A comparison between interfacial electron-transfer rate constants at metallic and graphite electrodes

William J. Royea, Thomas W. Hamann, Bruce S. Brunschwig, Nathan S. Lewis

Research output: Contribution to journalArticle

52 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)19433-19442
Number of pages10
JournalJournal of Physical Chemistry B
Volume110
Issue number39
DOIs
Publication statusPublished - Oct 5 2006

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Graphite electrodes
Rate constants
electron transfer
graphite
Electrodes
electrodes
Electrons
Graphite
pyrolytic graphite
Gold
Charge transfer
charge transfer
gold
formalism
Oxidation-Reduction
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A comparison between interfacial electron-transfer rate constants at metallic and graphite electrodes. / Royea, William J.; Hamann, Thomas W.; Brunschwig, Bruce S.; Lewis, Nathan S.

In: Journal of Physical Chemistry B, Vol. 110, No. 39, 05.10.2006, p. 19433-19442.

Research output: Contribution to journalArticle

Royea, William J. ; Hamann, Thomas W. ; Brunschwig, Bruce S. ; Lewis, Nathan S. / A comparison between interfacial electron-transfer rate constants at metallic and graphite electrodes. In: Journal of Physical Chemistry B. 2006 ; Vol. 110, No. 39. pp. 19433-19442.
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