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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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Related in: MedlinePlus

Influence of the Butler–Volmer kinetic parameters on the response of a one-electron reduction process in RPV at a (hemi)spherical microelectrode (r0=30 μm). t1=1 s, t1/t2=10. Id,p(t2)=FA .
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fig07: Influence of the Butler–Volmer kinetic parameters on the response of a one-electron reduction process in RPV at a (hemi)spherical microelectrode (r0=30 μm). t1=1 s, t1/t2=10. Id,p(t2)=FA .

Mentions: The RPV response under transient conditions shows a cathodic and an anodic branch (without requiring the initial presence of the product species), and the shape of the RPV curve is greatly affected by the electron transfer kinetics as shown in Figure 7. As k0 decreases, the RPV voltammogram gradually splits into a cathodic and an anodic wave. Also, when the process is sluggish (k0<10−3 cm s−1) and the second potential pulse is long enough (t2≈t1), a maximum (“bump”) is observed in the anodic wave that is more apparent at large electrodes.77d With regard to the transfer coefficient, the α-value affects both the position and slope of the cathodic and anodic branches such that the cathodic wave is steeper and shifts to smaller overpotentials as α takes larger values (Figure 7), the opposite being true for the anodic wave. Therefore, visual inspection of the RPV curve enables us to estimate the electrochemical reversibility of the system, as well as the transfer coefficient. A summary of the reversibility criteria for DDPV, ADPV, and RPV is found in Table 1.


Recent Advances in Voltammetry.

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

Influence of the Butler–Volmer kinetic parameters on the response of a one-electron reduction process in RPV at a (hemi)spherical microelectrode (r0=30 μm). t1=1 s, t1/t2=10. Id,p(t2)=FA .
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig07: Influence of the Butler–Volmer kinetic parameters on the response of a one-electron reduction process in RPV at a (hemi)spherical microelectrode (r0=30 μm). t1=1 s, t1/t2=10. Id,p(t2)=FA .
Mentions: The RPV response under transient conditions shows a cathodic and an anodic branch (without requiring the initial presence of the product species), and the shape of the RPV curve is greatly affected by the electron transfer kinetics as shown in Figure 7. As k0 decreases, the RPV voltammogram gradually splits into a cathodic and an anodic wave. Also, when the process is sluggish (k0<10−3 cm s−1) and the second potential pulse is long enough (t2≈t1), a maximum (“bump”) is observed in the anodic wave that is more apparent at large electrodes.77d With regard to the transfer coefficient, the α-value affects both the position and slope of the cathodic and anodic branches such that the cathodic wave is steeper and shifts to smaller overpotentials as α takes larger values (Figure 7), the opposite being true for the anodic wave. Therefore, visual inspection of the RPV curve enables us to estimate the electrochemical reversibility of the system, as well as the transfer coefficient. A summary of the reversibility criteria for DDPV, ADPV, and RPV is found in Table 1.

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