Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru-Nanoclusters-Coupled Mn 3 O 4 Catalysts Decorated with Atomically Dispersed Ru Atoms.

Electrochemical N 2 oxidation reaction (NOR), using water and N 2 in the atmosphere, represents a sustainable approach for nitric production to replace the conventional industrial synthesis with high energy consumption and greenhouse gas emission. Meanwhile, owing to chemical inertness of N 2 and sluggish kinetics for 10-electron transfer, emerging electrocatalysts remain largely underexplored. Herein, Ru-nanoclusters-coupled Mn 3 O 4 catalysts decorated with atomically dispersed Ru atoms (Ru-Mn 3 O 4 ) are designed and explored as an advanced electrocatalyst for ambient N 2 oxidation, with an excellent Faraday efficiency (28.87%) and a remarkable NO 3 - yield (35.34 µg h -1 mg -1 cat. ), respectively. Experiments and density functional theory calculations reveal that the outstanding activity is ascribed to the coexistence of Ru clusters and single-atom Ru. The synergistic effect between the Ru clusters and Mn 3 O 4 can effectively activate the chemically inert N 2 , lowering the kinetic barrier for the vital breakage of N≡N. The intensive *OH supply and enhanced conductivity are used to regulate the catalytic kinetics for optimized performance. This work provides brand-new ideas for the rational design of electrocatalysts in complicated electrocatalytic reactions with multiple dynamics-different steps.