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Recent Advances in Voltammetry.

Batchelor-McAuley C, Kätelhön E, Barnes EO, Compton RG, Laborda E, Molina A - ChemistryOpen (2015)

Bottom Line: The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity.This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry.The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford South Parks Road, Oxford, OX1 3QZ, UK.

ABSTRACT
Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

No MeSH data available.


Related in: MedlinePlus

Illustration of the effects of the thermodynamics and kinetics of coupled homogeneous chemical reactions on differential double pulse voltammetry (DDPV)[79a] (A) and reverse pulse voltammetry (RPV)[80] (B). Grey solid lines correspond to a simple reversible E mechanism.
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fig05: Illustration of the effects of the thermodynamics and kinetics of coupled homogeneous chemical reactions on differential double pulse voltammetry (DDPV)[79a] (A) and reverse pulse voltammetry (RPV)[80] (B). Grey solid lines correspond to a simple reversible E mechanism.

Mentions: In recent years the use of double potential pulse techniques for the study of electrode kinetics and reaction mechanisms has been developed both theoretically and experimentally at microelectrodes.77 The combination of pulse techniques and small-sized electrodes offers important advantages in terms of accuracy as a result of the reduction of distorting effects (mainly ohmic drop and charging current),26,78 which leads to well-defined signals adequate for electrochemical studies even in media of low conductivity. With respect to electrode reactions complicated by coupled (electro)chemical processes (Figure 5), analytical theory for double pulse techniques at microelectrodes of different geometries has been developed for the study of the (pseudo)first-order CE,79 EC,79,80 catalytic81 and equilibrium square82 mechanisms as well as multistep electrode processes.83 Analytical expressions for one-electron transfer processes of solution-phase redox systems of any reversibility degree have also been deduced for double potential pulse techniques at (hemi)spherical microelectrodes. The reversibility criteria and methodologies for kinetic analysis are appropriate for other microelectrode geometries and will be discussed in the following sections.


Recent Advances in Voltammetry.

Batchelor-McAuley C, Kätelhön E, Barnes EO, Compton RG, Laborda E, Molina A - ChemistryOpen (2015)

Illustration of the effects of the thermodynamics and kinetics of coupled homogeneous chemical reactions on differential double pulse voltammetry (DDPV)[79a] (A) and reverse pulse voltammetry (RPV)[80] (B). Grey solid lines correspond to a simple reversible E mechanism.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4522172&req=5

fig05: Illustration of the effects of the thermodynamics and kinetics of coupled homogeneous chemical reactions on differential double pulse voltammetry (DDPV)[79a] (A) and reverse pulse voltammetry (RPV)[80] (B). Grey solid lines correspond to a simple reversible E mechanism.
Mentions: In recent years the use of double potential pulse techniques for the study of electrode kinetics and reaction mechanisms has been developed both theoretically and experimentally at microelectrodes.77 The combination of pulse techniques and small-sized electrodes offers important advantages in terms of accuracy as a result of the reduction of distorting effects (mainly ohmic drop and charging current),26,78 which leads to well-defined signals adequate for electrochemical studies even in media of low conductivity. With respect to electrode reactions complicated by coupled (electro)chemical processes (Figure 5), analytical theory for double pulse techniques at microelectrodes of different geometries has been developed for the study of the (pseudo)first-order CE,79 EC,79,80 catalytic81 and equilibrium square82 mechanisms as well as multistep electrode processes.83 Analytical expressions for one-electron transfer processes of solution-phase redox systems of any reversibility degree have also been deduced for double potential pulse techniques at (hemi)spherical microelectrodes. The reversibility criteria and methodologies for kinetic analysis are appropriate for other microelectrode geometries and will be discussed in the following sections.

Bottom Line: The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity.This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry.The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford South Parks Road, Oxford, OX1 3QZ, UK.

ABSTRACT
Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

No MeSH data available.


Related in: MedlinePlus