Synergistic Co and P Co‐Doping in MoS 2 /NiO Heterostructures for Electronic Modulation Toward High‐Performance Alkaline Water Electrolysis

Abstract The development of highly active and durable electrocatalysts is critical for advancing large‐scale hydrogen production via renewable‐energy‐powered alkaline water electrolysis. Herein, a heteroatom co‐doping strategy is reported to engineer the electronic structure of a MoS 2 /NiO heterostructure catalyst supported on carbon cloth (CC). The constructed Co,P‐MoS 2 @NiO/CC electrode demonstrates exceptional bifunctional activity under alkaline conditions, achieving low overpotentials of 54.3 mV for the hydrogen evolution reaction (HER) and 160 mV for the oxygen evolution reaction (OER) at 10 mA cm −2 . When employed as both anode and cathode in an alkaline electrolyzer, the catalyst requires only a cell voltage of 1.82 V to reach a high current density of 1000 mA cm −2 at 60 °C and shows remarkable stability over 100 h at 500 mA cm −2 without degradation. Mechanistic studies reveal that Co and P doping facilitate electron transfer from NiO to MoS 2 , significantly enhancing the heterostructure's electrical conductivity. Furthermore, density functional theory (DFT) calculations indicate a reduced Gibbs free energy for the OER rate‐determining step (O * →OOH * ) and a decreased energy barrier for HER at Mo sites. This work offers a viable electronic modulation strategy through multi‐heteroatom doping in heterostructured catalysts for high‐current‐density water splitting.