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 |
| Publication status | Published - Feb 15 1996 |
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Keywords
- Cobalt complexes
- Cyclopentadienyl complexes
- Electron transfer
- Kinetics and mechanism
- Reduction
ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
Charge transfer rate constants for the reduction of cobaltocenium at accumulated n-Si electrodes. / Tan, Ming X.; Lewis, Nathan S.
In: Inorganica Chimica Acta, Vol. 242, No. 1-2, 15.02.1996, p. 311-321.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Charge transfer rate constants for the reduction of cobaltocenium at accumulated n-Si electrodes
AU - Tan, Ming X.
AU - Lewis, Nathan S
PY - 1996/2/15
Y1 - 1996/2/15
N2 - 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.
AB - 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.
KW - Cobalt complexes
KW - Cyclopentadienyl complexes
KW - Electron transfer
KW - Kinetics and mechanism
KW - Reduction
UR - http://www.scopus.com/inward/record.url?scp=0008757960&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0008757960&partnerID=8YFLogxK
M3 - Article
VL - 242
SP - 311
EP - 321
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 1-2
ER -