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Electrochemical Hydrogenation of CO on Cu(100): Insights from Accurate Multiconfigurational Wavefunction Methods

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3]
  1. Princeton Univ., NJ (United States); Northeastern Univ., Boston, MA (United States); Princeton Plasma Physics Laboratory
  2. Univ. of California, Los Angeles, CA (United States); Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States)
  3. Princeton Univ., NJ (United States); Univ. of California, Los Angeles, CA (United States)
+ Show Author Affiliations
Copper (Cu) remains the most efficacious electrocatalyst for electrochemical CO2 reduction (CO2R). Its activity and selectivity are highly facet-dependent. We recently examined the commonly proposed rate-limiting CO hydrogenation step on Cu(111) via embedded correlated wavefunction (ECW) theory and demonstrated that only this higher-level theory yields predictions consistent with potential-dependent experimental kinetics. Here, to understand the differing activities of Cu(111) and Cu(100) in catalyzing CO2R, we explore CO hydrogenation on Cu(100) using ECW theory. We predict that the preferred pathway involves the reduction of adsorbed CO (*CO) to *COH via proton-coupled electron transfer (PCET) at working potentials, although *CHO also may form with a kinetically accessible but higher barrier. In contrast, our earlier work on Cu(111) concluded that *COH and *CHO formation via PCET are equally feasible. Furthermore, this work illustrates one possible origin of the facet dependence of CO2R mechanisms and products on Cu electrodes and sheds light on how the selectivity of CO2R electrocatalysts can be controlled by the surface morphology.
Research Organization:
Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1962797
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 44 Vol. 13; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (4)

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Related Subjects

30 DIRECT ENERGY CONVERSION
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CO2 utilization
chemical reactions
density functional theory
proton coupled electron transfer
quantum mechanical simulations