Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu
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. 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 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. 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.
- Authors:
-
- 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
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1456958
- Grant/Contract Number:
- AC02-05CH11231; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 39; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., and Bell, Alexis T. Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b07612.
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., & Bell, Alexis T. Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. United States. https://doi.org/10.1021/jacs.6b07612
Singh, Meenesh R., Kwon, Youngkook, Lum, Yanwei, Ager, Joel W., and Bell, Alexis T. Wed .
"Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu". United States. https://doi.org/10.1021/jacs.6b07612. https://www.osti.gov/servlets/purl/1456958.
@article{osti_1456958,
title = {Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu},
author = {Singh, Meenesh R. and Kwon, Youngkook and Lum, Yanwei and Ager, Joel W. and Bell, Alexis T.},
abstractNote = {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 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. 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.},
doi = {10.1021/jacs.6b07612},
journal = {Journal of the American Chemical Society},
number = 39,
volume = 138,
place = {United States},
year = {Wed Sep 14 00:00:00 EDT 2016},
month = {Wed Sep 14 00:00:00 EDT 2016}
}
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