Benefiting from the synergism between adjacent bimetallic atoms, in comparison with single atom catalysts, the dual atom catalysts have displayed great potential in electrocatalytic CO2 reduction reaction (CO2RR). However, the further modulation of the electronic structure of dual atom sites to enhance CO2RR performance still remains a challenge. Herein, an atomically dispersed oxygen-bridged Ni2N6O/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 KHCO3 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 CO2. As a result, the Ni2N6OH/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 Ni2N6/NC with a Ni-Ni bonding interaction prepared by a similar procedure to that for Ni2N6O/NC but replacing microwave pyrolysis by a traditional heating process.
Keywords: CO2 electroreduction; dual atom catalysts; electrocatalysis; electronic structure; oxygen bridge.
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