Understanding the Activity Trends in Electrocatalytic Nitrate Reduction to Ammonia on Cu Catalysts

Cu-based catalysts possess great potential in the electrocatalytic nitrate (NO 3 – ) reduction reaction for ammonia (NH 3 ) synthesis. However, the low atomic economy limits their further application. Here we report a Cu single-atom (SA) incorporated in nitrogen-doped carbon (Cu SA/NC) with high atomic economy, which exhibits superior NH 3 Faradaic efficiency (FE) of 100% along with an impressive NH 3 yield rate of 7480 μg h –1 mg cat. –1 . As counterparts, Cu s+n /NC, with mixed SA and nanoparticles (NPs), shows decreasing NH 3 FE with decreasing SA content, but the production of N 2 and N 2 O increases gradually, which reaches the maximum on pure Cu NPs. In situ characterizations and theoretical calculations reveal that a higher NH 3 FE of Cu SA/NC is ascribed to a lower free energy of the rate-limiting step (HNO* → N*) and effective inhibition for the N-N coupled process. This work provides the intuitive activity trends of Cu-based catalysts, opening an avenue for subsequent catalysts design.