Synergistic Electronic Modulation of 1T/2H Mixed‐Phase MoS ₂ via Phosphorus Insertion and Carbon Coating for Enhanced Acidic Hydrogen Evolution Kinetics

ABSTRACT

MoS ₂ is considered a promising electrocatalyst for the hydrogen evolution reaction (HER) because of its low cost and excellent stability. However, its practical application is severely limited by the scarcity of edge active sites and poor intrinsic electrical conductivity. Herein, phosphorus‐doped and carbon‐coated 1T/2H mixed‐phase MoS ₂ nanosheets with abundant sulfur vacancies (P‐MoS ₂ /C) were synthesized through a facile hydrothermal method using a polyoxometalate precursor, followed by the introduction of glucose. Combined Raman spectroscopy, X‐ray photoelectron spectroscopy, and electron paramagnetic resonance analyses confirmed that glucose induced the phase transition of MoS ₂ from the 2H phase to the 1T phase. Meanwhile, P incorporation and the glucose‐derived carbon coating modulated the electronic structure of Mo atoms and generated abundant sulfur vacancies on the MoS ₂ basal plane, thereby increasing the number of active sites and improving electrical conductivity. Further experimental and theoretical investigations revealed that interfacial charge redistribution increased the density of states near the Fermi level and optimized both charge‐transfer kinetics and the adsorption energy of H*, leading to enhanced HER activity. Consequently, P‐MoS ₂ /C‐0.4 exhibited superior HER performance under acidic conditions, requiring low overpotentials of 129 and 243 mV to achieve current densities of 10 and 100 mA cm ⁻² , respectively, while maintaining high selectivity and good stability. This work presents a synergistic modulation strategy for constructing high‐performance MoS ₂ ‐based HER electrocatalysts with potential for practical applications.