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    Quantitative Analysis of Cyclic Voltammetry of Redox Monolayers Adsorbed on Semiconductors: Isolating Electrode Kinetics, Lateral Interactions, and Diode Currents

    79596.pdf (1.294Mb)
    Access Status
    Open access
    Authors
    Vogel, Yan
    Molina, A.
    Gonzalez, J.
    Ciampi, Simone
    Date
    2019
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Vogel, Y.B. and Molina, A. and Gonzalez, J. and Ciampi, S. 2019. Quantitative Analysis of Cyclic Voltammetry of Redox Monolayers Adsorbed on Semiconductors: Isolating Electrode Kinetics, Lateral Interactions, and Diode Currents. Analytical Chemistry. 91 (9): pp. 5929-5937.
    Source Title
    Analytical Chemistry
    DOI
    10.1021/acs.analchem.9b00336
    ISSN
    0003-2700
    Faculty
    Faculty of Science and Engineering
    School
    School of Molecular and Life Sciences (MLS)
    Funding and Sponsorship
    http://purl.org/au-research/grants/arc/DP190100735
    Remarks

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Analytical Chemistry, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.analchem.9b00336.

    URI
    http://hdl.handle.net/20.500.11937/79496
    Collection
    • Curtin Research Publications
    Abstract

    © 2019 American Chemical Society.

    The design of devices whose functions span from sensing their environments to converting light into electricity or guiding chemical reactivity at surfaces often 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-transfer kinetics for semiconductors than for metal electrodes. We have used cyclic voltammetry of ferrocene-modified silicon 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 literature values of charge-transfer kinetic constants at semiconductor electrodes are likely to be underestimates of their actual values. This is revealed by experiments and analytical models showing that the description of the potential distribution across the semiconductor-monolayer-electrolyte interface has been largely oversimplified.

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