Publication: Quantitative analysis of cyclic voltammetry of redox mono-layers adsorbed on semiconductors: isolating electrode kinetics, lateral interactions and diode currents
Authors
Vogel, Yan B. ; Molina, Angela ; GonzÁlez Sánchez, Joaquín ; Ciampi, Simone
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Publisher
American Chemical Society
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DOI
https://doi.org/10.1021/acs.analchem.9b00336
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info:eu-repo/semantics/article
Description
© 2019 American Chemical Society. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Analytical Chemistry. To access the final edited and published work see https://doi.org/10.1021/acs.analchem.9b00336
Abstract
The design of devices whose function span from sensing their environments, to convert light into electricity or to guide chemical reactivity at surfaces, hinges around a correct and complete understanding of the factors at play when charges are transferred across an electrified solid/liquid interface. For semiconductor electrodes in particular, published values for charge transfer kinetic constants are scattered. Furthermore, received wisdom suggests slower charge trans-fer kinetics for semiconductor than for metal electrodes. We have used cyclic voltammetry of ferrocene-modified sili-con photoanodes and photocathodes as the experimental model system, and described a systematic analysis to separate charge transfer kinetics from diode effects and interactions between adsorbed species. Our results suggest that litera-ture values of electron-transfer kinetic constants at semiconductor electrodes are likely to be an underestimate of their actual values. This is revealed by experiments and analytical models, showing that the description of the potential dis-tribution across the semiconductor/monolayer/electrolyte interface has been largely oversimplified.
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Citation
Analytical Chemistry, 2019, Vol. 91, Issue 9, pp. 5929–5937
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