Modulating the Local Electronic Property and Intermediate Binding Energy of ZnO by Heteroatom Doping for Efficient Electrocatalytic CO2 Reduction

Abstract Engineering the electronic properties of catalysts by element doping to obtain appropriate intermediate binding energy is a promising strategy to design efficient catalysts for electrocatalytic CO 2 reduction reaction (CO 2 RR). Herein, we dope ZnO with heteroatoms (Bi, Mn, Co) of different external electronic activities and electronegativities, which lead to different CO 2 RR performances. The introduction of Bi (p‐block metal element with stable external electrons and relatively high electronegativity) into ZnO results in enhanced CO 2 RR performance. Density functional theory (DFT) calculations demonstrate that Bi−ZnO could regulate the local charge distribution of ZnO, as well as weak the binding energy of *H and *COOH while increase the binding energy of *OCHO, thus significantly inhibit hydrogen evolution reaction (HER) and accelerate CO 2 RR. This work demonstrates the feasibility of modulating electronic property of electrocatalysts in optimizing CO 2 RR selectivity and activity.