Regulating Adsorption of Intermediates via d–p Orbital Electron Coupling for Boosting CO2RR

Electrochemical reduction of CO2 to high-value chemicals is one of the most promising approaches to achieving sustainable carbon cycles. However, it is confronted by large challenges in designing active electrocatalysts that exhibit both high product selectivity and current density. Here, we report an atomic iron–indium dual-atom catalyst anchored on nitrogenated carbon (Fe–In-NC), which serves as a robust electrocatalyst for CO2 reduction to CO. The Fe–In-NC catalyst demonstrates a superior CO Faradaic efficiency of 95% at −0.5 V vs RHE, surpassing that of the Fe-NC catalyst over a wide potential range from −0.7 V to −1.0 V vs RHE. Experiments and density functional theory calculations reveal that the d–p orbital electron coupling effect of Fe–In not only promotes the desorption of CO* but also reduces the barrier for the formation of COOH*. This work provides an effective strategy for tailoring the electronic structure of Fe single-atom catalysts, thereby enhancing their performance in energy conversion applications.