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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'.

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Simulated concentration profiles at a diffusion domain containing a spherical particle. Category 1: σ=1000. Category 2: σ=10. Category 3: σ=1. Category 4: σ=0.01, where σ is the dimensionless scan rate. Concentration profiles were taken at the linear sweeps peak potential. Reproduced with permission from Ref. 151b. Copyright 2007, American Chemical Society.
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fig26: Simulated concentration profiles at a diffusion domain containing a spherical particle. Category 1: σ=1000. Category 2: σ=10. Category 3: σ=1. Category 4: σ=0.01, where σ is the dimensionless scan rate. Concentration profiles were taken at the linear sweeps peak potential. Reproduced with permission from Ref. 151b. Copyright 2007, American Chemical Society.

Mentions: For an array of nanoparticles supported upon an electrochemically inert electrode substrate, the mass transport to and from the nanoparticulate surface, and hence the voltammetric behaviour of the electrode, depends upon: the nanoparticles size and morphology, the diffusion coefficient of the analyte and product, the experimental (voltammetric) time scale, and the interparticle separation (nanoparticle surface coverage).151 Assuming the substrate electrode is macroscopic in dimensions, then the diffusion regime may be categorised into four cases. Importantly, during the course of a voltammetric scan, the prevailing diffusion regime will likely transit from one case to another; consequently, insight into the voltammetry of such systems is best achieved through simulation. Figure 26 schematically outlines the four diffusional cases or categories.


Recent Advances in Voltammetry.

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

Simulated concentration profiles at a diffusion domain containing a spherical particle. Category 1: σ=1000. Category 2: σ=10. Category 3: σ=1. Category 4: σ=0.01, where σ is the dimensionless scan rate. Concentration profiles were taken at the linear sweeps peak potential. Reproduced with permission from Ref. 151b. Copyright 2007, American Chemical Society.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig26: Simulated concentration profiles at a diffusion domain containing a spherical particle. Category 1: σ=1000. Category 2: σ=10. Category 3: σ=1. Category 4: σ=0.01, where σ is the dimensionless scan rate. Concentration profiles were taken at the linear sweeps peak potential. Reproduced with permission from Ref. 151b. Copyright 2007, American Chemical Society.
Mentions: For an array of nanoparticles supported upon an electrochemically inert electrode substrate, the mass transport to and from the nanoparticulate surface, and hence the voltammetric behaviour of the electrode, depends upon: the nanoparticles size and morphology, the diffusion coefficient of the analyte and product, the experimental (voltammetric) time scale, and the interparticle separation (nanoparticle surface coverage).151 Assuming the substrate electrode is macroscopic in dimensions, then the diffusion regime may be categorised into four cases. Importantly, during the course of a voltammetric scan, the prevailing diffusion regime will likely transit from one case to another; consequently, insight into the voltammetry of such systems is best achieved through simulation. Figure 26 schematically outlines the four diffusional cases or categories.

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