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

Abstract

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.