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A Comparison between Interfacial Electron-Transfer Rate Constants at Metallic and Graphite Electrodes

Royea, William J. and Hamann, Thomas W. and Brunschwig, Bruce S. and Lewis, Nathan S. (2006) A Comparison between Interfacial Electron-Transfer Rate Constants at Metallic and Graphite Electrodes. Journal of Physical Chemistry B, 110 (39). pp. 19433-19442. ISSN 1520-6106. https://resolver.caltech.edu/CaltechAUTHORS:20170524-100829690

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Abstract

The Fermi golden rule formalism has been used to derive the rate constant for interfacial electron transfer from a semimetallic electrode, such as highly ordered pyrolytic graphite (HOPG), to a redox couple in solution. A simple expression is presented that semiquantitatively relates the electron-transfer rate constant at a semimetallic electrode to that at a metallic electrode. The approach allows for the estimation of the value of the rate constant for interfacial charge transfer to nonadsorbing outer-sphere redox species at semimetallic electrodes. Rate constants for interfacial electron transfer for a variety of one-electron redox couples at semimetallic electrodes have been calculated relative to the rate constant of the ferrocenium/ferrocene redox couple at a gold electrode. Good agreement is found, in general, between the calculated and observed rate constants.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp062141eDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp062141ePublisherArticle
ORCID:
AuthorORCID
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2006 American Chemical Society. Received: April 5, 2006; In Final Form: June 12, 2006. Publication Date (Web): September 2, 2006. We acknowledge the Department of Energy, Office of Basic Energy Sciences, for support of this work. We also acknowledge helpful discussions with Norman Sutin.
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Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
Issue or Number:39
Record Number:CaltechAUTHORS:20170524-100829690
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170524-100829690
Official Citation:A Comparison between Interfacial Electron-Transfer Rate Constants at Metallic and Graphite Electrodes William J. Royea, Thomas W. Hamann, Bruce S. Brunschwig, and Nathan S. Lewis The Journal of Physical Chemistry B 2006 110 (39), 19433-19442 DOI: 10.1021/jp062141e
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77705
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 May 2017 17:13
Last Modified:03 Oct 2019 18:00

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