Advances in electrochemical science and engineering

Title:

Publication Information:

Weinheim : Wiley-VCH, 2006

Physical Description:

ISBN:

9783527313174

General Note:

Library has volume 9

Subject Term:

Electrochemistry

Electrochemical analysis

Added Author:

Alkire, R. C., 1941-

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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.

Author Notes

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.

Christopher A. Lucas and Nenad M. MarkovicTakamasa SagaraDan Bizzotto and Jeff L. ShepherdDavid J. FerminSteven Baldelli and Andrew A. GewirthJean-Noel Chazalviel and Francois OzanamCarol KorzeniewskiMasatoshi OsawaVlad Zamlynny and Jacek LipkowskiBruno Pettinger

Series Preface	p. V
Volume Preface	p. XV
List of Contributors	p. XVII
1 In-situ X-ray Diffraction Studies of the Electrode/Solution Interface	p. 1
1.1 Introduction	p. 1
1.2 Experimental	p. 2
1.3 Adsorbate-induced Restructuring of Metal Substrates	p. 4
1.3.1 Surface Relaxation	p. 5
1.3.1.1 Pt Monometallic and Bimetallic Surfaces	p. 5
1.3.1.2 Group IB Metals	p. 12
1.3.2 Surface Reconstruction	p. 16
1.4 Adlayer Structures	p. 22
1.4.1 Anion Structures	p. 23
1.4.2 CO Ordering on the Pt(111) Surface	p. 28
1.4.3 Underpotential Deposition (UPD)	p. 31
1.5 Reactive Metals and Oxides	p. 36
1.6 Conclusions and Future Directions	p. 41
Acknowledgments	p. 42
References	p. 42
2 UV-visible Reflectance Spectroscopy of Thin Organic Films at Electrode Surfaces	p. 47
2.1 Introduction	p. 47
2.2 The Basis of UV-visible Reflection Measurement at an Electrode Surface	p. 49
2.3 Absolute Reflection Spectrum versus Modulated Reflection Spectrum	p. 50
2.4 Wavelength-modulated UV-visible Reflectance Spectroscopy	p. 53
2.5 Potential-modulated UV-visible Reflectance Spectroscopy	p. 54
2.6 Instrumentation of the Potential-modulated UV-visible Reflection Measurement	p. 55
2.7 ER Measurements for Redox-active Thin Organic Films	p. 57
2.8 Interpretation of the Reflection Spectrum	p. 62
2.9 Reflection Measurement at Special Electrode Configurations	p. 65
2.10 Estimation of the Molecular Orientation on the Electrode Surface	p. 68
2.10.1 Estimation of the Molecular Orientation on the Electrode Surface using the Redox ER Signal	p. 69
2.10.2 Estimation of the Molecular Orientation on the Electrode Surface using the Stark Effect ER Signal	p. 72
2.11 Measurement of Electron Transfer Rate using ER Measurement	p. 73
2.11.1 Redox ER Signal in Frequency Domain	p. 73
2.11.2 Examples of Electron Transfer Rate Measurement using ER Signal	p. 76
2.11.3 Improvement in Data Analysis	p. 78
2.11.4 Combined Analysis of Impedance and Modulation Spectroscopic Signals	p. 79
2.11.5 Upper Limit of Measurable Rate Constant	p. 82
2.11.6 Rate Constant Measurement using an ER Voltammogram	p. 82
2.12 ER Signal Originated from Non-Faradaic Processes - a Quick Overview	p. 83
2.13 ER Signal with Harmonics Higher than the Fundamental Modulation Frequency	p. 84
2.14 Distinguishing between Two Simultaneously Occurring Electrode Processes	p. 85
2.15 Some Recent Examples of the Application of ER Measurement for a Functional Electrode	p. 87
2.16 Scope for Future Development of UV-visible Reflection Measurements	p. 91
2.16.1 New Techniques in UV-visible Reflection Measurements	p. 91
2.16.2 Remarks on the Scope for Future Development of UV-visible Reflection Measurements	p. 92
Acknowledgments	p. 93
References	p. 93
3 Epi-fluorescence Microscopy Studies of Potential Controlled Changes in Adsorbed Thin Organic Films at Electrode Surfaces	p. 97
3.1 Introduction	p. 97
3.2 Fluorescence Microscopy and Fluorescence Probes	p. 99
3.3 Fluorescence near Metal Surfaces	p. 100
3.4 Description of a Fluorescence Microscope for Electrochemical Studies	p. 101
3.4.1 Microscope Resolution	p. 103
3.4.2 Image Analysis	p. 104
3.5 Electrochemical Systems Studied with Fluorescence Microscopy	p. 106
3.5.1 Adsorption of C[subscript 18]OH on Au(111)	p. 108
3.5.2 The Adsorption and Dimerization of 2-(2[prime]-Thienyl)pyridine (TP) on Au(111)	p. 114
3.5.3 Fluorescence Microscopy of the Adsorption of DOPG onto an Hg Drop	p. 115
3.5.4 Fluorescence Microscopy of Liposome Fusion onto a DOPC-coated Hg Interface	p. 118
3.5.5 Fluorescence Imaging of the Reductive Desorption of an Alkylthiol SAM on Au	p. 120
3.6 Conclusions and Future Considerations	p. 122
Structures and Abbreviations	p. 123
Acknowledgments	p. 124
References	p. 124
4 Linear and Non-linear Spectroscopy at the Electrified Liquid/Liquid Interface	p. 127
4.1 Introductory Remarks and Scope of the Chapter	p. 127
4.2 Linear Spectroscopy	p. 128
4.2.1 Total Internal Reflection Absorption/Fluorescence Spectroscopy	p. 128
4.2.2 Potential-modulated Reflectance/Fluorescence in TIR	p. 134
4.2.3 Quasi-elastic Laser Scattering (QELS)	p. 139
4.2.4 Other Linear Spectroscopic Studies at the Neat Liquid/Liquid Interface	p. 142
4.3 Non-linear Spectroscopy	p. 146
4.3.1 Second Harmonic Generation	p. 146
4.3.2 Vibrational Sum Frequency Generation	p. 151
4.4 Summary and Outlook	p. 154
Acknowledgments	p. 157
Symbols	p. 157
Abbreviations	p. 158
References	p. 159
5 Sum Frequency Generation Studies of the Electrified Solid/Liquid Interface	p. 163
5.1 Introduction	p. 163
5.1.1 Theoretical Background	p. 163
5.1.2 SFG Intensities	p. 164
5.1.3 Resonant Term	p. 165
5.1.4 Non-resonant Term	p. 166
5.1.5 Phase Interference	p. 167
5.1.6 Orientation Information in SFG	p. 168
5.1.7 Phase Matching	p. 169
5.1.8 Surface Optics	p. 169
5.1.9 Data Analysis Reference	p. 171
5.1.10 Experimental Designs	p. 172
5.1.11 Spectroscopy Cell	p. 173
5.2 Applications of SFG to Electrochemistry	p. 174
5.2.1 CO Adsorption	p. 176
5.2.1.1 Polarization Studies	p. 178
5.2.1.2 Potential Dependence	p. 178
5.2.1.3 CO on Alloys	p. 179
5.2.1.4 Solvent Effects	p. 180
5.2.2 Adsorption of upd and opd H	p. 180
5.2.3 CN on Pt and Au Electrodes	p. 180
5.2.3.1 CN/Pt	p. 180
5.2.3.2 CN/Au	p. 183
5.2.4 OCN and SCN	p. 183
5.2.5 Pyridine and Related Derivatives	p. 183
5.2.6 Dynamics of CO and CN Vibrational Relaxation	p. 185
5.2.7 Solvent Structure	p. 187
5.2.7.1 Nonaqueous Solvents	p. 187
5.2.7.2 Aqueous Solvents	p. 191
5.2.8 Monolayers and Corrosion	p. 193
5.3 Conclusion	p. 193
Acknowledgments	p. 194
References	p. 195
6 IR Spectroscopy of the Semiconductor/Solution Interface	p. 199
6.1 Introduction	p. 199
6.2 IR Spectroscopy at an Interface	p. 200
6.2.1 Basic Principles of IR Spectroscopy	p. 200
6.2.2 External versus Internal Reflection	p. 201
6.3 Practical Aspects at an Electrochemical Interface	p. 203
6.3.1 How Potential can Affect IR Absorption	p. 204
6.3.2 How to Isolate Potential-sensitive IR Absorption	p. 205
6.4 What can be Learnt from IR Spectroscopy at the Interface	p. 207
6.4.1 Vibrational Absorption of Interfacial and Double-Layer Species	p. 208
6.4.2 Vibrational Absorption of Species outside the Double-Layer	p. 211
6.4.3 Electronic Absorption	p. 213
6.5 Effect of Light Polarization in ATR Geometry	p. 217
6.5.1 Selection Rules for a Polarized IR Beam	p. 218
6.5.2 Case of Strongly Polar Species: LO-TO Splitting	p. 218
6.5.3 Polarization Modulation	p. 222
6.6 Dynamic Information from a Modulation Technique	p. 222
6.7 Case of Rough or Complex Interfaces	p. 224
6.7.1 Surface Roughness	p. 225
6.7.2 Composite Interface Films	p. 226
6.8 Conclusion	p. 229
References	p. 230
7 Recent Advances in in-situ Infrared Spectroscopy and Applications in Single-crystal Electrochemistry and Electrocatalysis	p. 233
7.1 Introduction	p. 233
7.2 Experimental	p. 234
7.2.1 Spectrometer Systems	p. 234
7.2.2 Spectrometer Throughput Considerations	p. 234
7.2.3 Detectors	p. 235
7.2.4 Signal-to-Noise Ratio Considerations	p. 236
7.2.5 Signal Digitization	p. 236
7.2.6 Signal Modulation and Related Data Acquisition Methods	p. 237
7.3 Applications	p. 238
7.3.1 Adsorption and Reactivity at Well-defined Electrode Surfaces	p. 238
7.3.1.1 Adsorption on Pure Metals	p. 238
7.3.1.2 Electrochemistry at Well-defined Bimetallic Electrodes	p. 241
7.3.2 SEIRAS	p. 244
7.3.3 Infrared Spectroscopy as a Probe of Surface Electrochemistry at Metal Catalyst Particles	p. 249
7.3.4 A Nanostructured Electrodes and Optical Considerations	p. 253
7.3.5 Emerging Instrumental Methods and Quantitative Approaches	p. 254
7.3.5.1 Step-scan Interferometry	p. 254
7.3.5.2 Two-dimensional Infrared Correlation Analysis	p. 256
7.3.5.3 Quantitation of Molecular Orientation	p. 259
7.4 Summary	p. 262
Acknowledgments	p. 263
References	p. 263
8 In-situ Surface-enhanced Infrared Spectroscopy of the Electrode/Solution Interface	p. 269
8.1 Introduction	p. 269
8.2 Electromagnetic Mechanism of SEIRA	p. 271
8.3 Experimental Procedures	p. 273
8.3.1 Electrochemical Cell and Optics	p. 273
8.3.2 Preparation of Thin-film Electrodes	p. 276
8.4 General Features of SEIRAS	p. 279
8.4.1 Comparison of SEIRAS with IRAS	p. 279
8.4.2 Surface Selection Rule and Molecular Orientation	p. 281
8.4.3 Comparison of SEIRA and SERS	p. 284
8.4.4 Baseline Shift by Adsorption of Molecules and Ions	p. 285
8.5 Selected Examples	p. 287
8.5.1 Reactions of a Triruthenium Complex Self-assembled on Au	p. 288
8.5.2 Cytochrome c Electrochemistry on Self-assembled Monolayers	p. 290
8.5.3 Molecular Recognition at the Electrochemical Interface	p. 293
8.5.4 Hydrogen Adsorption and Evolution on Pt	p. 296
8.5.5 Oxidation of C1 Molecules on Pt	p. 298
8.6 Advanced Techniques for Studying Electrode Dynamics	p. 302
8.6.1 Rapid-scan Millisecond Time-resolved FT-IR Measurements	p. 302
8.6.2 Step-scan Microsecond Time-resolved FT-IR Measurements	p. 303
8.6.3 Potential-modulated FT-IR Spectroscopy	p. 308
8.7 Summary and Future Prospects	p. 309
Acknowledgements	p. 310
References	p. 310
9 Quantitative SNIFTIRS and PM IRRAS of Organic Molecules at Electrode Surfaces	p. 315
9.1 Introduction	p. 315
9.2 Reflection of Light from Stratified Media	p. 316
9.2.1 Reflection and Refraction of Electromagnetic Radiation at a Two-phase Boundary	p. 317
9.2.2 Reflection and Refraction of Electromagnetic Radiation at a Multiple-phase Boundary	p. 323
9.3 Optimization of Experimental Conditions	p. 325
9.3.1 Optimization of the Angle of Incidence and the Thin-cavity Thickness	p. 327
9.3.2 The Effect of Incident Beam Collimation	p. 330
9.3.3 The Choice of the Optical Window Geometry and Material	p. 331
9.4 Determination of the Angle of Incidence and the Thin-cavity Thickness	p. 336
9.5 Determination of the Isotropic Optical Constants in Aqueous Solutions	p. 338
9.6 Determination of the Orientation of Organic Molecules at the Electrode Surface	p. 343
9.7 Development of Quantitative SNIFTIRS	p. 344
9.7.1 Description of the Experimental Set-up	p. 344
9.7.2 Fundamentals of SNIFTIRS	p. 347
9.7.3 Calculation of the Tilt Angle from SNIFTIRS Spectra	p. 348
9.7.4 Applications of Quantitative SNIFTIRS	p. 349
9.8 Development of Quantitative in-situ PM IRRAS	p. 356
9.8.1 Introduction	p. 356
9.8.2 Fundamentals of PM IRRAS and Experimental Set-up	p. 357
9.8.3 Principles of Operation of a Photoelastic Modulator	p. 360
9.8.4 Correction of PM IRRAS Spectra for the PEM Response Functions	p. 364
9.8.5 Background Subtraction	p. 366
9.8.6 Applications of Quantitative PM IRRAS	p. 368
9.9 Summary and Future Directions	p. 373
Acknowledgments	p. 373
References	p. 374
10 Tip-enhanced Raman Spectroscopy - Recent Developments and Future Prospects	p. 377
10.1 General Introduction	p. 377
10.2 SERS at Well-defined Surfaces	p. 379
10.3 Single-molecule Raman Spectroscopy	p. 384
10.4 Tip-enhanced Raman Spectroscopy (TERS)	p. 391
10.4.1 Near-field Raman Spectroscopy with or without Apertures	p. 391
10.4.2 First TERS Experiments	p. 395
10.4.3 TERS on Single-crystalline Surfaces	p. 401
10.5 Outlook	p. 409
10.5.1 Recent Results	p. 409
10.5.2 New Approaches on the Horizon	p. 409
Acknowledgment	p. 410
References	p. 411
Subject Index	p. 419

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