Zagal / Bedioui / Dodelet N4-Macrocyclic Metal Complexes

1. Auflage 2007
ISBN: 978-0-387-28430-9
Verlag: Springer US
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 814 Seiten

In response to significant developments in sensor science and technology, this book offers insight into the various extended applications and developments of N4 macrocycle complexes in biomimetic electrocatalysis. Chapters are devoted to the chemistry, electronic and electrochemical properties of porphyrin- based polymetallated supramolecular redox catalysts and their applications in analytical and photoelectrochemical molecular devices; the use of porphyrins, phthalocyanines and related complexes as electrocatalysts for the detection of a wide variety of environmentally polluting and biologically relevant molecules; and the use of electropolymerized metalloporphyrin and metallophthalocyanine films as powerful materials for analytical tools, especially for sensing biologically relevant species.

Autoren/Hrsg.

Bedioui, Fethi

Dodelet, Jean-Pol

Zagal, J. H.

Dodelet, J. P.

Inhaltsverzeichnis

1;Contents;5
2;Preface;15
3;Contributors;17
4;Billion-Year-Old Oxygen Cathode that Actually Works: Respiratory Oxygen Reduction and its Biomimetic Analogs;19
4.1;1. The Basic Concepts of Energy Metabolism;19
4.2;2. Biological Catalysis of Respiratory Oxygen Reduction;23
4.3;3. Biomimetic Catalysis of O2 Reduction;30
4.4;4. Summary and Conclusions: Lessons of Biomimetic O2 Reduction for the Design of Fuel Cell Catalysts;50
4.5;Acknowledgments;53
4.6;References;54
5;Fundamental Aspects on the Catalytic Activity of Metallomacrocyclics for the Electrochemical Reduction of O2;59
5.1;1. Introduction;59
5.2;2. Reaction Pathways for the Reduction of Molecular Oxygen;60
5.3;3. Interaction of O2 with Active Sites and the Redox Mechanism;64
5.4;4. Two-Electron Reduction Catalysts for the Reduction of Molecular Oxygen;75
5.5;5. Four-Electron Reduction Catalysts;78
5.6;6. Conclusions;91
5.7;Ackowledgments;93
5.8;References;93
6;Oxygen Reduction in PEM Fuel Cell Conditions: Heat- Treated Non- Precious Metal- N4 Macrocycles and Beyond;101
6.1;1. Why Search for a Non-Pt Based Catalyst for the Reduction of O2 in PEM Fuel Cells?;101
6.2;2. Activity of Electrocatalysts based on Fe - N4 and Co - N4 Macrocycles and Beyond;106
6.3;3. Kinetic and Mechanistic Aspects of Electrochemical Oxygen Reduction;139
6.4;4. Important Factors for the Use of Non-Noble Metal Electrocatalysts in PEM Fuel Cells for Automotive Applications;148
6.5;5. Conclusions;155
6.6;Acknowledgments;157
6.7;References;157
7;Biomimetic NOx Reductions by Heme Models and Proteins;166
7.1;1. Introduction;166
7.2;2. Native Enzymes for NOx Reductions;168
7.3;3. Electrochemical Investigations of NOX Reduction;176
7.4;4. Conclusions;197
7.5;Acknowledgments;198
7.6;References;198
8;Electroreduction of CO2 Catalyzed By Metallomacrocycles;208
8.1;1. Introduction;208
8.2;2. Electroreduction of CO2 on Metallic Cathodes;210
8.3;3. Biphenantroline and Bypiridine Hexaazacyclophane Systems;212
8.4;4. Cyclam and Derivative Systems;221
8.5;5. Phthalocyanines and Porphyrins Complexes;237
8.6;6. Conclusions;260
8.7;Acknowledgments;261
8.8;References;261
9;Supramolecular Porphyrins as Electrocatalysts;272
9.1;1. Build-up of Supramolecular Porphyrins Based on Metal- Ligand Coordination;272
9.2;2. Synthesis and Characterization of Tetrametallated Pyridyl Porphyrins;282
9.3;3. Catalytic and Electrocatalytic Properties;295
9.4;4. Electrochemical and Photoelectrochemical Properties of Porphyrin Films;304
9.5;5. Final Remarks;318
9.6;References;319
10;Electrodes Modified with Monomeric M - N4 Catalysts for the Detection of Environmentally Important Molecules;332
10.1;1. Introduction;332
10.2;2. Phenols, Organohalides, and Pesticides;335
10.3;3. Thiols;339
10.4;4. Sulfur Dioxide and Sulfur Oxoanions;346
10.5;5. Carbon Dioxide/Carbon Monoxide;349
10.6;6. Nitrites and Nitrates;356
10.7;7. Cyanides/Thiocyanades;359
10.8;8. Hydrazine/hydroxylamine;359
10.9;9. Conclusions;364
10.10;10. Acknowledgment;364
10.11;References;364
11;Electropolymerized Metalloporphyrin, Metallophthalocyanine and Metal Schiff Base Complex Films: Applications to Biomimetic Electrocatalysis and Bioelectroanalysis;379
11.1;1. Introduction;379
11.2;2. The Electrochemical Polymerization Strategy;381
11.3;3. Design and Characterization of Electropolymerized Metalloporphyrin and Metallophthalocyanine Film;381
11.4;4. Electrocatalytic and Electroanalytic Applications of Electropolymerized N4- Macrocyclic- Based Films;424
11.5;5. Conclusions;438
11.6;Acknowledgements;439
11.7;References;439
12;Electron Transfer Processes of ß- Pyrrole Brominated Porphyrins: Structural vs. Electronic Effects;455
12.1;1. Introduction;455
12.2;2. Synthesis;458
12.3;3. Effect of the Br Substituents and Solvent Interactions on the UV- Visible Spectra;461
12.4;4. Electrochemical Behavior of ß-Pyrrole Brominated Metalloporphyrins;462
12.5;5. Spectroelectrochemical Studies of ß-Pyrrole Brominated Metalloporphyrins;469
12.6;6. Effect of the Br Substituents on Axial Ligand Binding;472
12.7;7. Summary;474
12.8;Acknowledgments;476
12.9;References;476
13;Photoelectrochemical Reactions at Phthalocyanine Electrodes;483
13.1;1. Introduction;483
13.2;2. Essentials of Photoelectrochemical Reactions;484
13.3;3. Photoelectrochemical Experiments at Phthalocyanine Thin Films;486
13.4;4. Sensitization of Oxide Semiconductors by Phthalocyanines;510
13.5;5. Technology Outlook;517
13.6;6. Acknowledgment;519
13.7;References;519
14;Organisation And Photoelectrochemical Reactivity of Water- Soluble Metalloporphyrins at the Liquid/ Liquid Interface;532
14.1;1. Introduction;532
14.2;2. The Polarisable Liquid/Liquid Interface;533
14.3;3. Basic Photophysics of Metalloporphyrins and Chlorins;538
14.4;4. Organisation of Water-Soluble Porphyrins at the Liquid/ Liquid Interface;547
14.5;5. Photoelectrochemical Reactivity at Porphyrin- Sensitised Liquid/ Liquid Interfaces;560
14.6;6. Concluding Remarks;581
14.7;Acknowledgements;582
14.8;References;582
15;Theoretical Insights on the Chemical Reactivity of MetalloPorphyrins Using Density Functional Theory;590
15.1;1. Introduction;590
15.2;2. Computational Details;596
15.3;3. The Chemical Effects Tuning the Reactivity of M( II)- N4 Complexes;597
15.4;4. Conclusions;612
15.5;Acknowledgements;613
15.6;References;613
16;Organized Multiporphyrinic Assemblies for Photoconduction and Electroconduction;617
16.1;1. Introduction;617
16.2;2. The Porphyrinic Chromophore;619
16.3;3. Scope and Limitations;637
16.4;4. Covalent Species;637
16.5;5. Noncovalent Species;668
16.6;6. Cofacial Arrangements;698
16.7;7. Multiporphyrin Surface Assemblies;710
16.8;8. Conclusions;725
16.9;References;726
17;Vibrational Spectra and Surface- Enhanced Vibrational Spectra of Azamacrocycles;739
17.1;1. Introduction;739
17.2;2. Surface Phenomena and Applications of Azamacrocycles;739
17.3;3. Surface Vibrational Spectroscopy;740
17.4;4. Infrared, Raman and Resonant Raman Spectra Analysis of Azamacrocycles;745
17.5;5. Normal Coordinate Calculations;760
17.6;6. Surface-Enhanced Vibrational and RAIRS Studies;766
17.7;7. Adsorbate-Substrate Interaction Vibrations;794
17.8;8. New Trends;803
17.9;References;804
18;Index;815