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Title: Atomistic mechanisms underlying selectivities in C 1 and C 2 products from electrochemical reduction of CO on Cu(111)

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. Furthermore, 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.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Grant/Contract Number:
SC0004993
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 1; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
California Institute of Technology, Pasadena, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1347749
Alternate Identifier(s):
OSTI ID: 1347750