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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

Comparison of the voltage wave forms used for staircase (red) and true analogue (black) cyclic voltammetry. Zoomed inlay depicts an individual step showing the sampling alpha scale. When α=1 the current is sampled at the end of the step; alternatively, α=0 implies a current measurement at the beginning of the step. Data depicts the wave form used for a cyclic voltammogram (0–1 V) at a scan rate of 0.1 V s−1 and with a step potential of 20 mV.
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fig10: Comparison of the voltage wave forms used for staircase (red) and true analogue (black) cyclic voltammetry. Zoomed inlay depicts an individual step showing the sampling alpha scale. When α=1 the current is sampled at the end of the step; alternatively, α=0 implies a current measurement at the beginning of the step. Data depicts the wave form used for a cyclic voltammogram (0–1 V) at a scan rate of 0.1 V s−1 and with a step potential of 20 mV.

Mentions: Figure 10 depicts the variation of the potential used for ‘staircase’ (red) and true analogue (black) cyclic voltammetry. For a given electrochemical system studied via analogue cyclic voltammetry (CV), the measured response is simply a function of the scan rate (assuming appropriately chosen start, finish, and turning potentials). Conversely, for staircase cyclic voltammetry (SCV), the resulting voltammogram is a function of the scan rate (step height/step time=V s−1), the step size (Estep/V), and the point (or points) at which the current is sampled during each step. In the case that the current is sampled once during each step the time at which the current is sampled is expressed as the dimensionless value alpha (α), where an alpha value of one or zero implies the current is sampled at the end or beginning of each step respectively (see inlay of Figure 10). This sampling alpha value bears no relation to the transfer coefficient and the two should in no way be conflated!


Recent Advances in Voltammetry.

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

Comparison of the voltage wave forms used for staircase (red) and true analogue (black) cyclic voltammetry. Zoomed inlay depicts an individual step showing the sampling alpha scale. When α=1 the current is sampled at the end of the step; alternatively, α=0 implies a current measurement at the beginning of the step. Data depicts the wave form used for a cyclic voltammogram (0–1 V) at a scan rate of 0.1 V s−1 and with a step potential of 20 mV.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig10: Comparison of the voltage wave forms used for staircase (red) and true analogue (black) cyclic voltammetry. Zoomed inlay depicts an individual step showing the sampling alpha scale. When α=1 the current is sampled at the end of the step; alternatively, α=0 implies a current measurement at the beginning of the step. Data depicts the wave form used for a cyclic voltammogram (0–1 V) at a scan rate of 0.1 V s−1 and with a step potential of 20 mV.
Mentions: Figure 10 depicts the variation of the potential used for ‘staircase’ (red) and true analogue (black) cyclic voltammetry. For a given electrochemical system studied via analogue cyclic voltammetry (CV), the measured response is simply a function of the scan rate (assuming appropriately chosen start, finish, and turning potentials). Conversely, for staircase cyclic voltammetry (SCV), the resulting voltammogram is a function of the scan rate (step height/step time=V s−1), the step size (Estep/V), and the point (or points) at which the current is sampled during each step. In the case that the current is sampled once during each step the time at which the current is sampled is expressed as the dimensionless value alpha (α), where an alpha value of one or zero implies the current is sampled at the end or beginning of each step respectively (see inlay of Figure 10). This sampling alpha value bears no relation to the transfer coefficient and the two should in no way be conflated!

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