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Electrochemical reduction of CO2 to multi-carbon (C2) compounds presents an innovative strategy for the valorization of renewable energy into essential chemicals and fuels. However, the sluggish dynamics of carbon−carbon (C−C) coupling reaction directly impacts the efficiency and selectivity towards C2 products. Herein, we introduce a practical electrocatalytic design leveraging asymmetric *CO adsorption to facilitate C−C linkage. The synthesized a bimetallic catalyst, composed of single-atom zinc and copper clusters (Cu4), uniformly anchored on nitrogen-doped graphene (Zn1Cux/NC). In-situ Raman spectroscopy and theoretical calculations revealed that the high *CO coverage promoted the C−C coupling reaction. Moreover, optimizing the anodic reaction environment further augments C2 product yields. Notably, this catalytic system achieves a high CO2-to-C2 conversion yield of 84.9% at a commercially relevant current density of −100 mA/cm², alongside urea oxidation reaction at the anode, making a significant progress in the electrochemical reduction of CO2 to valuable C2 products.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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