Theoretical Insights into Dual-Atomic Catalysts for Electrochemical CO<sub>2</sub> Reduction
Yun Yang, Shixi Liu
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 CO 2 molecules and the lack of effective electrocatalysts pose fundamental challenges that hinder electrochemical CO 2 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 CO 2 reduction reaction (CO 2 RR). 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 CO 2 RR. Finally, the constant potential calculation reveals that the adsorption of *CO 2 – 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.