Diffraction and Spectroscopic Methods in Electrochemistry

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.

• Series Preface VVolume Preface XVList of Contributors XVII1 In-situ X-ray Diffraction Studies of the Electrode/Solution Interface 1Christopher A. Lucas and Nenad M. Markovic1.1 Introduction 11.2 Experimental 21.3 Adsorbate-induced Restructuring of Metal Substrates 41.3.1 Surface Relaxation 51.3.1.1 Pt Monometallic and Bimetallic Surfaces 51.3.1.2 Group IB Metals 121.3.2 Surface Reconstruction 161.4 Adlayer Structures 221.4.1 Anion Structures 231.4.2 CO Ordering on the Pt(111) Surface 281.4.3 Underpotential Deposition (UPD) 311.5 Reactive Metals and Oxides 361.6 Conclusions and Future Directions 41Acknowledgments 42References 422 UV-visible Reflectance Spectroscopy of Thin Organic Films at Electrode Surfaces 47Takamasa Sagara2.1 Introduction 472.2 The Basis of UV-visible Reflection Measurement at an Electrode Surface 492.3 Absolute Reflection Spectrum versus Modulated Reflection Spectrum 502.4 Wavelength-modulated UV-visible Reflectance Spectroscopy 532.5 Potential-modulated UV-visible Reflectance Spectroscopy 542.6 Instrumentation of the Potential-modulated UV-visible Reflection Measurement 552.7 ER Measurements for Redox-active Thin Organic Films 572.8 Interpretation of the Reflection Spectrum 622.9 Reflection Measurement at Special Electrode Configurations 652.10 Estimation of the Molecular Orientation on the Electrode Surface 682.10.1 Estimation of the Molecular Orientation on the Electrode Surface using the Redox ER Signal 692.10.2 Estimation of the Molecular Orientation on the Electrode Surface using the Stark Effect ER Signal 722.11 Measurement of Electron Transfer Rate using ER Measurement 732.11.1 Redox ER Signal in Frequency Domain 732.11.2 Examples of Electron Transfer Rate Measurement using ER Signal 762.11.3 Improvement in Data Analysis 782.11.4 Combined Analysis of Impedance and Modulation Spectroscopic Signals 792.11.5 Upper Limit of Measurable Rate Constant 822.11.6 Rate Constant Measurement using an ER Voltammogram 822.12 ER Signal Originated from Non-Faradaic Processes – a Quick Overview 832.13 ER Signal with Harmonics Higher than the Fundamental Modulation Frequency 842.14 Distinguishing between Two Simultaneously Occurring Electrode Processes 852.15 Some Recent Examples of the Application of ER Measurement for a Functional Electrode 872.16 Scope for Future Development of UV-visible Reflection Measurements 912.16.1 New Techniques in UV-visible Reflection Measurements 912.16.2 Remarks on the Scope for Future Development of UV-visible Reflection Measurements 92Acknowledgments 93References 933 Epi-fluorescence Microscopy Studies of Potential Controlled Changes in Adsorbed Thin Organic Films at Electrode Surfaces 97Dan Bizzotto and Jeff L. Shepherd3.1 Introduction 973.2 Fluorescence Microscopy and Fluorescence Probes 993.3 Fluorescence near Metal Surfaces 1003.4 Description of a Fluorescence Microscope for Electrochemical Studies 1013.4.1 Microscope Resolution 1033.4.2 Image Analysis 1043.5 Electrochemical Systems Studied with Fluorescence Microscopy 1063.5.1 Adsorption of C18OH on Au(111) 1083.5.2 The Adsorption and Dimerization of 2-(2_-Thienyl)pyridine (TP) on Au(111) 1143.5.3 Fluorescence Microscopy of the Adsorption of DOPC onto an Hg Drop 1153.5.4 Fluorescence Microscopy of Liposome Fusion onto a DOPC-coated Hg Interface 1183.5.5 Fluorescence Imaging of the Reductive Desorption of an Alkylthiol SAM on Au 1203.6 Conclusions and Future Considerations 122Structures and Abbreviations 123Acknowledgments 124References 1244 Linear and Non-linear Spectroscopy at the Electrified Liquid/Liquid Interface 127David J. Fermín4.1 Introductory Remarks and Scope of the Chapter 1274.2 Linear Spectroscopy 1284.2.1 Total Internal Reflection Absorption/Fluorescence Spectroscopy 1284.2.2 Potential-modulated Reflectance/Fluorescence in TIR 1344.2.3 Quasi-elastic Laser Scattering (QELS) 1394.2.4 Other Linear Spectroscopic Studies at the Neat Liquid/Liquid Interface 1424.3 Non-linear Spectroscopy 1464.3.1 Second Harmonic Generation 1464.3.2 Vibrational Sum Frequency Generation 1514.4 Summary and Outlook 154Acknowledgments 157Symbols 157Abbreviations 158References 1595 Sum Frequency Generation Studies of the Electrified Solid/Liquid Interface 163Steven Baldelli and Andrew A. Gewirth5.1 Introduction 1635.1.1 Theoretical Background 1635.1.2 SFG Intensities 1645.1.3 Resonant Term 1655.1.4 Non-resonant Term 1665.1.5 Phase Interference 1675.1.6 Orientation Information in SFG 1685.1.7 Phase Matching 1695.1.8 Surface Optics 1695.1.9 Data Analysis Reference 1715.1.10 Experimental Designs 1725.1.11 Spectroscopy Cell 1735.2 Applications of SFG to Electrochemistry 1745.2.1 CO Adsorption 1765.2.1.1 Polarization Studies 1785.2.1.2 Potential Dependence 1785.2.1.3 CO on Alloys 1795.2.1.4 Solvent Effects 1805.2.2 Adsorption of upd and opd H 1805.2.3 CN on Pt and Au Electrodes 1805.2.3.1 CN/Pt 1805.2.3.2 CN/Au 1835.2.4 OCN and SCN 1835.2.5 Pyridine and Related Derivatives 1835.2.6 Dynamics of CO and CN Vibrational Relaxation 1855.2.7 Solvent Structure 1875.2.7.1 Nonaqueous Solvents 1875.2.7.2 Aqueous Solvents 1915.2.8 Monolayers and Corrosion 1935.3 Conclusion 193Acknowledgments 194References 1956 IR Spectroscopy of the Semiconductor/Solution Interface 199Jean-Noël Chazalviel and François Ozanam6.1 Introduction 1996.2 IR Spectroscopy at an Interface 2006.2.1 Basic Principles of IR Spectroscopy 2006.2.2 External versus Internal Reflection 2016.3 Practical Aspects at an Electrochemical Interface 2036.3.1 How Potential can Affect IR Absorption 2046.3.2 How to Isolate Potential-sensitive IR Absorption 2056.4 What can be Learnt from IR Spectroscopy at the Interface 2076.4.1 Vibrational Absorption of Interfacial and Double-Layer Species 2086.4.2 Vibrational Absorption of Species outside the Double-Layer 2116.4.3 Electronic Absorption 2136.5 Effect of Light Polarization in ATR Geometry 2176.5.1 Selection Rules for a Polarized IR Beam 2186.5.2 Case of Strongly Polar Species: LO-TO Splitting 2186.5.3 Polarization Modulation 2226.6 Dynamic Information from a Modulation Technique 2226.7 Case of Rough or Complex Interfaces 2246.7.1 Surface Roughness 2256.7.2 Composite Interface Films 2266.8 Conclusion 229References 2307 Recent Advances in in-situ Infrared Spectroscopy and Applications in Single-crystal Electrochemistry and Electrocatalysis 233Carol Korzeniewski7.1 Introduction 2337.2 Experimental 2347.2.1 Spectrometer Systems 2347.2.2 Spectrometer Throughput Considerations 2347.2.3 Detectors 2357.2.4 Signal-to-Noise Ratio Considerations 2367.2.5 Signal Digitization 2367.2.6 Signal Modulation and Related Data Acquisition Methods 2377.3 Applications 2387.3.1 Adsorption and Reactivity at Well-defined Electrode Surfaces 2387.3.1.1 Adsorption on Pure Metals 2387.3.1.2 Electrochemistry at Well-defined Bimetallic Electrodes 2417.3.2 SEIRAS 2447.3.3 Infrared Spectroscopy as a Probe of Surface Electrochemistryat Metal Catalyst Particles 2497.3.4 Nanostructured Electrodes and Optical Considerations 2537.3.5 Emerging Instrumental Methods and Quantitative Approaches 2547.3.5.1 Step-scan Interferometry 2547.3.5.2 Two-dimensional Infrared Correlation Analysis 2567.3.5.3 Quantitation of Molecular Orientation 2597.4 Summary 262Acknowledgments 263References 2638 In-situ Surface-enhanced Infrared Spectroscopy of the Electrode/Solution Interface 269Masatoshi Osawa8.1 Introduction 2698.2 Electromagnetic Mechanism of SEIRA 2718.3 Experimental Procedures 2738.3.1 Electrochemical Cell and Optics 2738.3.2 Preparation of Thin-film Electrodes 2768.4 General Features of SEIRAS 2798.4.1 Comparison of SEIRAS with IRAS 2798.4.2 Surface Selection Rule and Molecular Orientation 2818.4.3 Comparison of SEIRA and SERS 2848.4.4 Baseline Shift by Adsorption of Molecules and Ions 2858.5 Selected Examples 2878.5.1 Reactions of a Triruthenium Complex Self-assembled on Au 2888.5.2 Cytochrome c Electrochemistry on Self-assembled Monolayers 2908.5.3 Molecular Recognition at the Electrochemical Interface 2938.5.4 Hydrogen Adsorption and Evolution on Pt 2968.5.5 Oxidation of C1 Molecules on Pt 2988.6 Advanced Techniques for Studying Electrode Dynamics 3028.6.1 Rapid-scan Millisecond Time-resolved FT-IR Measurements 3028.6.2 Step-scan Microsecond Time-resolved FT-IR Measurements 3038.6.3 Potential-modulated FT-IR Spectroscopy 3088.7 Summary and Future Prospects 309Acknowledgments 310References 3109 Quantitative SNIFTIRS and PM IRRAS of Organic Molecules at Electrode Surfaces 315Vlad Zamlynny and Jacek Lipkowski9.1 Introduction 3159.2 Reflection of Light from Stratified Media 3169.2.1 Reflection and Refraction of Electromagnetic Radiation at a Two-phase Boundary 3179.2.2 Reflection and Refraction of Electromagnetic Radiation at a Multiple-phase Boundary 3239.3 Optimization of Experimental Conditions 3259.3.1 Optimization of the Angle of Incidence and the Thin-cavity Thickness 3279.3.2 The Effect of Incident Beam Collimation 3309.3.3 The Choice of the Optical Window Geometry and Material 3319.4 Determination of the Angle of Incidence and the Thin-cavity Thickness 3369.5 Determination of the Isotropic Optical Constants in Aqueous Solutions 3389.6 Determination of the Orientation of Organic Molecules at the Electrode Surface 3439.7 Development of Quantitative SNIFTIRS 3449.7.1 Description of the Experimental Set-up 3449.7.2 Fundamentals of SNIFTIRS 3479.7.3 Calculation of the Tilt Angle from SNIFTIRS Spectra 3489.7.4 Applications of Quantitative SNIFTIRS 3499.8 Development of Quantitative in-situ PM IRRAS 3569.8.1 Introduction 3569.8.2 Fundamentals of PM IRRAS and Experimental Set-up 3579.8.3 Principles of Operation of a Photoelastic Modulator 3609.8.4 Correction of PM IRRAS Spectra for the PEM Response Functions 3649.8.5 Background Subtraction 3669.8.6 Applications of Quantitative PM IRRAS 3689.9 Summary and Future Directions 373Acknowledgments 373References 37410 Tip-enhanced Raman Spectroscopy – Recent Developments and Future Prospects 377Bruno Pettinger10.1 General Introduction 37710.2 SERS at Well-defined Surfaces 37910.3 Single-molecule Raman Spectroscopy 38410.4 Tip-enhanced Raman Spectroscopy (TERS) 39110.4.1 Near-field Raman Spectroscopy with or without Apertures 39110.4.2 First TERS Experiments 39510.4.3 TERS on Single-crystalline Surfaces 40110.5 Outlook 40910.5.1 Recent Results 40910.5.2 New Approaches on the Horizon 409Acknowledgment 410References 411Subject Index 419

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