Rational Design of Dual-Atom Catalysts for Electrochemical CO2 Reduction to C1 and C2 Products with High Activity and Selectivity: A Density Functional Theory Study

Carbon dioxide (CO2) electroreduction using renewable energy provides a sustainable solution to mitigate greenhouse effects and achieve carbon neutrality. Developing high-performance electrocatalysts for the CO2 reduction reaction (CO2RR) is key to promoting such a technology. Herein, we systematically explored the CO2RR catalytic activity of 325 dual-metal-site catalysts (DMSCs) through density functional theory (DFT) calculations. Among them, the Sc/Tc DMSC is particularly advantageous for HCOOH, CH4, and CH3CH2OH production, with limiting potentials of −0.45 V, −0.45 V, and −0.46 V, respectively. The Ti/Rh DMSC can selectively convert CO2 to CH3CH2OH at ultralow overpotentials (UL = −0.21 V). HCOOH is the preferred product of the CO2RR on the Mn/Fe site with a UL of −0.30 V. Mn/Fe presents the highest inhibitory effects on the side reaction, the hydrogen evolution reaction (HER), with a UL of −0.66 V. Moreover, electronic analysis was conducted to further explain the enhancement for the CO2RR of explored catalysts at the subatomic level. Our work offers a strategy for screening of high-performance DMSCs and reveals the mechanisms of the CO2RR to target products for selected catalysts, benefiting the further development of CO2RR electrocatalysts.