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. doi:10.1021/jp062141e. 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.
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| 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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| Issue or Number: | 39 | |||||||||
| DOI: | 10.1021/jp062141e | |||||||||
| 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: | 15 Nov 2021 17:33 |
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