Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry, 2nd Edition
Rights Contact Login For More Details
- Wiley
More About This Title Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry, 2nd Edition
English
Written by two of the world's leading authorities in the field of electrochemistry, this book comprehensively addresses workhorse electrochemical reactions that serve as the basis of modern research for alternative energy solutions.
- Provides an accessible and readable summary on the use of electrochemical techniques and the applications of electrochemical concepts to functional molecular-level systems
- Includes a new chapter on proton coupled electron transfer, a completely revamped chapter on molecular catalysis of electrochemical reactions, and added sections throughout the book
- Bridges a gap and strengthens the relationship between electrochemists, molecular and biomolecular chemists—showing a variety of functions that may be obtained by multi-component systems designed using the paradigms of both chemistries
English
Jean-Michel Savéant is a Professor of Chemistry at Paris Diderot University and a CNRS Research Director in the Laboratoire d'Électrochimie Moléculaire, France. He is a member of the French Academy of Sciences and a foreign associate of the National Academy of Sciences of the USA
Cyrille Costentin is a Professor of Chemistry at Paris Diderot University, France.
English
Preface
CHAPTER 1. Single electron transfer at an electrode
1.1. Introduction
1.2. Cyclic voltammetry of fast electron transfers. Nernstian waves
1.2.1. One-electron transfer to molecules attached to the electrode surface
1.2.2. One-electron transfer to free moving molecules
1.3. Technical aspects
1.3.1. The cyclic voltammetry experiment. Faradaic and double layer charging currents. Ohmic drop
1.3.2. Other techniques. Convolution
1.4. Electron transfer kinetics
1.4.1. Introduction
1.4.2. Butler-Volmer law and Marcus-Hush-Levich (MHL) model
1.4.3. Extraction of electron transfer kinetics from cyclic voltammetric signals. Comparison with other techniques
1.4.4. Experimental testing of the electron transfer models
1.5. Successive one-electron transfers vs. two-electron transfers
1.5.1. Introduction
1.5.2. Cyclic voltammetric responses. Convolution
1.5.3. Response of molecules containing identical and independent reducible or oxidizable groups
1.5.4. An example of the predominating role of solvation: the oxidoreduction of carotenoids
1.5.5. An example of the predominating role of structural changes: the reduction of trans-2,3-dinitro-2 butene
1.6. References and Notes
CHAPTER 2. Coupling of electrode electron transfers with homogeneous chemical reactions.
2.1. Introduction
2.2. Establishing the mechanism and measuring the rate constants for homogeneous reactions by means of cyclic voltammetry and potential step chronoamperometry.
2.2.1. The EC mechanism
2.2.2. The CE mechanism
2.2.3. The square scheme mechanism
2.2.4. The ECE and DISP mechanisms
2.2.5. Electrodimerization
2.2.6. Homogeneous catalytic reaction schemes
2.2.7. Electrodes as catalysts. Electron-transfer catalyzed reactions
2.2.8. Numerical computations. Simulations. Diagnostic criteria. Working curves
2.3. Product distribution in preparative electrolysis
2.3.1. Introduction
2.3.2.General features
2.3.3. Product distribution resulting from competition between follow-up reactions
2.3.4. The ECE-DISP competition
2.3.5. Other reactions schemes
2.4. Classification and examples of electron transfer coupled chemical reactions
2.4.1. Coupling of single electron transfer with acid-base reactions
2.4.2. Electrodimerizations
2.4.3. Electropolymerization
2.4.4. Reduction of carbon dioxide
2.4.5. H-atom transfer vs. electron + proton transfer
2.4.6. The SRN1 substitution. Electrodes and electrons as catalysts
2.4.7. Conformational changes, isomerization and electron transfer
2.5. Redox properties of transient radicals.
2.5.1. Introduction 2.5.2. The direct electrochemical approach.
2.5.3. Laser flash electron injection 2.5.4. Photomodulaltion voltammetry
2.6. Electrochemistry as a trigger for radical chemistry or for ionic chemistry
2.7. References and notes
CHAPTER 3. Coupling between electron transfer and heavy atom-bond breaking and formation
3.1. Introduction
3.2. Dissociative electron transfer
3.2.1. Thermodynamics. Microscopic reversibility
3.2.2. The Morse curve model
3.2.3. Values of the symmetry factor and variation with the driving force
3.2.4. Entropy of activation
3.3. Interactions between fragments in the product cluster
3.3.1. Influence on the dynamics of dissociative electron transfers
3.3.2. A typical example: dissociative electron transfer to carbon tetrachloride
3.3.3. Stabilities of ion-radical adducts as a function of the solvent
3.3.4. Dependency of in-cage ion-radical interactions upon the leaving group
3.4. Stepwise vs. concerted mechanisms
3.4.1. Introduction
3.4.2. Diagnostic criteria
3.4.3. How molecular structure controls the mechanism?
3.4.4. Passage from one mechanism to the other upon changing the driving force
3.4.5. Photoinduced vs. thermal processes
3.4.6. Does concerted mechanism means that the intermediate 'does not exist'?
3.4.7. π and σ ion radicals. Competition between reaction pathways
3.5. Cleavage of ion radicals. Reaction of radicals with nucleophiles
3.5.1. Introduction3
3.5.2. Heterolytic cleavages. Reaction of radicals with nucleophiles
3.5.3.Homolytic cleavages
3.6. Role of solvent in ion radical cleavage and in stepwise vs. concerted competitions
3.6.1. Introduction
3.6.2. Experimental clues
3.6.3. A simplified model system
3.7. Dichotomy and connections between SN2 reactions and dissociative electron transfers
3.7.1. Introduction
3.7.2. Experimental approaches
3.7.3. Theoretical aspects
3.8. References and Notes
CHAPTER 4. Proton-coupled electron transfers.
4.1. Introduction
4.2. Fundamentals
4.2.1. Concerted and stepwise pathways in proton-coupled electron transfer reactions
4.2.2. Thermal (electrochemical and homogeneous) and photoinduced reactions
4.2.3. Modeling concerted proton electron transfers
4.3. Examples
4.3.1. PCET in hydrogen bounded systems. H-bond relays
4.3.2. PCET in water
4.4. Breaking bonds with protons and electrons.
4.5. References and notes
CHAPTER 5. Molecular catalysis of electrochemical reactions.
5.1. Introduction.
5.2. Homogenous molecular catalysis
5.2.1. Contrasting redox and chemical catalysis
5.2.2. Applications of homogeneous redox catalysis to the characterization of short lived intermediates
5.2.3. Overpotential, turnover frequency, catalysts’ benchmarking, catalytic Tafel plots, maximal turnover number
5.2.4. Inhibition by intermediates and other secondary phenomena. Remedies
5.2.5. Multi-electron multistep mechanisms
5.2.6. Competition between heterolytic and homolytic catalytic mechanisms
5.2.7. Intelligent design of molecular catalysts
5.3. Supported molecular catalysis (immobilized catalysts)
5.3.1. Redox and chemical catalysis at monolayer and multilayer coated electrodes
5.3.2. Catalysis at monolayer coated electrodes
5.3.3. Permeation through electrode coatings. Inhibition
5.3.4. Electron hopping conduction in assemblies of redox centers
5.3.5. Ohmic conduction in mesoporous electrodes
5.3.6. Catalysis at multilayer coated electrodes.
5.3.7. Combining an electron-shuttling mediator with a chemical catalyst in a multilayer electrode coating
5.4. References and Notes
CHAPTER 6. Enzymatic catalysis of electrochemical reactions.
6.1. Introduction
6.2. Homogenous enzymatic catalysis
6.2.1. Introduction
6.2.2. The ‘ping-pong mechanism’. Kinetic control by substrate and/or cosubstrate
6.2.3. A model example: glucose oxidase with excess glucose
6.2.5. Molecular recognition of an enzyme by artificial one-electron cosubstrates
6.2.5. Deciphering a complex electro-enzymatic response: horseradish peroxidase
6.3. Immobilized enzymes in monomolecular layers
6.3.1. Introduction
6.3.2. The ‘ping-pong mechanism’ with an immobilized enzyme and the cosubstrate in solution
6.3.3. Antigen-antibody immobilization of glucose oxidase. Kinetic analysis.
6.3.4. Application to the kinetic characterization of biomolecular recognition
6.3.5. Immobilized horseradish peroxidase
6.3.6. Immobilization of both the enzyme and the cosubstrate. Electron transfer and electron transport in integrated systems
6.4. Spatially ordered multi-monomolecular layered enzyme coatings
6.4.1. Step-by-step antigen-antibody construction of multi-mono-molecular layer enzyme coatings
6.4.2. Reaction dynamics with the cosubstrate in solution. Evidence for spatial order
6.5. References and Notes
CHAPTER 7. Appendixes
7.1. Single electron transfer at an electrode
7.1.1. Laplace transformation. Useful definitions and relationships
7.1.2. Cyclic voltammetry of one-electron Nernstian systems. Current- and charge-potential curves
7.1.3. Double layer charging in cyclic voltammetry. Oscillating and non-oscillating behaviors
7.1.4. Effect of ohmic drop and double layer charging on Nernstian cyclic voltammograms
7.1.5. Potential step and double potential step chronoamperometry of Nernstian systems
7.1.6. Overlapping of double layer charging and faradaic currents in potential step and double potential step chronoamperometry. Oscillating and non-oscillating behaviors
7.1.7. Solvent reorganization in Marcus-Hush-Levich model
7.1.8. Effect of the multiplicity of electronic states in the electrode
7.1.9. Cyclic voltammetry of two-electron Nernstian systems. Disproportionation
7.2. Coupling of homogeneous chemical reactions with electron transfer
7.2.1. The EC mechanism
7.2.2. The CE mechanism
7.2.3. Double potential step responses for processes involving first- order or second-order follow-up reactions
7.2.4. The ECE and DISP mechanisms
7.2.5. Electrodimerization
7.2.6. Competition between dimerization of and electron transfer to intermediates
7.2.7. Homogeneous catalysis
7.2.8. Product distribution in preparative electrolysis
7.3. Electron transfer, bond breaking and bond formation
7.3.1. Contribution of the cleaving bond stretching to internal reorganization of the first step of the stepwise mechanism
7.3.2. Morse curve model of intramolecular dissociative electron transfer
7.4. Proton-coupled electron transfers
7.4.1. Rate law for electrochemical CPET
7.4.2. Current-potential relationship for PCET in water
7.4.3. Competition between dimerization and CPET kinetics
7.5. Analysis of supported molecular catalysis by rotating disk electrode voltammetry and cyclic voltammetry
7.5.1. Catalysis at monolayer electrode coatings
7.5.2. Inhibition of electron transfer at partially blocked electrodes
7.5.3. Equivalent diffusion and migration laws for electron hopping between fixed sites
7.5.4. Ohmic conduction in mesoporous electrodes
7.5.5. Catalysis at multilayered electrode coatings. RDVE
7.5.6. Ohmic transport in electrocatalytic film
7.5.7. Catalysis at multilayered electrode coatings. Cyclic Voltammetry
7.6. Enzymatic catalysis responses
7.6.1. The ‘ping-pong’ mechanism in homogeneous enzymatic catalysis
7.6.2. Catalysis and inhibition in homogeneous systems
7.6.3. Catalysis at multilayered electrode coatings
7.7. References and Notes
CHAPTER 1. Single electron transfer at an electrode
1.1. Introduction
1.2. Cyclic voltammetry of fast electron transfers. Nernstian waves
1.2.1. One-electron transfer to molecules attached to the electrode surface
1.2.2. One-electron transfer to free moving molecules
1.3. Technical aspects
1.3.1. The cyclic voltammetry experiment. Faradaic and double layer charging currents. Ohmic drop
1.3.2. Other techniques. Convolution
1.4. Electron transfer kinetics
1.4.1. Introduction
1.4.2. Butler-Volmer law and Marcus-Hush-Levich (MHL) model
1.4.3. Extraction of electron transfer kinetics from cyclic voltammetric signals. Comparison with other techniques
1.4.4. Experimental testing of the electron transfer models
1.5. Successive one-electron transfers vs. two-electron transfers
1.5.1. Introduction
1.5.2. Cyclic voltammetric responses. Convolution
1.5.3. Response of molecules containing identical and independent reducible or oxidizable groups
1.5.4. An example of the predominating role of solvation: the oxidoreduction of carotenoids
1.5.5. An example of the predominating role of structural changes: the reduction of trans-2,3-dinitro-2 butene
1.6. References and Notes
CHAPTER 2. Coupling of electrode electron transfers with homogeneous chemical reactions.
2.1. Introduction
2.2. Establishing the mechanism and measuring the rate constants for homogeneous reactions by means of cyclic voltammetry and potential step chronoamperometry.
2.2.1. The EC mechanism
2.2.2. The CE mechanism
2.2.3. The square scheme mechanism
2.2.4. The ECE and DISP mechanisms
2.2.5. Electrodimerization
2.2.6. Homogeneous catalytic reaction schemes
2.2.7. Electrodes as catalysts. Electron-transfer catalyzed reactions
2.2.8. Numerical computations. Simulations. Diagnostic criteria. Working curves
2.3. Product distribution in preparative electrolysis
2.3.1. Introduction
2.3.2.General features
2.3.3. Product distribution resulting from competition between follow-up reactions
2.3.4. The ECE-DISP competition
2.3.5. Other reactions schemes
2.4. Classification and examples of electron transfer coupled chemical reactions
2.4.1. Coupling of single electron transfer with acid-base reactions
2.4.2. Electrodimerizations
2.4.3. Electropolymerization
2.4.4. Reduction of carbon dioxide
2.4.5. H-atom transfer vs. electron + proton transfer
2.4.6. The SRN1 substitution. Electrodes and electrons as catalysts
2.4.7. Conformational changes, isomerization and electron transfer
2.5. Redox properties of transient radicals.
2.5.1. Introduction 2.5.2. The direct electrochemical approach.
2.5.3. Laser flash electron injection 2.5.4. Photomodulaltion voltammetry
2.6. Electrochemistry as a trigger for radical chemistry or for ionic chemistry
2.7. References and notes
CHAPTER 3. Coupling between electron transfer and heavy atom-bond breaking and formation
3.1. Introduction
3.2. Dissociative electron transfer
3.2.1. Thermodynamics. Microscopic reversibility
3.2.2. The Morse curve model
3.2.3. Values of the symmetry factor and variation with the driving force
3.2.4. Entropy of activation
3.3. Interactions between fragments in the product cluster
3.3.1. Influence on the dynamics of dissociative electron transfers
3.3.2. A typical example: dissociative electron transfer to carbon tetrachloride
3.3.3. Stabilities of ion-radical adducts as a function of the solvent
3.3.4. Dependency of in-cage ion-radical interactions upon the leaving group
3.4. Stepwise vs. concerted mechanisms
3.4.1. Introduction
3.4.2. Diagnostic criteria
3.4.3. How molecular structure controls the mechanism?
3.4.4. Passage from one mechanism to the other upon changing the driving force
3.4.5. Photoinduced vs. thermal processes
3.4.6. Does concerted mechanism means that the intermediate 'does not exist'?
3.4.7. π and σ ion radicals. Competition between reaction pathways
3.5. Cleavage of ion radicals. Reaction of radicals with nucleophiles
3.5.1. Introduction3
3.5.2. Heterolytic cleavages. Reaction of radicals with nucleophiles
3.5.3.Homolytic cleavages
3.6. Role of solvent in ion radical cleavage and in stepwise vs. concerted competitions
3.6.1. Introduction
3.6.2. Experimental clues
3.6.3. A simplified model system
3.7. Dichotomy and connections between SN2 reactions and dissociative electron transfers
3.7.1. Introduction
3.7.2. Experimental approaches
3.7.3. Theoretical aspects
3.8. References and Notes
CHAPTER 4. Proton-coupled electron transfers.
4.1. Introduction
4.2. Fundamentals
4.2.1. Concerted and stepwise pathways in proton-coupled electron transfer reactions
4.2.2. Thermal (electrochemical and homogeneous) and photoinduced reactions
4.2.3. Modeling concerted proton electron transfers
4.3. Examples
4.3.1. PCET in hydrogen bounded systems. H-bond relays
4.3.2. PCET in water
4.4. Breaking bonds with protons and electrons.
4.5. References and notes
CHAPTER 5. Molecular catalysis of electrochemical reactions.
5.1. Introduction.
5.2. Homogenous molecular catalysis
5.2.1. Contrasting redox and chemical catalysis
5.2.2. Applications of homogeneous redox catalysis to the characterization of short lived intermediates
5.2.3. Overpotential, turnover frequency, catalysts’ benchmarking, catalytic Tafel plots, maximal turnover number
5.2.4. Inhibition by intermediates and other secondary phenomena. Remedies
5.2.5. Multi-electron multistep mechanisms
5.2.6. Competition between heterolytic and homolytic catalytic mechanisms
5.2.7. Intelligent design of molecular catalysts
5.3. Supported molecular catalysis (immobilized catalysts)
5.3.1. Redox and chemical catalysis at monolayer and multilayer coated electrodes
5.3.2. Catalysis at monolayer coated electrodes
5.3.3. Permeation through electrode coatings. Inhibition
5.3.4. Electron hopping conduction in assemblies of redox centers
5.3.5. Ohmic conduction in mesoporous electrodes
5.3.6. Catalysis at multilayer coated electrodes.
5.3.7. Combining an electron-shuttling mediator with a chemical catalyst in a multilayer electrode coating
5.4. References and Notes
CHAPTER 6. Enzymatic catalysis of electrochemical reactions.
6.1. Introduction
6.2. Homogenous enzymatic catalysis
6.2.1. Introduction
6.2.2. The ‘ping-pong mechanism’. Kinetic control by substrate and/or cosubstrate
6.2.3. A model example: glucose oxidase with excess glucose
6.2.5. Molecular recognition of an enzyme by artificial one-electron cosubstrates
6.2.5. Deciphering a complex electro-enzymatic response: horseradish peroxidase
6.3. Immobilized enzymes in monomolecular layers
6.3.1. Introduction
6.3.2. The ‘ping-pong mechanism’ with an immobilized enzyme and the cosubstrate in solution
6.3.3. Antigen-antibody immobilization of glucose oxidase. Kinetic analysis.
6.3.4. Application to the kinetic characterization of biomolecular recognition
6.3.5. Immobilized horseradish peroxidase
6.3.6. Immobilization of both the enzyme and the cosubstrate. Electron transfer and electron transport in integrated systems
6.4. Spatially ordered multi-monomolecular layered enzyme coatings
6.4.1. Step-by-step antigen-antibody construction of multi-mono-molecular layer enzyme coatings
6.4.2. Reaction dynamics with the cosubstrate in solution. Evidence for spatial order
6.5. References and Notes
CHAPTER 7. Appendixes
7.1. Single electron transfer at an electrode
7.1.1. Laplace transformation. Useful definitions and relationships
7.1.2. Cyclic voltammetry of one-electron Nernstian systems. Current- and charge-potential curves
7.1.3. Double layer charging in cyclic voltammetry. Oscillating and non-oscillating behaviors
7.1.4. Effect of ohmic drop and double layer charging on Nernstian cyclic voltammograms
7.1.5. Potential step and double potential step chronoamperometry of Nernstian systems
7.1.6. Overlapping of double layer charging and faradaic currents in potential step and double potential step chronoamperometry. Oscillating and non-oscillating behaviors
7.1.7. Solvent reorganization in Marcus-Hush-Levich model
7.1.8. Effect of the multiplicity of electronic states in the electrode
7.1.9. Cyclic voltammetry of two-electron Nernstian systems. Disproportionation
7.2. Coupling of homogeneous chemical reactions with electron transfer
7.2.1. The EC mechanism
7.2.2. The CE mechanism
7.2.3. Double potential step responses for processes involving first- order or second-order follow-up reactions
7.2.4. The ECE and DISP mechanisms
7.2.5. Electrodimerization
7.2.6. Competition between dimerization of and electron transfer to intermediates
7.2.7. Homogeneous catalysis
7.2.8. Product distribution in preparative electrolysis
7.3. Electron transfer, bond breaking and bond formation
7.3.1. Contribution of the cleaving bond stretching to internal reorganization of the first step of the stepwise mechanism
7.3.2. Morse curve model of intramolecular dissociative electron transfer
7.4. Proton-coupled electron transfers
7.4.1. Rate law for electrochemical CPET
7.4.2. Current-potential relationship for PCET in water
7.4.3. Competition between dimerization and CPET kinetics
7.5. Analysis of supported molecular catalysis by rotating disk electrode voltammetry and cyclic voltammetry
7.5.1. Catalysis at monolayer electrode coatings
7.5.2. Inhibition of electron transfer at partially blocked electrodes
7.5.3. Equivalent diffusion and migration laws for electron hopping between fixed sites
7.5.4. Ohmic conduction in mesoporous electrodes
7.5.5. Catalysis at multilayered electrode coatings. RDVE
7.5.6. Ohmic transport in electrocatalytic film
7.5.7. Catalysis at multilayered electrode coatings. Cyclic Voltammetry
7.6. Enzymatic catalysis responses
7.6.1. The ‘ping-pong’ mechanism in homogeneous enzymatic catalysis
7.6.2. Catalysis and inhibition in homogeneous systems
7.6.3. Catalysis at multilayered electrode coatings
7.7. References and Notes
