Abstract
A theoretical description of heterogeneous charge transfer rate constants has been developed for accumulated semiconductor electrodes in contact with outer sphere redox couples. Analysis of the rate constants using a Fermi Golden Rule formalism in a non-adiabatic electron transfer framework has facilitated a theoretical comparison between the rate constants of metal and accumulated semiconductor electrodes in contact with a common electrolyte-redox couple solution. Chronoamperometric measurements of n-Si electrodes in contact with CH3OH-cobaltocenium (CoCp2)+-CoCp2 have been performed to investigate these predictions experimentally. A standard rate constant, ko, of (2-4) × 10-2 cm s-1 was obtained for n-SiAZH3OH-CoCp2+/0 contacts, while the CoCp2+/0 redox couple was found to be electrochemically reversible (ko > 0.1 cm s-1) at Hg electrodes under the same conditions.
Original language | English |
---|---|
Pages (from-to) | 311-321 |
Number of pages | 11 |
Journal | Inorganica Chimica Acta |
Volume | 242 |
Issue number | 1-2 |
DOIs | |
Publication status | Published - Feb 15 1996 |
Keywords
- Cobalt complexes
- Cyclopentadienyl complexes
- Electron transfer
- Kinetics and mechanism
- Reduction
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry