Atomistic Mechanisms Underlying Selectivities in C1 and C2 Products from Electrochemical Reduction of CO on Cu(111)
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Practical environmental and energy applications of the electrochemical reduction of CO 2 to chemicals and fuels require far more efficient and selective electrocatalysts beyond the only working material Cu, but the wealth of experimental data on Cu can serve to validate any proposed mechanisms. To provide design guidelines, we use quantum mechanics to predict the detailed atomistic mechanisms responsible for C 1 and C 2 products on Cu. Thus, we report the pH dependent routes to the major products, methane and ethylene, and identify the key intermediates where branches to methanol, ketene, ethanol, acetylene, and ethane are kinetically blocked. We discovered that surface water on Cu plays a key role in the selectivity for hydrocarbon products over the oxygen-containing alcohol products by serving as a strong proton donor for electrochemical dehydration reductions. We suggest new experiments to validate our predicted mechanisms.
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Surface water either serves as a proton donor for dehydration steps or directly reacts with the adsorbates, playing an important role in modulating the selectivity between hydrocarbons and oxygenates.
“Surface water either serves as a proton donor for dehydration steps or directly reacts with the adsorbates, thereby playing an important role in modulating the selectivity between hydrocarbons and oxygenates.[56][57]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [56]
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- Authors
- Xiao, H., Cheng, T., & Goddard, W. A.
- Affiliations
- California Institute of Technology (US)
- Corresponding author
- Goddard, William A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-12-21
- Volume
- 139
- Issue
- 1
- Pages
- 130-136
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2560832335
- Cited by
- 458
- References
- 43
- Citations by year
- 2026: 41 · 2025: 55 · 2024: 66 · 2023: 53 · 2022: 54 · 2021: 57 · 2020: 44 · 2019: 39 · 2018: 33 · 2017: 14 · 2016: 1 · 2015: 1
- FWCI
- 7.86
- 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)
- CaltechAUTHORS (California Institute of Technology) (submittedVersion)
- Funders
- Office of Science (DE-SC0004993)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Keywords
- electrochemical CO2 reduction, copper electrocatalysts, Cu(111), reaction mechanism, product selectivity, methane, ethylene, surface water, proton transfer, methanol, ketenes, ethanol, acetylene, ethane, pH dependence, quantum chemical calculations
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