Self-Accommodated Electronic Metal−Support Interaction on a Platinum-Anchored Nickel−Molybdenum Nitride Catalyst for Energy-Saving Overall Hydrazine Splitting

Integrating metallic platinum species with the appropriate platform to trigger the electronic metal−support interaction (EMSI) is the most feasible strategy to achieve the modulation optimization of the electronic structure and obtain outstanding electrocatalytic activity for overall hydrazine splitting (OHzS). Herein, we report a promising catalyst consisting of platinum nanoparticles anchored on the nickel−molybdenum nitride and grown on a nickel foam (labeled as Pt-NiMoN) and employed as a bifunctional catalyst toward robust alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). Through combined experimental and theoretical investigations, we elucidate how electronic metal−support interactions (EMSI) enhance bifunctional catalysis in the Pt-NiMoN catalyst. The alternating contact between platinum and nickel−molybdenum−nitrogen mediates the adaptive optimization of valence band electronic states. Both act as a dual-active species in synergy to promote the water dissociation (Volmer step) and proton migration (Heyrovsky step) processes in HER, while also helping to accelerate the proton-coupled electron transfer kinetics in the HzOR reaction. The engineered Pt-NiMoN catalyst demonstrates exceptional activity, achieving an ηHER of 11 mV at 10 mA cm −2; in the 1 M KOH + 0.5 M N 2 H 4 system, Pt-NiMoN exhibits excellent hydrazine oxidation reaction (HzOR) activity with an onset potential of −62.4 mV and η 100 = 269 mV and when configured in an OHzS reactor achieves a considerable energy-saving performance of 0.45 V at 100 mA cm −2 . This work provides inspiration for the development of advanced bifunctional electrocatalysts based on the EMSI effect.