetry, 34 data analysis, 34 experimental studies aprotic oxidation of ferrocene, 40–2 aqueous reduction of hexamineruthenium(III), 36–8, 39–40 aqueous reduction of hexacyanoferrate(III), 42–3 future developments, 44–5 improvements, 44 sinusoidal, 33 square wave, 33 theory-experiment comparison, 35–6 acetic acid, 229 acetonitrile, 85, 316–17 acrylonitrile, 78–9, 85, 229 active sites, 67–8, 69–70 adaptive grids, 29 adiponitrile, 78–9 alamethicin, 205 alkali metals, 119 alkenes, 80 alkyl bromides, 80 alkyl halides, 80 alkynes, 80 anthraquinone, 79 antibiotics, 89 aprotic solvents, 40–2, 85 aqueous solutions, 167 arc plasmas, 310 aryl borates, 319, 319 arylpropionic acids, 88 atomic force microscopy (AFM), 68–9, 163, 164 chemical sensitivity, 176 electric double layer, 170–3 principle of operation, 166–7 SECM and, 232 band gap, 335 Bardeen perturbation, 164 BASF, 101, 102 beaker cells, 90 benzimidazole, 148 benzoquinones, 81 benzotriazole (BTAH), 147–8, 149, 152, 153 benzyl alcohol, 324 benzyl chloride, 154–5 benzylamine, 148 bioelectrochemistry, 205–7 biphasic systems, 85–6 bipolar cell stacks, 99 4, 4’-bipyridine (BPY), 174 bismuth film electrodes, 227 Bockris, John, Developments in Electrochemistry: Science Inspired by Martin Fleischmann, First Edition Edited by Derek Pletcher, Zhong-Qun Tian and David E Williams © 2014 John Wiley & Sons, Ltd Published 2014 by John Wiley & Sons, Ltd 368 Index Boltzmann function, 334 BP Statistical Review of World Energy, 331 break junction, 173–6 bromide adlayer adsorption, 268 bubble evolution, 215 Butler-Volmer parametrization, 24 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4 ), 168 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIBF6 ), 171–3 calorimetry, 249–50, 254–6 data integration, 252–4 carbon dioxide, 316, 316–17, 324–5 carbon fibers, 227 carbon nanotubes, 303, 305 carboxylation, 324 Carlisle, Anthony, 183 catalysis, 303 Ceftibuten, 89 cell design, 96 cell current scaling, 100 cell potential, 96–7 divided and undivided, 98–9 interelectrode gap, 101–2 monopolar and bipolar electrode connections, 99–100 parallel plates, 105–6 porous 3D electrodes, 100–1 redox flow batteries, 106–7 rotating cylinder electrode, 107–8 strategic decisions, 98 X-ray diffraction, 263 X-ray scattering, 266, 267 cell potential, 96–7 cerium(IV), 79 charge transfer, 295–6 electron transfer, 299–300 hydrogen evolution reaction, 302–3 ion transfer, 296–8 micro- and nano- interfaces, 304–5 oxygen reduction reaction (ORR), 300, 301–2 photoinitiated, 299–300 semiconductors, 337 chemical change rate, 97–8 chemical mechanical polishing, 282 chemically irreversible systems see irreversible systems, 25–6 chlor-alkali production, 102–3, 104 chlorine, 102–3 plasma, 310 chronoamperometry, 224 cobalt, 57–8, 58, 60–1, 170 electrocrystallization, 57–8, 58, 60–1 cobalt-chromium-molybdenum (CoCrMo) alloy, 291 coinage metals, 118, 146, 167 cold fusion, 5, 245 calorimetric issues, 249–54 palladium-deuterium loading, 247–9 present status, 257–8 reaction products, 256–7 tritium, 256–7 reproducibility, 247, 247–9 COMSOL Multiphysics, 233 Condensed Matter Nuclear Science, 246, 258 Conway, Brian, copper, 175 corrosion inhibition, 147–9, 149 deposition from supercritical fluids, 322 electrodes 167 electroplating additives, 146 lithium batteries, 154 pyridine reduction on, 139 SERS, 118 copper ions, 229 corrosion, 147–8 erosion, 213–14 monitoring, 287–90 erosion-corrosion, depassivation, 284–5 hip joints, 291–2 iron, 149–50, 152 noise analysis, 209–15 self-generated potential fluctuations, 209–10 stainless steel, 209–12 stress corrosion cracking, 213 tribocorrosion, 281–2 de- and repassivation, 283–4 Index cracking, 213 crystal truncation rods, 264, 269 current noise, 203, 204 current scaling, 100 current-time characteristics electrocrystallization, 54–5, 56 lead dioxide, 58–60 cyclic voltammetry, 298 data analysis, 43 data processing, 26–9, 43 modeling, 28–9 double-layer capacitance, 27–8 experimental studies aprotic oxidation of ferrocene, 40–2 aqueous reduction of hexacyanoferrate(III), 42 aqueous reduction of hexamineruthenium(III), 37–8 flames, 312–13, 313 irreversible systems, 25–6 look-up tables, 26 microelectrodes, 224–5 principles, 23–6 semi-integration, 29–32 see also AC voltammetry cyclobutane derivatives, 86 cyclohexane, 78, 86 cylinder in pipe cells, 101 cytochrome oxidase, 301–2 decamethylferrocene, 301, 321 density functional theory (DFT), 139, 139–40, 155 depassivation, 283–5, 284–6 Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, 171 deuterium oxide, 245 Dewar calorimeters, 249–50 diamond microelectrodes, 227 diamond substrates, 62 diaphragm cells, 103 𝛼-𝛼-dibromo-1,2-dialkylbenzenes, 81 differential pulse voltammetry, 298 diffusion, 22, 226 nonplanar, 31–2 diffusion-controlled growth, 67–8 369 difluoromethane, 321 DigiElch, 28, 35, 235 DigiSim, 28 dimensionally stable anodes, 89, 103 1,2-dimethoxyethane, 85 1,2-di(pyridin-4-yl)ethene (BPY-EE), 174 Dished Electrode Cell, 105 double-layer capacitance, 21–2, 27–8 Eco-cells, 107 edge diffusion effects, 32, 34, 38 electric double layer, 167 atomic force microscopy, 170–3 ionic liquids, 171–2 Electrocatalytic/EA Technology, 105 Electrocell, 105 electrochemical calorimetry, 249–50 Electrochemical Kinetics, 66 electrochemical noise analysis see noise analysis electrochemical step edge decoration (ESED), 70 electrocrystallization, 49–53 cobalt, 57–8, 58, 60–1 current-time characteristics, 54–5, 56, 57, 58 diamond substrates, 62 electrode coverage by depositing phase, 50–1 first-order nucleation law, 61–2 lead dioxide, 58–60 modeling, 53–6 3D models, 54–5 monolayer formation, 53–4, 60–1 noise analysis, 207–9 nucleation, 49–50, 65–6 free energy, 49–50 electrodes electrical connections, 99–100 enhancement factors, 101 interelectrode gap, 101–2 iron and silver, 150 macrodisk, 25 microelectrodes, 227 organic electrosynthesis, 87–8 370 Index electrodes (Continued) platinum, 191–2 porous, 100–2 reference, 312 electrolysis, 77 drawbacks, 90 electrolyte solutions, for EC-SERS, 125 electron energy loss spectroscopy (EELS), 197, 261 electron transfer, 21, 299–300 Bulmer-Volmer parametrization, 23–4 in plasmas, 312–13 water splitting, 343–4 electron-hole recombination, 338–9 electronic tongues, 227–8 electroplating additives, 146–7 ElectroSyn, 105 electrosynthesis, 78 Electrosynthesis Co., 89 energy consumption, chlor-alkali production, 102–4 energy storage, 106–7 enhancement factors, 101 erosion, 213–14, 282–3 models and mapping, 287–9 monitoring, 290–1 repassivation, 286–7 extended semi-integrals, 32 Faraday cages, 203 Fast Fourier Transform (FFT), 203 fast-scan voltammetry, 224–5 fenoprofen, 89 Fermi levels, 334 splitting, 339–41 Fermi-Dirac function, 334 ferrocene, 40–2, 301 ferrocene carboxylic acid, 321 ferromagnetic metals, 170 film over nanosphere, 130–1 filter press design, 101 flame plasmas, 310–14 reference electrodes, 312 Fleischmann, Martin, 1–5, 23, 49, 77, 95, 143–4, 235 areas of contribution, cold fusion, 245–6 see also cold fusion microelectrodes, 223, 224 noise, 202 nucleation, 66–7 organic electrosynthesis, 77 soft interfaces, 295 X-ray diffraction, 261–3 contributions cold fusion, 245–6 see also cold fusion X-ray diffraction, 261–3 early career, 2–3 early life, family, later life, publications, 5–19 biological science, 16 cold fusion, 16–17 electrochemical nucleation, 5–8 equipment design, 10 microelectrodes, 10–12 nuclear magnetic resonance, organic electrochemictry, 12–14 quantum electrodynamics, 17 surface-enhanced Raman spectroscopy, 8–9 X-ray techniques, 10 Fleischmann-Pons heat effect, 245, 246 calorimetric examples, 254–6 electrochemical calorimetry, 249–50 numerical integration, 252–4 palladium-deuterium loading, 247–9 reaction products, 256 helium-4, 256 tritium, 256–7 reproducibility, 247 calorimetry, 249–50 fluorination, 84–5 fluorosulfonic acid, 78 FM01-LC, 105–6 FM21 electrolyser, 105 focused ion beam (FIB), 289 food analysis, 227–8 force curves, 166, 171–2, 172 N-formylpyrrolidine, 90 Index Fourier transform, 32 Fourier transform AC voltammetry, 39–40, 44–5 frequency domain noise analysis, 203 Frumkin isotherm, 192 Fuoss-Kraus equation, 319 gelatin, 208 germanium, 323 Gibbs energy, 72, 205, 297 glassy carbon, 72 glassy carbon (GC), 37, 50 glycosyl cation, 82 gold, 272–3 electrodes ionic liquids, 168–9 scanning tunneling microscopy, 167 electroplating additives, 146 liquid mirrors, 305 nanoparticles, 121, 305 pyridine reduction on, 139 SERS, 118 water adsorption, 143 Gouy-Chapman-Stern model, 171 graphene, 303 green chemistry, 79, 90, 324 harpoon mechanisms, 297 heat-after-death, 254–5 helium-4, 256 hematite, 343–5, 344 Hendra, Pat, heterocyclic compounds, 83 hexacyanoferrate(III), 42 hexamineruthenium(III), 36–40, 43 highly ordered pyrrolytic graphite (HOPG), 70 hole transport, 340–5 hydrodynamics, 215 hydrofluorocarbons (HFC), 317 hydrogen adsorption, 275 hydrogen evolution reaction (HER), 183, 300, 332 at soft interfaces, 302–3 in-situ sum frequency generation spectroscopy (SFG), 193–4 371 noise, 205 platinum, 184 single-crystal surfaces, 184–6, 194–7 SNIFTIRS, 186–9 surface-enhanced IR absorption spectroscopy (SEIRAS), 190–3 surface-enhanced Raman spectroscopy (SERS), 189–90 hydrogen formation, 215 hydrogen oxidation reaction (HOR), 183 single-crystal surfaces, 194–5 hydrogen production, 305 HydroQuebec, 80 hydroxide film formation, 268–70 ibuprofen, 88 ICI, 105 imaging, 234 in-situ sum frequency generation spectroscopy (SFG), 193–4 indirect electrolysis, 79–80 indium tin oxide electrodes, 122 Instrumental Methods in Electrochemistry, 66 integration, 252–4 intensity-modulated photocurrent spectroscopy (IMPS), 344 interelectrode gap, 101–2, 102 International Society of Electrochemistry, inverse Fourier transform, 32 iodine, 202 ion adsorption, 268 ion transfer reactions, 296–8 assisted, 298 ion transfer voltammetry, 304 ion-permeable membranes, 96 ionic liquids, 85, 125, 167–8, 175 electric double layer, 171–2 ionophores, 295–6 iridium oxide, 228 iron, 175 corrosion, 149–50 iron electrodes, 153 iron trichloride, 170 372 Index irreversible systems, 25–6 isoperobolic calorimetry Jansson, Bob, 95 Johnson noise, 201–2 Johnson-Matthey, 247 Joint Center for Artificial Photosynthesis (JCAP), 334 joint implants, 291–2 jump-to-contact process, 174, 175 ketoprofen, 88 Kolbe reaction, 86 Kolmogorov-Johnson-Mehl-Avrami theory (KJMA), 68–9 Langevin equations, 205 lead, 87, 267 lead dioxide, 67, 72 electrocrystallization, 58–60 ligands, 298 lighting rod effect, 119 linear sweep voltammetry, 224 lipid bilayer membranes, 205–7 liquid mirrors, 305 lithium, 119 lithium batteries, 152–4 lithium-air batteries, 154 local density of states (LDOS), 164 low-energy electron diffraction (LEED), 261 Lugin capillary, 41 macrocycles, 80 macrodisk electrodes, 21–2, 25, 37 maltol, 84 Marcus-Hush theory, 24–5 martensite, 213 mass transport regime, 100 supercritical fluids, 315 variation using SECM, 234 material erosion, 285 May Electrochemical Society, 250 MECSim, 35 2-mercaptobenzoxazole, 148 mercury, 65, 72, 87, 267, 272–3 microelectrodes, 226, 227 metal-on-metal hip joints, 291–2 metallocenes, 302–3 see also ferrocene metastable pits, 210, 211 methanol, 316 methoxylation, 83, 84 methyl 2-methylcyclopent-1-enyl ketone, 78 methylene chloride, 78 methylene dichloride, 82 MH theory, 24–5 Michael reactions, 81 microdisc radius, 233 microelectrodes, 4, 223, 309 advantages, 224–6 applications, 224 food analysis, 227–8 arrays, 226 concentrated industrial liquors, 229–30 history, 223 materials, 226–7 nanoparticle detection, 228 stripping analysis, 225–6 tip geometries, 233 Microflow, 105 microholes, 305 micropipettes, 304 Mie theory, 305 Mitsubishi Heavy Industries, 257 mixing reactions, 305–7, 307 modeling, 28 erosion-corrosion, 287–9 ion transfer, 297 molecular junctions, 175 molybdenum carbide, 303 molybdenum disulfide, 303 Monash University, 35 monolayer formation, 60–1, 122 electrocrystallization, 53–4, 60–1 underpotential deposition, 270–5 X-ray diffraction, 262 monopolar cells, 99 Monsanto, 78 Index Nafion, 99, 103 nanoparticles, 121 detection using microelectrodes, 228 palladium, 303 platinum, 303 silver and gold, 305 nanoporous electrodes, 228–9 nanoscale structures, 321 nanosphere films, 129 nanostructuring, 173–6 naproxen, 88 napthalene, 79 napthaquinone, 79–80 Naval Air Warfare Center Weapons Division (NAWCWD), 247, 256 Nernst equation, 296, 299 neutrons, 257 New Hydrogen Energy, 250 Nicholson method, 26 Nicholson technique, 37–8, 42 Nicholson, William, 183 nickel, 67, 87, 268 nickel alloys, 150 𝛼-nickel hydroxide, 262 Nimrod, 35–6, 40 NIR Fourier transform SERS, 148 noise, 201–2 elementary phenomena, 204–5 instrumentation, 202–3 noise analysis bubble evolution, 215 corrosion, 209–15, 290 metastable pits, 212–13 stress corrosion cracking, 213 electrocrystallization, 207–9 fingerprinting, 208 hydrodynamics, 215 nonsteroidal antiinflammatory drugs (NSAID), 88 nucleation, 65 active sites, 69–70 atomistic theory, 66 classical theory, 65–6 diffusion-controlled growth, 67–8 Fleischmann’s contributions, 66–7 373 kinetics, 53–4, 67 concurrent processes and, 70 nucleus growth and nucleation rate, 70 speed, 54 nucleophiles, 82 Ohm’s law, 21 oblique incidence reflectivity difference (OI-RD), 69 olefins, 83, 86 ordered nanostructures, 129–30 organic compounds, 77–8 electrode materials, 87–8 future prospects, 90–1 methoxylation, 83 Michael addition, 81 pharmaceuticals, 88–90 reaction intermediates, 80–4 selective fluorination, 84–5 two-phase electrolysis, 85–6 osmium, 86 overparameterization, 44–5 overpotential, 337 overpotentially deposited copper, 322 overpotentially deposited hydrogen, 186, 195 oxidation/reduction cycles, 128–31 oxide film formation, 268–70 oxygen evolution reaction (OER), 332 oxygen production, 305 oxygen reduction reaction (ORR), 300, 301–2 palladium, 154–5, 175, 245, 247 deuterium loading, 247–8 nanoparticles, 303 palladium-boron cathodes, 254–5 Papyrex, 262 parallel plate cells, 105, 105–6 Parsons, Roger, particle-surface interactions, 283 passivity, 149–50 pattern recognition, 44 pencil sharpener cells, 89 Peter, Laurence, pharmaceutical products, 88–90 374 Index phenolphtalein, 250 Phillips process, 84 photoelectrolysis electron-hole recombination, 338–9 minority carrier reactions at semiconductor electrodes, 336–7 thermodynamics and kinetics, 334–6 photoelectrolysis cells (PEC), 332–3 photoinitiated reactions, 299–300 photovoltage, 335 physical vapor deposition, 129 picking-mode SECM, 231 pitting, 211–14 Placzek polarizability theory, 115 plasmas, 310–14 plasmonic materials, 118 plasmonics, 305 platinum, 65–6, 87, 140, 194 electrodes, 191–2 plasmas, 311 hydrogen evolution reaction (HER), 184 nanoparticles, 228 SERS, 119 SNIFTIRS, 195, 196 water adsorption, 143 Pletcher, Derek, 3–4 polarization potential, 203 poly(3,4-ethylenedioxythiophene), 86 polyaniline, 234 polycyclic compounds, 83 polymer electrolyte membrane (PEM) cell, 99, 276 poly(tetrafluoroethylene) (PTFE), 276 Pons, Stan, porous electrodes, 100 porphyrins, 301 positive feedback, 254 potassium ions, 268 potential, potential of zero charge (PZC), 124–5, 139, 168, 267 potentiometric microelectrodes, 223 potentiostats, 38, 66 Preparata, Giuliano, 246 pulse voltammetry, 32 pyridine, 117, 117, 124, 138–41, 150 quantum tunneling, 164 through-bond, 165–6 through-space, 165–6 Raman spectroscopy sensitivity, 137 see also surface-enhanced Raman scattering; tip-enhanced Raman spectroscopy ˇ cik relationship, 37, 38–9 Randles-Sevˇ reaction engineering, 96 reaction intermediates organic compounds, 80–4 surface-enhanced Raman spectroscopy, 154–6 reactor design, 96 reciprocal space, 265 redox flow batteries, 106–7, 108 reference electrodes, 312 Regenesys battery, 107, 108 repassivation, 286–7 rocking curve, 264–6, 265 room-temperature ionic liquids (RTIL), 167–8 ruthenium, 120–1 rutile, 332 scanning electrochemical microscopy (SECM) AC impedance and, 232–3 applications, 234 atomic force microscopy and, 232 direct mode, 230 history, 230–1 intermittent contact, 232 mass transport variation, 234 picking mode, 231 scanning ion conductance microscopy and, 232 shear force, 231–2 tip geometries, 233 tip position modulation, 231 Index scanning electron microscopy (SEM), 322 scanning ion conductance microscopy (SICM), 232 scanning tunneling microscopy (STM), 114 scanning tunneling microscopy (STM), 114, 163–4, 230 aqueous solutions, 167 chemical sensitivity, 176 jump-to-contact process, 174 principle of operation, 164–6 room-temperature ionic liquids (RTIL), 167–70 spatial resolution, 163–4 surface nanostructuring, 173–6 Schottky’s theorem, 202 Schwinger, Julian, 246 selective fluorination, 84–5 semi-integration, 29–32, 34, 38, 38–9 limitations, 31–2 semiconductors, 332, 332–4 charge transfer, 337 electron-hole recombination, 338–9 Fermi level splitting, 339–40 light-driven water splitting, 341–3 shear force SECM, 231 shell-isolated nanoparticle-enhanced Raman Spectroscopy (SHINERS), 123–4, 140 copper corrosion, 149 silicon wafers, 282 silicon-germanium, 323 silver, 72 electroplating additives, 146 iron corrosion and, 150 on iron electrodes, 151 nanoparticles, 121, 305 on platinum electrodes, 315 pyridine reduction on, 139 SERS, 118 water adsorption, 143 silver electrodes, 116, 153–4, 271 scanning tunneling microscopy, 167 silver nitrate, 315 silver sulfate, 67 375 simulations cyclic voltammetry, 28–9 quality of agreement, 29 ion transfer, 304 single-crystal surfaces, 184–6, 194–7 surface X-ray scattering (SXS), 275 SNPE, 88 sodium chloride, 103 sodium hydroxide, 103, 104 soft interfaces, 295–6 software, 28–9, 235 solar energy, 331 solar fuels, 331 solid-electrolyte interface, 152 solvents, 28, 125 Southampton Group, 3, 67, 78, 113 space charge layer, 337, 338 space-time yield, 100 square wave voltammetry, 32, 33 stainless steel, 209–10 staircase voltammetry, 24–5 standard hydrogen electrode (SHE), 299 stress corrosion cracking (SCC), 213 stripping analysis, 224–5, 225 substrate generation-tip collection, 230 subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS), 186–8, 195, 196 succinic acid, 175–6 sulfur, 197–8 sum frequency generation (SFG), 114, 193–4 supercritical fluids, 314–21, 316 applications, 321–2 critical temperatures, 316 definition, 314–15 early studies, 315–16 electrodeposition from, 321 transport properties, 315 supersaturation, 67–8 surface differential diffraction (SDD), 271, 305 surface nanostructuring, 173–6 surface plasmon resonance, 118 surface recombination, 339 376 Index surface water, 141–3 surface X-ray scattering (SXS), 266 high surface area electrodes, 275–7 interfacial water, 266–7 ion adsorption, 268 oxide/hydroxide formation, 268–70 single-crystal surfaces, 275 surface-enhanced IR absorption spectroscopy (SEIRAS), 190–3 surface-enhanced Raman spectroscopy (SERS), 4, 113, 114, 262–3 borrowed SERS activity, 121–3 distance dependence, 120–1 early history, 116–17 electrochemical double layer, 124–5 electrolyte solutions, 125 electromagnetic enhancement, 118–19 electroplating additives, 146–7 experimental setup, 127 hydrogen evolution reaction (HER), 189–90 interfacial water, 141–3 iron corrosion, 149–51 lithium batteries, 152–4 material dependence, 119 measurement procedures, 125–7 nanoparticle size and shape, 121 principles and methods, 117–18 pyridine, 117, 117 pyridine adsorption, 138–41 Raman intensity, 115 reaction intermediates, 154–6 SERS intensity, 118 substrate preparation, 128–31 surface enhancement factor, 117 thiourea and inorganic anion adsorption, 143–6 wavelength dependence, 119–20 surface-extended X-ray absorption fine structure (SEXAFS), 261 surfactants, 228 Symons process, 84 synchrotron, 264–6 Tafel extrapolation, 209 tantalum, 271 TEMPO, 80 tetrabutylammonium hexafluorophosphate, 318 tetrabutylammonium iodide, 316 tetrachlorohydroquinone, 301 tetracyanodimethane (TCNQ), 305 tetramethoxyfuranose, 83 5,10,15,20-tetraphenyl21H,23H-porphine, 301 tetrathiafulvalene, 305 thiourea, 125, 143–6, 146, 208 3D electrodes, 100–1 3DDC processes, 68–9, 208 tiaprofenic acid, 88 tip position modulation, 231 tip-enhanced Raman spectroscopy, 123, 177 titanium dioxide, 332, 335–6 tolyltriazole, 148 transition metals, 119 transmutation, 257 tribocorrosion, 281–2, 291–2 depassivation, 284–6 particle-surface reactions, 283 tritium, 256–7 tunneling electron microscopy, 289 tunneling see quantum tunneling tunneling current, 165 two-phase electrolysis, 85–6 ultrahigh vacuum (UHV), 185–6, 261 ultramicroelectrodes, 223 underpotential deposition, 122 hydrogen, 185, 197 lead on silver, 272–3 mercury on gold, 272 monolayers, 270–5 tantalum on silver, 271 United States Navy, 254 valinomycin, 298 Van der Walls forces, 166 Index vibrational spectroscopy, 177 vitreous carbon see glassy carbon Volmer-Tafel mechanism, 192 voltammograms, 24–5, 304 double-layer capacitance, 27–8 semi-integration, 31 waste products, 90 water, 141–3, 266–7 electrolysis, 183–4 supercritical, 316 water-splitting, 305 Williams, David, 4, W.R Grace & Co., 80 377 X-ray diffraction (XRD) early work, 262–3 electrode surfaces, 275–7 synchrotron-based, 264–6 X-ray photoelectron spectroscopy (XPS), 261 X-ray voltammograms (XRV), 268 X-rays, 257 XL200 cell, 107 yttria-stabilized zirconia, 312–13 zero gap cells, 101–2, 102 zinc oxide, 335 ... by the expression: ( ( ( ) )) F(E − E0 ) F(E − E0 ) Red Ox (t) ⋅ exp (1 − ? ?) ⋅ (t) ⋅ exp −