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Theoretical and Experimental Upper Bounds on Interfacial Charge-Transfer Rate Constants between Semiconducting Solids and Outer-Sphere Redox Couples

Pomykal, Katherine E. and Fajardo, Arnel M. and Lewis, Nathan S. (1996) Theoretical and Experimental Upper Bounds on Interfacial Charge-Transfer Rate Constants between Semiconducting Solids and Outer-Sphere Redox Couples. Journal of Physical Chemistry, 100 (9). pp. 3652-3664. ISSN 0022-3654. doi:10.1021/jp951779f. https://resolver.caltech.edu/CaltechAUTHORS:20180720-151949312

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Abstract

Theoretical expressions for the charge-transfer rate constant at a semiconductor/liquid junction have been modified to include the effects of adiabaticity and the existence of a Helmholtz layer at the solid/liquid interface. These expressions have yielded an estimate of the maximum interfacial charge-transfer rate constant, at optimal exoergicity, for a semiconductor in contact with a random distribution of nonadsorbing, outer-sphere redox species. An experimental upper bound on this interfacial charge-transfer rate constant has been obtained through the determination of key energetic and kinetic properties for stable semiconductor electrodes in contact with outer-sphere redox species. For this purpose, n-Si/CH_3OH−dimethylferrocenium−dimethylferrocene, n-GaAs/CH_3CN−ferrocenium−ferrocene, and p-InP/CH_3CN−cobaltocenium−cobaltocene contacts were investigated using a combination of current density-potential and differential capacitance-potential methods. The upper limits for the interfacial charge-transfer rate constant at these semiconductor/liquid contacts were found to be consistent with the upper limits predicted by theory. The current density-potential behavior of n-InP and p-InP/Fe(CN)_6^(3-/4-)(aq) junctions was also examined in order to assess the validity of prior kinetic measurements on these interfaces.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/jp951779fDOIArticle
ORCID:
AuthorORCID
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 1996 American Chemical Society. Received: June 27, 1995; In Final Form: November 8, 1995. We acknowledge the National Science Foundation (NSF), Grant CHE-9221311, for support of this work. K.E.P. also acknowledges the NSF for a predoctoral fellowship.
Funders:
Funding AgencyGrant Number
NSFCHE-9221311
NSF Predoctoral FellowshipUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Division of Chemistry and Chemical Engineering9107
Issue or Number:9
DOI:10.1021/jp951779f
Record Number:CaltechAUTHORS:20180720-151949312
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180720-151949312
Official Citation:Theoretical and Experimental Upper Bounds on Interfacial Charge-Transfer Rate Constants between Semiconducting Solids and Outer-Sphere Redox Couples Katherine E. Pomykal, Arnel M. Fajardo, and Nathan S. Lewis The Journal of Physical Chemistry 1996 100 (9), 3652-3664 DOI: 10.1021/jp951779f
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88093
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Jul 2018 21:16
Last Modified:16 Nov 2021 00:23

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