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Electrochemical CO reduction builds solvent water into oxygenate products

Lum, Yanwei and Cheng, Tao and Goddard, William A., III and Ager, Joel W. (2018) Electrochemical CO reduction builds solvent water into oxygenate products. Journal of the American Chemical Society, 140 (30). pp. 9337-9340. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180716-093223969

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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 18O, 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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/jacs.8b03986DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b03986PublisherSupporting Information
ORCID:
AuthorORCID
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Ager, Joel W.0000-0001-9334-9751
Additional Information:© 2018 American Chemical Society. Received: April 13, 2018; Published: July 16, 2018. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993. Y.L. acknowledges the support of an A*STAR National Science Scholarship. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562. We thank Lingfei Wei for assistance with technical illustrations. Author Contributions: Y.L. and T.C. contributed equally. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
NSFACI-1548562
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1291
Issue or Number:30
Record Number:CaltechAUTHORS:20180716-093223969
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180716-093223969
Official Citation:Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products Yanwei Lum, Tao Cheng, William A. Goddard, III, and Joel W. Ager Journal of the American Chemical Society 2018 140 (30), 9337-9340 DOI: 10.1021/jacs.8b03986
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87870
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:16 Jul 2018 16:46
Last Modified:03 Oct 2019 20:00

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