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 (Zn₁Cu_x/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.

Single atom catalysts (SACs) have become one of research focuses in heterogeneous catalysis for their effective utilization of active metal atoms and unique properties in various catalytic reactions. However, due to their high surface energy, noble metal single atoms like Pt tend to migrate and agglomerate to form larger clusters or nanoparticles, which makes it a challenge to fabricate noble metal SACs with high loading (> 5 wt.%). Furthermore, the decisive factors of loading maximum are still not clear. Here, we reported a manganese oxide supported Pt SAC with a high loading of 5.6 wt.% synthesized by selective dissolution strategy. The pre-stabilization of Pt by coordinated oxygen and the abundant surface defects of support are the determinants of high loading. The Pt SAC exhibited much better H₂ spill-over and hydrocarbon oxidation abilities with lower adsorption and dissociation energies than the manganese oxide support because of its local electronic structure with less repulsion.