Direct electrosynthesis of acetamide from CO₂ and nitrate via an atomically engineered dual-site catalyst

The electrocatalytic synthesis of amides from abundant small molecules offers a sustainable route for green chemical production, yet faces fundamental challenges due to kinetic competition between C-C and C-N bond formation. Here we show an atomically engineered dual-site catalyst featuring nickel single atoms adjacent to copper nanoclusters (Ni-SA/Cu-NCs) on a nitrogen-doped carbon matrix for efficient CO₂ and NO₃^- co-reduction to acetamide. This architecture enables complementary functions, with Ni sites selectively converting CO₂ to CO and neighboring Cu nanoclusters promoting C-C coupling to form the *CCO intermediate while concurrently reducing NO₃^- to form the *NH₂ intermediate. The resulting synergy facilitates rapid intermediate transfer and C-N coupling, delivering an acetamide yield rate of 257.3 mmol h^-1 g_cat.^-1 at an industrial current density of 215.7 mA cm^-2, with stable operation over 160 h. In situ spectroscopic studies and theoretical calculations suggest that strong Ni-Cu electronic coupling promotes reactant adsorption and reduces the activation barriers for critical steps, including *CO dimerization and *CCO-*NH₂ coupling. This work provides an atomic-level design strategy for multi-site catalysts to steer complex electrocatalytic reactions toward value-added products.