Atomic-Scale Tailoring C–N Coupling Sites for Efficient Acetamide Electrosynthesis over Cu-Anchored Boron Nitride Nanosheets

Electrochemical conversion of carbon and nitrogen sources into valuable chemicals provides a promising strategy for mitigating CO₂ emissions and tackling pollutants. However, efficiently scaling up C–N products beyond basic compounds like urea remains a significant challenge. Herein, we upgrade the C–N coupling for acetamide synthesis through coreducing CO and nitrate (NO₃^–) on atomic-scale Cu dispersed on boron nitride (Cu/BN) nanosheets. The specific form of Cu, such as single atom, nanocluster, and nanoparticles, endows Cu/BN different adsorption capacity for CO and NO₃^–, thereby dictating the catalytic activity and selectivity for acetamide formation. The Cu nanocluster-anchored BN (Cu NCs/BN) catalyst achieves an industrial-level current density of 178 mA cm^–2 for the C–N coupling reaction and an average acetamide yield rate of 137.0 mmol h^–1 g_cat.^–1 at −1.6 V versus the reversible hydrogen electrode. Experimental and theoretical analyses uncover the pivotal role of the strong electronic interaction between Cu nanoclusters and BN, which activates CO and NO₃^–, facilitates the formation of key *CCO and *NH₂ intermediates, and expedites the C–N coupling pathway to acetamide. This work propels the development of atomic structure catalysts for the efficient conversion of small molecules to high-value chemicals through electrochemical processes.