Diffraction and Spectroscopic Methods in Electrochemistry

This ninth volume in the series concentrates on in situ spectroscopic methods and combines a balanced mixture of theory and applications, making it highly readable for chemists and physicists, as well as for materials scientists and engineers. As with the previous volumes, all the chapters continue the high standards of this series, containing numerous references to further reading and the original literature, for easy access to this new field. The editors have succeeded in selecting highly topical areas of research and in presenting authors who are leaders in their fields, covering such diverse topics as diffraction studies of the electrode-solution interface, thin organic films at electrode surfaces, linear and non-linear spectroscopy as well as sum frequency generation studies of the electrified solid-solution interface, plus quantitative SNIFTIRS and PM-IRRAS. Special attention is paid to recent advances and developments, which are critically and thoroughly discussed.
The result is a compelling set of reviews, serving equally well as an excellent and up-to-date source of information for experienced researchers in the field, as well as as an introduction for newcomers.

Auteur

Richard C. Alkire is Professor Emeritus of Chemical & Biomolecular Engineering Charles and Dorothy Prizer Chair at the University of Illinois, Urbana, USA. He obtained his degrees at Lafayette College and University of California at Berkeley. He has received numerous prizes, including Vittorio de Nora Award and Lifetime National Associate award from National Academy.

Dieter M. Kolb is Professor of Electrochemistry at the University of Ulm, Germany. He received his undergraduate and PhD degrees at the Technical University of Munich. He was a Postdoctoral Fellow at Bell Laboratories, Murray Hill, NJ, USA. He worked as a Senior Scientist at the Fritz-Haber-Institute of the Max-Planck-Society, Berlin and completed his habilitation at the Free University of Berlin, where he also was Professor. Prof. Kolb has received many prizes and is a member of several societies.

Jacek Lipkowski is Professor at the Department of Chemistry and Biochemistry at the University of Guelph, Canada. His research interests focus on surface analysis and interfacial electrochemistry. He has authored over 120 publications and is a member of several societies, including a Fellow of the International Society of Electrochemistry.

Philip N. Ross has recently retired from his position as a Senior Scientist at the Lawrence Berkeley National Laboratory. He received his academic degrees at Yale University, New Haven, CT, and University of Delaware, Newark, DL. He has received the David C. Grahame Award of the Electrochemical Society, and is a member of several Committees and Advisory Boards.

Contenu

Series Preface V

Volume Preface XV

List of Contributors XVII

1 In-situ X-ray Diffraction Studies of the Electrode/Solution Interface 1
Christopher A. Lucas and Nenad M. Markovic

1.1 Introduction 1

1.2 Experimental 2

1.3 Adsorbate-induced Restructuring of Metal Substrates 4

1.3.1 Surface Relaxation 5

1.3.1.1 Pt Monometallic and Bimetallic Surfaces 5

1.3.1.2 Group IB Metals 12

1.3.2 Surface Reconstruction 16

1.4 Adlayer Structures 22

1.4.1 Anion Structures 23

1.4.2 CO Ordering on the Pt(111) Surface 28

1.4.3 Underpotential Deposition (UPD) 31

1.5 Reactive Metals and Oxides 36

1.6 Conclusions and Future Directions 41

Acknowledgments 42

References 42

2 UV-visible Reflectance Spectroscopy of Thin Organic Films at Electrode Surfaces 47
Takamasa Sagara

2.1 Introduction 47

2.2 The Basis of UV-visible Reflection Measurement at an Electrode Surface 49

2.3 Absolute Reflection Spectrum versus Modulated Reflection Spectrum 50

2.4 Wavelength-modulated UV-visible Reflectance Spectroscopy 53

2.5 Potential-modulated UV-visible Reflectance Spectroscopy 54

2.6 Instrumentation of the Potential-modulated UV-visible Reflection Measurement 55

2.7 ER Measurements for Redox-active Thin Organic Films 57

2.8 Interpretation of the Reflection Spectrum 62

2.9 Reflection Measurement at Special Electrode Configurations 65

2.10 Estimation of the Molecular Orientation on the Electrode Surface 68

2.10.1 Estimation of the Molecular Orientation on the Electrode Surface using the Redox ER Signal 69

2.10.2 Estimation of the Molecular Orientation on the Electrode Surface using the Stark Effect ER Signal 72

2.11 Measurement of Electron Transfer Rate using ER Measurement 73

2.11.1 Redox ER Signal in Frequency Domain 73

2.11.2 Examples of Electron Transfer Rate Measurement using ER Signal 76

2.11.3 Improvement in Data Analysis 78

2.11.4 Combined Analysis of Impedance and Modulation Spectroscopic Signals 79

2.11.5 Upper Limit of Measurable Rate Constant 82

2.11.6 Rate Constant Measurement using an ER Voltammogram 82

2.12 ER Signal Originated from Non-Faradaic Processes a Quick Overview 83

2.13 ER Signal with Harmonics Higher than the Fundamental Modulation Frequency 84

2.14 Distinguishing between Two Simultaneously Occurring Electrode Processes 85

2.15 Some Recent Examples of the Application of ER Measurement for a Functional Electrode 87

2.16 Scope for Future Development of UV-visible Reflection Measurements 91

2.16.1 New Techniques in UV-visible Reflection Measurements 91

2.16.2 Remarks on the Scope for Future Development of UV-visible Reflection Measurements 92

Acknowledgments 93

References 93

3 Epi-fluorescence Microscopy Studies of Potential Controlled Changes in Adsorbed Thin Organic Films at Electrode Surfaces 97
Dan Bizzotto and Jeff L. Shepherd

3.1 Introduction 97

3.2 Fluorescence Microscopy and Fluorescence Probes 99

3.3 Fluorescence near Metal Surfaces 100

3.4 Description of a Fluorescence Microscope for Electrochemical Studies 101

3.4.1 Microscope Resolution 103

3.4.2 Image Analysis 104

3.5 Electrochemical Systems Studied with Fluorescence Microscopy 106

3.5.1 Adsorption of C18OH on Au(111) 108

3.5.2 The Adsorption and Dimerization of 2-(2_-Thienyl)pyridine (TP) on Au(111) 114

3.5.3 Fluorescence Microscopy of the Adsorption of DOPC onto an Hg Drop 115

3.5.4 Fluorescence Microscopy of Liposome Fusion onto a DOPC-coated Hg Interface 118

3.5.5 Fluorescence Imaging of the Reductive Desorption of an Alkylthiol SAM on Au 120

3.6 Conclusions and Future Considerations 122

Structures and Abbreviations 123

Acknowledgments 124

References 124 **4 Linear and Non-linear Spectr...