Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory

Zhao, Qing; Martirez, John P.; Carter, Emily A.

doi:10.1021/jacs.1c00880

Revisiting Understanding of Electrochemical CO₂ Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory

Journal Article · Wed Apr 14 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c00880· OSTI ID:1808091

Zhao, Qing ^[1]; ^[2]; ^[3]

Princeton Univ., NJ (United States); Princeton University
Univ. of California, Los Angeles, CA (United States)
Princeton Univ., NJ (United States); Univ. of California, Los Angeles, CA (United States)

Copper (Cu) electrodes, as the most efficacious of CO₂ reduction reaction (CO₂RR) electrocatalysts, serve as prototypes for determining and validating reaction mechanisms associated with electrochemical CO₂ reduction to hydrocarbons. As in situ electrochemical mechanism determination by experiments is still out of reach, such mechanistic analysis typically is conducted using density functional theory (DFT). The semilocal exchange-correlation (XC) approximations most often used to model such catalysis unfortunately engender a basic error: predicting the wrong adsorption site for CO (a key CO₂RR intermediate) on the most ubiquitous facet of Cu, namely, Cu(111). This longstanding inconsistency casts lingering doubt on previous DFT predictions of the attendant CO₂RR kinetics. Here, we apply embedded correlated wavefunction (ECW) theory, which corrects XC functional error, to study the CO₂RR on Cu(111) via both surface hydride (*H) transfer and proton-coupled electron transfer (PCET). We predict that adsorbed CO (*CO) reduces almost equally to two intermediates, namely, hydroxymethylidyne (*COH) and formyl (*CHO) at –0.9 V vs the RHE. In contrast, semilocal DFT approximations predict a strong preference for *COH. With increasing applied potential, the dominance of *COH (formed via potential-independent surface *H transfer) diminishes, switching to the competitive formation of both *CHO and *COH (both formed via potential-dependent PCET). Furthermore, our results also demonstrate the importance of including explicitly modeled solvent molecules in predicting electron-transfer barriers and reveal the pitfalls of overreliance on simple surface *H transfer models of reduction reactions.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1808091

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 16 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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54 ENVIRONMENTAL SCIENCES
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Transfer reactions
chemical reactions
chemical structure
electrochemistry
free energy
proton coupled electron transfer

Revisiting Understanding of Electrochemical CO2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory

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Revisiting Understanding of Electrochemical CO₂ Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory