Atomic Bridging Structure of Nickel–Nitrogen–Carbon for Highly Efficient Electrocatalytic Reduction of CO2

Abstract To meet strategic applications, electrochemical reduction of CO 2 into value‐added chemical molecules would be improved by the rational design of advanced electrocatalysts with atomically dispersed active sites. Herein an electrospun‐pyrolysis cooperative strategy is presented to not only modulate the porous structure of the carbon support for favorable charge and mass transfer, but also adjust the bridging structure of atomically dispersed metal species. Typically, the experimental results and theoretical calculations revealed that the unique chemical structure of binuclear nickel bridging with nitrogen and carbon atoms (namely Ni 2 −N 4 −C 2 ) tunes the electronic nature of the d‐states for the optimal adsorption of carbon dioxide and intermediates, thus inducing the substantial enhancement of CO 2 reduction via the thermodynamically more favorable pathway. The identification of such a structure demonstrates the large space to modulate the atomic bridging status for optimizing electrocatalysis.