Insights into Nonelectroactive C–C Bond Formation on Cu(100) during Electrochemical CO2 Reduction from Multiconfigurational Wavefunction Theory

Martirez, John Mark P.; Carter, Emily A.

doi:10.1021/acs.jpcc.5c07792

Title: Insights into Nonelectroactive C–C Bond Formation on Cu(100) during Electrochemical CO₂ Reduction from Multiconfigurational Wavefunction Theory

Journal Article · Fri Feb 27 00:00:00 UTC 2026 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.5c07792 · OSTI ID:3022854

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Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)
Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States); Princeton Univ., NJ (United States)

Carbon–carbon (C–C) bond formation is necessary for hydrocarbon (and oxygenate) synthesis beyond methane (and formate/formic acid) during electrochemical CO and CO₂ reduction (ECOR and ECO₂R). Cu has notable ability to form hydrocarbons compared to other pure metals. In particular, the (100) facet of face-centered cubic Cu forms ethylene competitively with H₂ and methane during both ECOR and ECO₂R. Past simulations based on density functional theory (DFT) with standard exchange-correlation functional approximations predict fast nonelectroactive C–C bond formation channels involving adsorbed (*) CO together with another *CO, formyl (*CHO), or hydroxymethylidyne (*COH), forming OC*–*CO, OC*–CHO*, and OC*–*COH, respectively. Such simulations support the prevailing hypothesis that emergence of C₂ products is kinetically determined at the early stages of the reduction chemistry. Here we show, via simulations with more accurate many-body, i.e., “correlated”, wavefunction theory (enabled by an embedding scheme), that the coupling of *CO with a *CO or a *COH (previously predicted at the same level of theory to kinetically dominate over *CHO as the one-electron reduction product of *CO) is highly activated (kinetically impeded), with free energy barriers >1 eV, in contradiction to previous DFT-based simulations. Intriguingly, we find that the coupling of two adjacent *COHs incurs only a small barrier (<0.3 eV) and is exoergic (< –1 eV); however, given the predicted low surface mobility of *COH, the emergence of HOC*–*COH is also improbable, at least at low *COH coverages. We therefore conclude that it is highly unlikely for *CO to participate in nonelectroactive C–C bond formation on pristine Cu(100), contrary to conventional wisdom, and that the energetically favorable *COH dimerization may occur only after substantial buildup of *COH on the surface.

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Research Organization:: Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC02-09CH11466

OSTI ID:: 3022854

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 10 Vol. 130; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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