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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.


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Schematic of the two types of diffusion that contribute to current at a carbon-nanotube-modified electrode. Reproduced with permission from Ref. 144a. Copyright 2008, Elsevier.
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fig21: Schematic of the two types of diffusion that contribute to current at a carbon-nanotube-modified electrode. Reproduced with permission from Ref. 144a. Copyright 2008, Elsevier.

Mentions: The effects predicted for thin-layer versus semi-infinite diffusion voltammetry are consistent with observations made using a range of systems.144a–144c In particular, there has been very considerable work in using carbon nanotubes (or chemically modified nanotubes) to create porous layers on the surface of electrodes. The observed voltammetry is consistent with the ideas outlined in the previous section (refs. 144a–144c and refs. therein). Figure 21 shows the basic model in which the trapped products of analyte-containing solution act as small thin-layer cells. A key indicator of this behavior is the observation that the peak currents flowing associated with the thin-layer behavior can be significantly larger than those seen for semi-infinite diffusion at an electrode of the same geometric area. Note, as discussed above, such large enhancements are not understandable in terms of altered electrode kinetics per se. The work of Henstridge et al.144b contains tables of examples of CNT and other modified electrodes in which the thin-layer behavior may operate. Similarly Kozub et al.143 report ‘electrocatalytic’ systems developed allegedly for the detection of nitrite.


Recent Advances in Voltammetry.

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

Schematic of the two types of diffusion that contribute to current at a carbon-nanotube-modified electrode. Reproduced with permission from Ref. 144a. Copyright 2008, Elsevier.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig21: Schematic of the two types of diffusion that contribute to current at a carbon-nanotube-modified electrode. Reproduced with permission from Ref. 144a. Copyright 2008, Elsevier.
Mentions: The effects predicted for thin-layer versus semi-infinite diffusion voltammetry are consistent with observations made using a range of systems.144a–144c In particular, there has been very considerable work in using carbon nanotubes (or chemically modified nanotubes) to create porous layers on the surface of electrodes. The observed voltammetry is consistent with the ideas outlined in the previous section (refs. 144a–144c and refs. therein). Figure 21 shows the basic model in which the trapped products of analyte-containing solution act as small thin-layer cells. A key indicator of this behavior is the observation that the peak currents flowing associated with the thin-layer behavior can be significantly larger than those seen for semi-infinite diffusion at an electrode of the same geometric area. Note, as discussed above, such large enhancements are not understandable in terms of altered electrode kinetics per se. The work of Henstridge et al.144b contains tables of examples of CNT and other modified electrodes in which the thin-layer behavior may operate. Similarly Kozub et al.143 report ‘electrocatalytic’ systems developed allegedly for the detection of nitrite.

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