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

Abstract

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 *N₂ H₂ 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 .