An Accurate Electrochemical CO 2 Reduction Description on Transitional Metal Doped Cu (100) Surface

The combustion of fossil fuels leads to excessive CO 2 emissions, triggering global warming and energy crisis. Electrocatalytic CO 2 reduction (eCO 2 RR) offers a feasible way to convert CO 2 into high‐value‐added chemicals. Extensive investigations have been made on Cu‐based catalysts, which have been proven to be highly efficient in eCO 2 RR; however, deviations exist, i.e., different potentialdetermining steps (PDS) obtained from theoretical and experimental results. We show that the PBE + D3/M06 hybrid computational scheme of Araujo et al. (Nature Communications, 2022, 13, 6853) that combines periodic PBE + D3 structural optimization with cluster‐model M06 energy corrections could match the eCO 2 RR experimental data on Cu based catalysts. It shows that for the eCO 2 RR on the Cu (100) surface, the PDS for methane formation is the *CO → *CHO hydrogenation step. The limiting potential calculated by this method (0.81 eV) closely matches the experimental value (0.80 eV). We further use this method to predict the PDS on transition metal‐doped Cu (100) surfaces to accurately predict PDS. This work confirms that PBE + D3/M06 provides a precise and efficient method to predict the experimental eCO 2 RR reaction process.