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Tafel-Volmer electrode reactions: The influence of electron-transfer kinetics

Abstract:
A typical Tafel-Volmer electrode reaction, embracing a preceding chemisorption step and a following electron transfer, is explored by simulation. Two different electron transfer formalisms, Butler-Volmer and a Marcus-Hush like approach, are utilised in interpreting the potential-dependent kinetics of the electrochemical process. Under non-reversible electron transfer conditions, the steady-state voltammetric response at a microdisk electrode is sensitive to the underlying electron transfer kinetics, such that with weak adsorption conditions, the discrepancies between the two electron-transfer models are more pronounced. At high overpotentials, a non-diffusion limited current may either arise from slow adsorption or be a result of Marcus-Hush type kinetics.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/acs.jpcc.5b08044

Authors

More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author


Publisher:
American Chemical Society
Journal:
Journal of Physical Chemistry C More from this journal
Volume:
119
Issue:
39
Pages:
22415-22424
Publication date:
2015-09-14
Acceptance date:
2015-08-18
DOI:
EISSN:
1932-7455
ISSN:
1932-7447


Keywords:
Pubs id:
pubs:570656
UUID:
uuid:f73db60f-6a26-4e32-a9a3-da4a5d11be4f
Local pid:
pubs:570656
Source identifiers:
570656
Deposit date:
2016-04-01
ARK identifier:

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