Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products

Lum, Yanwei; Cheng, Tao; Goddard, William A.; Ager, Joel W.

doi:10.1021/jacs.8b03986

Cited by 251CO2 Reduction Techniques and CatalystsElectrocatalysts for Energy ConversionCarbon dioxide utilization in catalysis

Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products

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Lum, Yanwei, Cheng, Tao, Goddard, William A., Ager, Joel W.·2018·Journal of the American Chemical Society

DOI 10.1021/jacs.8b03986

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Abstract

Numerous studies have examined the electrochemical reduction of CO (COR) to oxygenates (e.g., ethanol). None have considered the possibility that oxygen in the product might arise from water rather than from CO. To test this assumption, C 16 O reduction was performed in H 2 18 O electrolyte. Surprisingly, we found that 60–70% of the ethanol contained 18 O, which must have originated from the solvent . We extended our previous all-solvent density functional theory metadynamics calculations to consider the possibility of incorporating water, and indeed, we found a new mechanism involving a Grotthuss chain of six water molecules in a concerted reaction with the *C–CH intermediate to form *CH–CH( 18 OH), subsequently leading to ( 18 O)ethanol. This competes with the formation of ethylene that also arises from *C–CH. These unforeseen results suggest that all previous studies of COR under aqueous conditions must be reexamined.

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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 2 Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [57]

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Authors: Lum, Y., Cheng, T., Goddard, W. A., & Ager, J. W.
Affiliations: Lawrence Berkeley National Laboratory (US)
California Institute of Technology (US)
Corresponding author: Goddard, William A.
Ager, Joel W.
ORCID: Lum, Yanwei
Cheng, Tao
Goddard, William A.
Ager, Joel W.
Venue: Journal of the American Chemical Society
Publisher: American Chemical Society (ACS)
Published: 2018-07-16
Volume: 140
Issue: 30
Pages: 9337-9340
ISSN: 0002-7863 (ISSN-L)
1520-5126
DOI: 10.1021/jacs.8b03986
OpenAlex: W2883018259
Cited by: 251
References: 32
Citations by year: 2026: 12 · 2025: 33 · 2024: 42 · 2023: 41 · 2022: 39 · 2021: 34 · 2020: 22 · 2019: 26 · 2018: 2
FWCI: 4.86
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)
eScholarship (California Digital Library) (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 › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
Keywords: CO electroreduction, oxygenate production, aqueous electrolyte solutions, ethylene production, reaction mechanism

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Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products

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