The Bidentate Adsorption Mode of Re‐Ni Atomic Pairs Inducing the Ultralow Overpotential in CO 2 Electroreduction

ABSTRACT Developing highly efficient, selective, and low‐overpotential electrocatalysts for the electrochemical carbon dioxide reduction reaction (eCO 2 R) is crucial for mitigating atmospheric CO 2 levels and enabling carbon‐neutral energy cycles. Herein, inspired by the activation mechanism of natural carbon monoxide dehydrogenase, we fabricated a Re‐Ni dual‐atom catalyst supported on a nitrogen‐doped carbon catalyst (ReNi‐N/C), featuring adjacent Re‐Ni atomic pairs, that exhibits outstanding eCO 2 R performance with a CO partial current density of −427.6 mA cm −2 and near 100% Faradaic efficiency for CO (FE CO ). Notably, it operates at an ultralow overpotential of 0.16 V to achieve a CO partial current density of −27.0 mA cm −1 and maintains over 95% FE CO within a broad potential range from −0.27 V to −0.80 V. In situ spectroscopy and density functional theory (DFT) calculations reveal that the formation of Re‐Ni pairs not only induces a downshift by 0.22 eV of the Ni d‐band center but also enables a bidentate adsorption configuration of the *COOH intermediate on the Ni−Re site, which accelerates *COOH formation and *CO desorption, thereby achieving high activity and selectivity in eCO 2 R. This work demonstrates a new strategy and theoretical basis for the rational design of bimetallic sites toward efficient CO 2 reduction electrocatalysts.