Theoretical Insights into Dual-Atomic Catalysts for Electrochemical CO₂ Reduction

Abstract

Electrochemical reduction of carbon dioxide into value-added products is expected to be a promising approach to mitigate climate and energy crises. However, the inert nature of CO2 molecules and the lack of effective electrocatalysts pose fundamental challenges that hinder electrochemical CO2 reduction. In this work, density functional theory was employed to explore a series of dual-atom catalysts (DACs) supported on four-type nitrogen-doped graphene for the CO2 reduction reaction (CO2RR). Based on the correlation between the adsorption free energies of the reaction intermediates, we find that the scaling relations in the multi-intermediate reactions still persist, which distinguishes them from previous studies. In addition, we construct a universal descriptor based on the intrinsic properties of catalysts, which can well assess the catalytic activity of different transition metal dual-atoms on different supports for the CO2RR. Finally, the constant potential calculation reveals that the adsorption of *CO2– exhibits insensitivity toward changes in applied potential for CoCo-3A DACs. The thermochemical step was found to be the limiting step at a low electrode potential. This research elucidates the underlying principles of reaction mechanisms and simultaneously furnishes a systematic framework for expedited exploration of proficient catalysts.