Asymmetric Local Electric Field Induced by Dual Heteroatoms on Copper Boosts Efficient CO2 Reduction Over Ultrawide Potential Window

Abstract Electrocatalytic reduction of CO 2 powered by renewable electricity provides an elegant route for converting CO 2 into valuable chemicals and feedstocks, but normally suffers from a high overpotential and low selectivity. Herein, Ag and Sn heteroatoms were simultaneously introduced into nanoporous Cu (np‐Ag/Sn−Cu) mainly in the form of an asymmetric local electric field for CO 2 electroreduction to CO in an aqueous solution. The designed np‐Ag/Sn−Cu catalyst realizes a recorded 90 % energy efficiency and a 100 % CO Faradaic efficiency over ultrawide potential window (ΔE=1.4 V), outperforming state‐of‐the‐art Au and Ag‐based catalysts. Density functional theory calculations combined with in situ spectroscopy studies reveal that Ag and Sn heteroatoms incorporated into Cu matrix could generate strong and asymmetric local electric field, which promotes the activation of CO 2 molecules, enhances the stabilization of the *COOH intermediate, and suppresses the hydrogen evolution reaction, thus favoring the production of CO during CO 2 RR.