Published October 5, 2006 | public
Journal Article

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

An error occurred while generating the citation.

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.

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.

Additional details

Created:
August 19, 2023
Modified:
October 25, 2023