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Electrochemical Capacitance of CO-Terminated Pt(111) Dominated by the CO–Solvent Gap

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    Electrochemical Capacitance of CO-Terminated Pt(111) Dominated by the CO–Solvent Gap
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    † Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, New York 12189, United States
    ‡ Department of Chemistry, Nano-Science Center Universitetsparken, University of Copenhagen, 5 2100 Copenhagen, Denmark
    Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands
    § Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States
    *E-mail: [email protected] (R.S.).
    *E-mail: [email protected] (K.A.S.).
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2017, 8, 21, 5344–5348
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    https://doi.org/10.1021/acs.jpclett.7b02383
    Published October 17, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    The distribution of electric fields within the electrochemical double layer depends on both the electrode and electrolyte in complex ways. These fields strongly influence chemical dynamics in the electrode–electrolyte interface but cannot be measured directly with submolecular resolution. We report experimental capacitance measurements for aqueous interfaces of CO-terminated Pt(111). By comparing these measurements with first-principles density functional theory (DFT) calculations, we infer microscopic field distributions and decompose contributions to the inverse capacitance from various spatial regions of the interface. We find that the CO is strongly electronically coupled to the Pt and that most of the interfacial potential difference appears across the gap between the terminating O and water and not across the CO molecule, as previously hypothesized. This “gap capacitance” resulting from hydrophobic termination lowers the overall capacitance of the aqueous Pt–CO interface and makes it less sensitive to electrolyte concentration compared to the bare metal.

    Copyright © 2017 American Chemical Society

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    • Experimental voltammograms and details on extracting electrochemical capacitance from these measurements (PDF)

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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2017, 8, 21, 5344–5348
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.7b02383
    Published October 17, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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