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

Electrochemical N oxidation reaction (NOR), using water and N 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 and sluggish kinetics for 10-electron transfer, emerging electrocatalysts remain largely underexplored. Herein, Ru-nanoclusters-coupled Mn O catalysts decorated with atomically dispersed Ru atoms (Ru-Mn O ) are designed and explored as an advanced electrocatalyst for ambient N oxidation, with an excellent Faraday efficiency (28.87%) and a remarkable NO yield (35.34 µg h mg ), 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 O can effectively activate the chemically inert N , 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.