Self‐Derivation and Surface Reconstruction of Fe‐Doped Ni3S2 Electrode Realizing High‐Efficient and Stable Overall Water and Urea Electrolysis

Abstract Exploring earth‐abundant, highly effective, and stable electrocatalysts for overall water and urea electrolysis is urgent and essential for developing hydrogen energy technology. Herein, a simple self‐derivation method is used to fabricate a Fe‐doped Ni 3 S 2 electrode. The electrode exhibits an impressive trifunctional catalyst, with low overpotentials of 290, 198, and 254 mV at 100 mA cm −2 for the oxygen evolution reaction (OER), urea oxidation reaction (UOR), and hydrogen evolution reaction (HER). The durability is higher than 3500 h (146 days) at 100 mA cm −2 for the OER without obvious change. In situ Raman spectra reveal the incorporation of Fe inhibited S dissolution and facilitates the catalyst reconstruction. The density functional theory calculations indicate that the doping of Fe optimizes the adsorption of the rate‐determining step and the d‐band center is closer to the Fermi level, which accelerates the OER process. The two‐electrode electrolyzer needs the cell voltages of only 1.76 and 1.57 V to achieve a current density of 100 mA cm −2 and remarkable durability for more than 500 h at 100 and 500 mA cm −2 for overall water and urea splitting. This work holds great promise for industrial water and urea splitting applications.