Synergistic Catalysis of Mo Single Atoms and Nanoclusters Boosts NO ₃ ^– +HCOOH Coelectrolysis for Urea Synthesis

Current urea electrosynthesis via NO3–+CO2 coelectrolysis is challenged by a low C–N coupling efficiency and competitive side reactions. To address these issues, we employ an alternative NO3–+HCOOH coelectrolysis using a catalyst comprising hybrid Mo single atoms and nanoclusters anchored on BN nanosheets (Mo1+NC/BN). Comprehensive experimental and theoretical analyses reveal the synergistic catalysis of Mo single atoms and Mo nanoclusters to promote the formation of key *NH2 and *COOH intermediates, steering their C–N coupling toward urea formation, while suppressing the competing side reactions. Impressively, by combining plasma-assisted air-to-NOx– conversion and NOx–+HCOOH coelectrolysis, we achieve an exceptional urea yield rate of 432.61 mmol h–1 g–1 and a Faradaic efficiency of 77.16%, representing a significant performance advancement for urea electrosynthesis.