N4-Macrocyclic Metal Complexes (eBook)

Contents 5
Preface 15
Contributors 17
Billion-Year-Old Oxygen Cathode that Actually Works: Respiratory Oxygen Reduction and its Biomimetic Analogs 19
1. The Basic Concepts of Energy Metabolism 19
2. Biological Catalysis of Respiratory Oxygen Reduction 23
3. Biomimetic Catalysis of O2 Reduction 30
4. Summary and Conclusions: Lessons of Biomimetic O2 Reduction for the Design of Fuel Cell Catalysts 50
Acknowledgments 53
References 54
Fundamental Aspects on the Catalytic Activity of Metallomacrocyclics for the Electrochemical Reduction of O2 59
1. Introduction 59
2. Reaction Pathways for the Reduction of Molecular Oxygen 60
3. Interaction of O2 with Active Sites and the Redox Mechanism 64
4. Two-Electron Reduction Catalysts for the Reduction of Molecular Oxygen 75
5. Four-Electron Reduction Catalysts 78
6. Conclusions 91
Ackowledgments 93
References 93
Oxygen Reduction in PEM Fuel Cell Conditions: Heat- Treated Non- Precious Metal- N4 Macrocycles and Beyond 101
1. Why Search for a Non-Pt Based Catalyst for the Reduction of O2 in PEM Fuel Cells? 101
2. Activity of Electrocatalysts based on Fe - N4 and Co - N4 Macrocycles and Beyond 106
3. Kinetic and Mechanistic Aspects of Electrochemical Oxygen Reduction 139
4. Important Factors for the Use of Non-Noble Metal Electrocatalysts in PEM Fuel Cells for Automotive Applications 148
5. Conclusions 155
Acknowledgments 157
References 157
Biomimetic NOx Reductions by Heme Models and Proteins 166
1. Introduction 166
2. Native Enzymes for NOx Reductions 168
3. Electrochemical Investigations of NOX Reduction 176
4. Conclusions 197
Acknowledgments 198
References 198
Electroreduction of CO2 Catalyzed By Metallomacrocycles 208
1. Introduction 208
2. Electroreduction of CO2 on Metallic Cathodes 210
3. Biphenantroline and Bypiridine Hexaazacyclophane Systems 212
4. Cyclam and Derivative Systems 221
5. Phthalocyanines and Porphyrins Complexes 237
6. Conclusions 260
Acknowledgments 261
References 261
Supramolecular Porphyrins as Electrocatalysts 272
1. Build-up of Supramolecular Porphyrins Based on Metal- Ligand Coordination 272
2. Synthesis and Characterization of Tetrametallated Pyridyl Porphyrins 282
3. Catalytic and Electrocatalytic Properties 295
4. Electrochemical and Photoelectrochemical Properties of Porphyrin Films 304
5. Final Remarks 318
References 319
Electrodes Modified with Monomeric M - N4 Catalysts for the Detection of Environmentally Important Molecules 332
1. Introduction 332
2. Phenols, Organohalides, and Pesticides 335
3. Thiols 339
4. Sulfur Dioxide and Sulfur Oxoanions 346
5. Carbon Dioxide/Carbon Monoxide 349
6. Nitrites and Nitrates 356
7. Cyanides/Thiocyanades 359
8. Hydrazine/hydroxylamine 359
9. Conclusions 364
10. Acknowledgment 364
References 364
Electropolymerized Metalloporphyrin, Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis 379
1. Introduction 379
2. The Electrochemical Polymerization Strategy 381
3. Design and Characterization of Electropolymerized Metalloporphyrin and Metallophthalocyanine Film 381
4. Electrocatalytic and Electroanalytic Applications of Electropolymerized N4- Macrocyclic- Based Films 424
5. Conclusions 438
Acknowledgements 439
References 439
Electron Transfer Processes of ß- Pyrrole Brominated Porphyrins: Structural vs. Electronic Effects 455
1. Introduction 455
2. Synthesis 458
3. Effect of the Br Substituents and Solvent Interactions on the UV- Visible Spectra 461
4. Electrochemical Behavior of ß-Pyrrole Brominated Metalloporphyrins 462
5. Spectroelectrochemical Studies of ß-Pyrrole Brominated Metalloporphyrins 469
6. Effect of the Br Substituents on Axial Ligand Binding 472
7. Summary 474
Acknowledgments 476
References 476
Photoelectrochemical Reactions at Phthalocyanine Electrodes 483
1. Introduction 483
2. Essentials of Photoelectrochemical Reactions 484
3. Photoelectrochemical Experiments at Phthalocyanine Thin Films 486
4. Sensitization of Oxide Semiconductors by Phthalocyanines 510
5. Technology Outlook 517
6. Acknowledgment 519
References 519
Organisation And Photoelectrochemical Reactivity of Water- Soluble Metalloporphyrins at the Liquid/ Liquid Interface 532
1. Introduction 532
2. The Polarisable Liquid/Liquid Interface 533
3. Basic Photophysics of Metalloporphyrins and Chlorins 538
4. Organisation of Water-Soluble Porphyrins at the Liquid/ Liquid Interface 547
5. Photoelectrochemical Reactivity at Porphyrin- Sensitised Liquid/ Liquid Interfaces 560
6. Concluding Remarks 581
Acknowledgements 582
References 582
Theoretical Insights on the Chemical Reactivity of MetalloPorphyrins Using Density Functional Theory 590
1. Introduction 590
2. Computational Details 596
3. The Chemical Effects Tuning the Reactivity of M( II)- N4 Complexes 597
4. Conclusions 612
Acknowledgements 613
References 613
Organized Multiporphyrinic Assemblies for Photoconduction and Electroconduction 617
1. Introduction 617
2. The Porphyrinic Chromophore 619
3. Scope and Limitations 637
4. Covalent Species 637
5. Noncovalent Species 668
6. Cofacial Arrangements 698
7. Multiporphyrin Surface Assemblies 710
8. Conclusions 725
References 726
Vibrational Spectra and Surface- Enhanced Vibrational Spectra of Azamacrocycles 739
1. Introduction 739
2. Surface Phenomena and Applications of Azamacrocycles 739
3. Surface Vibrational Spectroscopy 740
4. Infrared, Raman and Resonant Raman Spectra Analysis of Azamacrocycles 745
5. Normal Coordinate Calculations 760
6. Surface-Enhanced Vibrational and RAIRS Studies 766
7. Adsorbate-Substrate Interaction Vibrations 794
8. New Trends 803
References 804
Index 815