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 (<i>U</i> _L = -0.21 V). HCOOH is the preferred product of the CO₂RR on the Mn/Fe site with a <i>U</i> _L of -0.30 V. Mn/Fe presents the highest inhibitory effects on the side reaction, the hydrogen evolution reaction (HER), with a <i>U</i> _L 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.