Unique Oxygen‐Bridged Nickel Atomic Pairs Efficiently Boost Electrochemical Reduction of Carbon Dioxide

Abstract Benefiting from the synergism between adjacent bimetallic atoms, in comparison with single atom catalysts, the dual atom catalysts have displayed great potential in electrocatalytic CO 2 reduction reaction (CO 2 RR). However, the further modulation of the electronic structure of dual atom sites to enhance CO 2 RR performance still remains a challenge. Herein, an atomically dispersed oxygen‐bridged Ni 2 N 6 O/NC catalyst with unique Ni‐O‐Ni sites is successfully synthesized through the microwave pyrolysis of the supported mixture containing the dinuclear nickel phthalocyanine and glucose on N‐doped carbon nanosheets. Experiments and density functional theory calculation reveal that the Ni‐O‐Ni sites can adsorb H + from the KHCO 3 electrolyte to in situ‐form the unique Ni‐OH‐Ni sites without Ni─Ni bonding interaction, which effectively lowers the energy barrier towards the formation of *COOH from CO 2 . As a result, the Ni 2 N 6 OH/NC catalyst exhibits a 99.4% of CO Faradaic efficiency with a 32.4 mA·cm −2 of CO partial current density at −0.7 V versus RHE in H‐cell, much superior to the Ni 2 N 6 /NC with a Ni‐Ni bonding interaction prepared by a similar procedure to that for Ni 2 N 6 O/NC but replacing microwave pyrolysis by a traditional heating process.