Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

Xiao, Hai; Cheng, Tao; Goddard, III, William A.; Sundararaman, Ravishankar

doi:10.1021/jacs.5b11390

Title: Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

Journal Article · Mon Jan 04 00:00:00 EST 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b11390· OSTI ID:1328819

Xiao, Hai ^[1]; Cheng, Tao ^[1]; Goddard, III, William A. ^[1]; Sundararaman, Ravishankar ^[1]

Materials and Process Simulation Center (MSC) and Joint Center for Artificial Photosynthesis (JCAP), California Institute of Technology, Pasadena, California 91125, United States

Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO₂ to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C₁ pathway proceeds through COH to CHOH to form CH₄ while C₂ (C₃) pathways are kinetically blocked; (2) at neutral pH, the C₁ and C₂ (C₃) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C₁ pathways by kinetics, thereby boosting selectivity for multi-carbon products.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0004993

OSTI ID:: 1328819

Alternate ID(s):: OSTI ID: 1436113

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 2; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 284 works

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Title: Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)

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