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    Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu

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    Date
    2016-10-05
    Author
    Singh, Meenesh R.
    Kwon, Youngkook
    Lum, Yanwei
    Ager III, Joel W.
    Bell, Alexis T.
    Publisher
    American Chemical Society
    Metadata
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    Abstract
    Electrolyte cation size is known to influence the electrochemical reduction of CO2 over metals; however, a satisfactory explanation for this phenomenon has not been developed. We report here that these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in vicinity of the cathode. With increasing cation size, the pKa for cation hydrolysis decreases and is sufficiently low for hydrated K+ , Rb+ , and Cs+ to serve as buffering agents. Buffering lowers the pH near the cathode leading to an increase in the local concentration of dissolved CO2. The consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H2 and CH4 and an increase in Faradaic efficiencies for CO, C2H4, and C2H5OH in full agreement with experimental observations for CO2 reduction over Ag and Cu.
    Subject
    Electrochemical CO2 Reduction
    Cation hydrolysis
    Polarization loss
    Type
    Article
    Date available in INDIGO
    2017-11-18T10:30:09Z
    URI
    http://hdl.handle.net/10027/21471
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    • Publications - Chemical Engineering

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