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

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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
Issue number39
Publication statusPublished - Oct 5 2006


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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