Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO 2 over Ag and Cu
Open accessAbstract
Electrolyte cation size is known to influence the electrochemical reduction of CO 2 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 the vicinity of the cathode. With increasing cation size, the p K 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 CO 2 . The consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H 2 and CH 4, and an increase in Faradaic efficiencies for CO, C 2 H 4, and C 2 H 5 OH, in full agreement with experimental observations for CO 2 reduction over Ag and Cu.
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On pressurized Ni and Fe, the selectivity towards longer chain hydrocarbon products increased with temperature up to 80°C.
“On pressurized Ni and Fe, the selectivity towards longer chain hydrocarbon products increased with temperature up to 80°C.[228,248]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [228]
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- Authors
- Singh, M. R., Kwon, Y., Lum, Y., Ager, J. W., & Bell, A. T.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- Corresponding author
- Bell, Alexis T.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-09-26
- Volume
- 138
- Issue
- 39
- Pages
- 13006-13012
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2520778196
- Cited by
- 985
- References
- 32
- Citations by year
- 2026: 96 · 2025: 131 · 2024: 155 · 2023: 116 · 2022: 108 · 2021: 96 · 2020: 89 · 2019: 95 · 2018: 57 · 2017: 39 · 2016: 3
- FWCI
- 17.53
- Type
- journal article
- Language
- en
- Open access
- green
- www.osti.gov
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- eScholarship (California Digital Library) (submittedVersion)
- Scholarworks@UNIST (Ulsan National Institute of Science and Technology) (submittedVersion)
- Funders
- Agency for Science, Technology and Research
- Basic Energy Sciences (DE-SC0004993)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Keywords
- electrochemical CO2 reduction, cation hydrolysis, pH buffering, Faradaic efficiency, silver electrodes, copper electrode, alkali metal cations, dissolved CO2, hydrogen production, methane production, co-production, ethylene production, ethanol production
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