Construction of Nitrogen‐Doped Biphasic Transition‐Metal Sulfide Nanosheet Electrode for Energy‐Efficient Hydrogen Production via Urea Electrolysis

Abstract Urea‐assisted hybrid water splitting is a promising technology for hydrogen (H 2 ) production, but the lack of cost‐effective electrocatalysts hinders its extensive application. Herein, it is reported that Nitrogen‐doped Co 9 S 8 /Ni 3 S 2 hybrid nanosheet arrays on nickel foam (N‐Co 9 S 8 /Ni 3 S 2 /NF) can act as an active and robust bifunctional catalyst for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), which could drive an ultrahigh current density of 400 mA cm −2 at a low working potential of 1.47 V versus RHE for UOR, and gives a low overpotential of 111 mV to reach 10 mA cm −2 toward HER. Further, a hybrid water electrolysis cell utilizing the synthesized N‐Co 9 S 8 /Ni 3 S 2 /NF electrode as both the cathode and anode displays a low cell voltage of 1.40 V to reach 10 mA cm −2 , which can be powered by an AA battery with a nominal voltage of 1.5 V. The density functional theory (DFT) calculations decipher that N‐doped heterointerfaces can synergistically optimize Gibbs free energy of hydrogen and urea, thus accelerating the catalytic kinetics of HER and UOR. This work significantly advances the development of the promising cobalt–nickel‐based sulfide as a bifunctional electrocatalyst for energy‐saving electrolytic H 2 production and urea‐rich innocent wastewater treatment.