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 CO 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 (NO) 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 NO, 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 for the C-N coupling reaction and an average acetamide yield rate of 137.0 mmol h g 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 NO, facilitates the formation of key *CCO and *NH 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.