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Atomistic Mechanisms Underlying Selectivities in C_1 and C_2 Products from Electrochemical Reduction of CO on Cu(111)

Xiao, Hai and Cheng, Tao and Goddard, William A., III (2017) Atomistic Mechanisms Underlying Selectivities in C_1 and C_2 Products from Electrochemical Reduction of CO on Cu(111). Journal of the American Chemical Society, 139 (1). pp. 130-136. ISSN 0002-7863. doi:10.1021/jacs.6b06846.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Xiao, Hai0000-0001-9399-1584
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2016 American Chemical Society. Received: July 2, 2016. Publication Date (Web): December 7, 2016. This work was supported 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 No. DE-SC0004993. We are grateful to Dr. Ravishankar Sundararaman, Dr. Robert J. Nielsen, and Prof. Manuel P. Soriaga for helpful discussions. The calculations were carried out on the Zwicky (Caltech) and NERSC computing resources. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Issue or Number:1
Record Number:CaltechAUTHORS:20161209-133639283
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Official Citation:Atomistic Mechanisms Underlying Selectivities in C1 and C2 Products from Electrochemical Reduction of CO on Cu(111) Hai Xiao, Tao Cheng, and William A. Goddard, III Journal of the American Chemical Society 2017 139 (1), 130-136 DOI: 10.1021/jacs.6b06846
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:72694
Deposited By: Tony Diaz
Deposited On:09 Dec 2016 22:13
Last Modified:11 Nov 2021 05:05

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