Chapter 1 | Nanoparticle Surfaces Studied by Electrochemical NMR | |
I. | Introduction | 1 |
II. | Experimental | 4 |
III. | Results and Discussion | 5 |
1. | Selected Topics in [superscript 195]Pt-NMR | 5 |
2. | Other Pt Nanoparticles (Unsupported and Supported) | 7 |
3. | Correlation Between the [superscript 195]Pt NMR Shift and Adsorbates Electronegativity | 9 |
4. | Spatially-Resolved Oscillation of the E[subscript f]-LDOS in a Pt Catalyst | 14 |
IV. | [superscript 13]C NMR at the Electrochemical Interface | 17 |
1. | [superscript 13]C NMR Knight Shift | 17 |
2. | EC-NMR Under Potential Control | 18 |
3. | Correlation of NMR to FTIR Data | 20 |
4. | Correlation Between Clean Surface E[subscript f]-LDOS of Metals and the Adsorbate Knight Shift | 22 |
5. | NMR Comparison of CO Adsorbed on Pt-Black from Different Sources | 25 |
6. | Effect of Surface Charge on the Chemisorption Bond: CO Chemisorption on Pd | 27 |
7. | Pt Electrodes Modified by Ruthenium: A Study in Tolerance | 29 |
8. | EC-NMR of Pt/Ru Alloy Nanoparticles | 37 |
V. | Summary and Conclusions | 40 |
| Appendix | 42 |
| References | 48 |
Chapter 2 | Ab Initio Quantum-Chemical Calculations in Electrochemistry | |
I. | Introduction | 51 |
II. | Ab Initio Quantum Chemistry | 54 |
1. | General Aspects of Quantum Chemistry and Electronic Structure Calculations | 54 |
2. | Wave-Function-Based Methods | 56 |
3. | Density Functional Theory Methods | 57 |
4. | Basis Sets and Effective Potentials | 60 |
5. | Structure, Energetics, and Vibrational Frequencies | 61 |
6. | Methods of Analysis | 61 |
7. | Ab Initio Molecular Dynamics | 63 |
III. | Selected Applications | 64 |
1. | Clusters and Slabs | 64 |
2. | How to Model the Electrode Potential | 65 |
3. | Chemisorption of Halogens and Halides | 67 |
4. | Chemisorption of Carbon Monoxide on Metals and Alloys | 78 |
5. | Field Dependent Chemisorption and the Interfacial Stark Effect: General Relationships | 88 |
6. | Field-Dependent Chemisorption of Carbon Monoxide | 98 |
7. | Chemisorption of Water and Water Dissociation Products | 106 |
8. | Ab Initio Approaches to Modeling Electrode Reactions | 115 |
IV. | Outlook | 125 |
| References | 127 |
Chapter 3 | Macroscopic and Molecular Models of Adsorption Phenomena on Electrode Surfaces | |
I. | Introduction | 131 |
II. | Features of Electrosorption and Factors Affecting Them | 132 |
III. | Macroscopic Models | 136 |
1. | PC Approach | 136 |
2. | STE Approach | 138 |
IV. | Molecular Models | 140 |
1. | Guidealli's Approach | 140 |
2. | Models Based on the LBS Approach | 145 |
V. | Complicated Adsorption Phenomena | 153 |
1. | Co-Adsorption and Reorientation | 153 |
2. | Polylayer Formation | 161 |
3. | Surface Segregation | 164 |
4. | Phase Transitions | 166 |
VI. | Polarization Catastrophe and Other Artifacts | 171 |
VII. | The Role of the Metal Electrode--The Case of Solid Electrodes | 177 |
VIII. | Computer Simulation | 182 |
IX. | Conclusions | 184 |
| References | 185 |
Chapter 4 | Electrochemical Promotion of Catalysis | |
I. | Introduction | 191 |
II. | The Phenomenon of Electrochemical Promotion | 193 |
1. | Description of a Typical Electrochemical Promotion Experiment | 194 |
2. | The Mechanism of Electrochemical Promotion | 197 |
3. | Promotional Transients | 203 |
III. | Fundamental Studies of Electrochemical Promotion | 207 |
1. | Catalytic Model Systems | 207 |
2. | Experimental Aspects | 209 |
3. | Electrochemical Characterization of the Single-Pellet Cell | 212 |
4. | Cyclic Voltammetry | 216 |
5. | Fast-Galvanostatic Transients | 219 |
6. | Permanent Electrochemical Promotion | 224 |
7. | Electrochemical Activation of a Catalyst | 228 |
8. | Electrochemical Promotion and Catalyst-Support Interactions | 230 |
9. | Work Function Measurements | 233 |
IV. | Cell Development for Electrochemical Promotion | 236 |
1. | Bipolar Con guration for Electrochemical Promotion | 236 |
2. | Ring-Shaped Electrochemical Cell | 241 |
3. | Multiple-Channel Electrochemical Cell | 244 |
4. | Perspectives | 248 |
V. | Conclusions | 250 |
| References | 252 |
Chapter 5 | Mechanisms of Lithium Transport Through Transition Metal Oxides and Carbonaceous Materials | |
I. | Introduction | 255 |
II. | Bird's Eye View of the Models for Current Transients in Lithium Intercalation Systems: Diffusion Controlled Lithium Transport | 257 |
1. | The Geometry of the Electrode Surface | 259 |
2. | The Growth of a New Phase in the Electrode | 260 |
3. | The Electric Field in the Electrode | 261 |
III. | General Perspective on Current Transients from Transition Metal Oxides and Graphite | 261 |
1. | Non-Cottrell behavior throughout the Lithium Intercalation/Deintercalation | 264 |
2. | Intersection of Anodic and Cathodic Current Transients | 267 |
3. | (Quasi-)Current Plateau | 268 |
4. | Depression of the Initial Current Value | 273 |
IV. | Physical Origin of the Current Transients | 273 |
1. | Linear Relation Between Current and Electrode Potential | 273 |
2. | Comparison of Cell Resistances Determined by the Current Transient Technique and by Electrochemical Impedance Spectroscopy | 278 |
V. | Theoretical Description of Cell-Impedance Controlled Lithium Transport | 283 |
1. | Governing Equation and Boundary Condition | 283 |
2. | Calculation Procedure of the Cell-Impedance Controlled Current Transients | 284 |
3. | Theoretical Current Transients and their Comparison with Experimental Current Transients | 286 |
4. | Some Model Parameters Affecting the Shape and Magnitude of the Cell-Impedance Controlled Current Transients | 294 |
VI. | Concluding Remarks | 297 |
| References | 298 |
| Index | 303 |