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

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). 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.

Automated summary

Copper electrodes are widely used in CO2 reduction reaction and play a key role in determining the reaction mechanisms using DFT. This study corrected the XC functional error using ECW theory and predicted the formation of different intermediates on Cu(111) under different mechanisms and applied potentials. Including explicitly modeled solvent molecules is important in predicting electron-transfer barriers and overreliance on simple surface models may lead to pitfalls in predicting reduction reactions.