Cooperative Ni(Co)‐Ru‐P Sites Activate Dehydrogenation for Hydrazine Oxidation Assisting Self‐powered H2 Production

Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever‐growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm−2, respectively. Inspiringly, two‐electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record‐high current density of 522 mA cm−2 at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru1−NiCoP optimize H* adsorption, and enhance adsorption of *N2H2 to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self‐powered H2 production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h−1 m−2. Unique atomic Ni(Co)−Ru−P interfacial sites on a matrix of NiCoP nanowire arrays were designed as highly active and stable catalysts for alkaline hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER). A self‐powered H2 production system utilizing an overall hydrazine splitting device driven by a direct hydrazine fuel cell achieved a promising rate of 24.0 mol h−1 m−2.