Catalytic Kinetics Regulation for Enhanced Electrochemical Nitrogen Oxidation by Ru‐Nanoclusters‐Coupled Mn₃O₄ Catalysts Decorated with Atomically Dispersed Ru Atoms

Abstract

Electrochemical N₂ oxidation reaction (NOR), using water and N₂ 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 N₂ and sluggish kinetics for 10-electron transfer, emerging electrocatalysts remain largely underexplored. Herein, Ru-nanoclusters-coupled Mn₃ O₄ catalysts decorated with atomically dispersed Ru atoms (Ru-Mn₃ O₄ ) are designed and explored as an advanced electrocatalyst for ambient N₂ oxidation, with an excellent Faraday efficiency (28.87%) and a remarkable NO₃ ^- 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 Mn₃ O₄ can effectively activate the chemically inert N₂ , 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.