Elements of Molecular and Biomolecular Electrochemistry

Name: Elements of Molecular and Biomolecular Electrochemistry | An Electrochemical Approach to Electron Transfer Chemistry
Brand: Wiley
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An Electrochemical Approach to Electron Transfer Chemistry

Jean-Michel Savéant Cyrille Costentin(Autor*in)

Wiley (Verlag)

2. Auflage

Erschienen am 7. Juni 2019

640 Seiten

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Inhalt

Cover
Title Page
Copyright
Contents
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
References
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
2.2.6.1 Homogeneous Electron Transfer as the Rate-Determining Step
2.2.6.2 Homogeneous Catalytic EC Mechanism
2.2.6.3 Deactivation of the Mediator
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 Electrodimerization
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 Photomodulation Voltammetry
2.6 Electrochemistry as a Trigger for Radical Chemistry or for Ionic Chemistry
References
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 on 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 Mean that the Intermediate ``Does Not Exist''?
3.4.7 &rmpi
and &rmsigma
Ion Radicals: Competition Between Reaction Pathways
3.5 Cleavage of Ion Radicals: Reaction of Radicals with Nucleophiles
3.5.1 Introduction
3.5.2 Heterolytic Cleavages: Coupling 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
References
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
References
Chapter 5 Molecular Catalysis of Electrochemical Reactions
5.1 Introduction
5.2 Homogeneous 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
5.2.2.1 Principle and Achievements of the Method
5.2.2.2 Comparison with Fast Cyclic Voltammetry and Laser Flash Photolysis
5.2.2.3 Determination of the Standard Potential for the Formation of Very Unstable Primary Intermediates
5.2.2.4 Redox Catalysis of Electrocatalytic Processes
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
5.2.7.1 Redox vs. Chemical Catalysis: The Reduction of Vicinal Dibromides. Rates and Stereoselectivity
5.2.7.2 Correlation Between Catalysis Kinetics and Thermodynamics: The ``Iron Law'' Restraining Through-Structure Substituent Effect Within a Catalyst Family
5.2.7.3 Escaping the ``Iron Law'': Through-Space Substituent Effects
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
References
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
6.2.4 Molecular Recognition of an Enzyme by Artificial One-Electron Cosubstrates
6.2.5 Deciphering a Complex Electroenzymatic 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-monomolecular Layer Enzyme Coatings
6.4.2 Reaction Dynamics with the Cosubstrate in Solution: Evidence for Spatial Order
References
Chapter 7 Appendices
7.1 Single-Electron Transfer at an Electrode
7.1.1 Laplace Transformation: Useful Definitions and Relationships
7.1.2 Cyclic Voltammetry of Nernstian Systems: Current- and Charge-Potential Curves
7.1.3 Double-Layer Charging in Cyclic Voltammetry: Oscillating and Nonoscillating 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 Nonoscillating 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- 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
7.2.7.1 Homogeneous Electron Transfer as the Rate-Determining Step
7.2.7.2 Homogeneous Catalytic EC Mechanism
7.2.7.3 Deactivation of the Mediator
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
7.5.6.1 Governing Equations
7.5.6.2 Dimensionless Formulation
7.5.6.3 Semianalytical Resolution
7.5.6.4 Asymptotes of the Catalytic Tafel Plots for E ±8
7.5.7 Catalysis at Multilayered Electrode Coatings: Cyclic Voltammetry
7.5.7.1 Formulation
7.5.7.2 Resolution in the Absence of Substrate Consumption
7.5.7.3 Resolution in Pure Kinetics Conditions (Fast Kinetics) with Possible Substrate Consumption
7.5.7.4 Resolution in Fast-conducting Conditions with Possible Substrate Consumption
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
7.6.2.1 Derivation of Eq. (6.10)
7.6.2.2 Control by Substrate Diffusion
7.6.3 Catalysis at Multilayered Electrode Coatings
References
Glossary of Symbols
Index
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