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

Singh, Meenesh R.; Kwon, Youngkook; Lum, Yanwei; Ager, Joel W.; Bell, Alexis T.

doi:10.1021/jacs.6b07612

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

Journal Article · Wed Sep 14 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b07612· OSTI ID:1456958

Singh, Meenesh R. ^[1]; Kwon, Youngkook ^[2]; Lum, Yanwei ^[3]; Ager, Joel W. ^[3]; Bell, Alexis T. ^[4]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of Chicago, IL (United States). Department of Chemical Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Korea Research Institute of Chemical Technology, Daejeon (Korea). Carbon Resources Institute
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Department of Materials Science & Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Material Science Division; Univ. of California, Berkeley, CA (United States). Department of Chemical & Biomolecular Engineering

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. In this paper, we report that these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in the vicinity of the cathode. With increasing cation size, the pK_a 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. Finally, 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1456958

Journal Information:: Journal of the American Chemical Society, Vol. 138, Issue 39; Related Information: © 2016 American Chemical Society.; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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