Electron Redistributed S‐Doped Nickel Iron Phosphides Derived from One‐Step Phosphatization of MOFs for Significantly Boosting Electrochemical Water Splitting

Abstract Nonprecious transition metal‐organic frameworks (MOFs) are one of the most promising precursors for developing electrocatalysts with high porosity and structural rigidity. This study reports the synthesis of high efficiency electrocatalysts based on S‐doped NiFeP. MOF‐derived S‐doped NiFeP structure is synthesized by a one‐step phosphorization process with using S‐doped MOFs as the precursor, which is more convenient and environment friendly, and also helps retain the samples’ framework. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of the NiFeP catalysts can be improved after partially replacing P by S due to the tunable electronic structure. The optimized CCS‐NiFeP‐10 reaches a current density of 10 mA cm –2 for OER with an overpotential of 201 mV and outperforms most NiFe‐based catalysts. The S doping plays an important role in tuning the Δ G values for intermediates formation in Ni atoms to a suitable value and exhibits a pronouncedly improved the OER performance. CCS‐NiFeP‐20 sample presents excellent HER performance due to the d‐band center downshifting from the Fermi level. When the voltage of the electrolytic cell is 1.50 V, a current density of 10 mA cm –2 can be obtained. This strategy paves the way for designing highly active none‐noble metal catalysts.