Durable hierarchical phosphorus‐doped biphase MoS₂ electrocatalysts with enhanced H* adsorption

Abstract Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions. Herein, phase engineering was employed to prepare high‐performance phosphorous‐doped biphase (1T/2H) MoS₂ (P‐BMS) nanoflakes for hydrogen evolution reaction (HER). The doping of MoS₂ with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics, which significantly enhances its electrical conductivity and structural stability, which are verified by various characterization tools, including X‐ray photoelectron spectroscopy, high‐resolution transmission electron microscopy, X‐ray absorption near‐edge spectroscopy, and extended X‐ray absorption fine structure. Moreover, the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites, which remarkably enhance its HER activity. The optimized P‐BMS electrocatalysts exhibit low overpotentials (60 and 72 mV at 10 mA cm⁻²) in H₂SO₄ (0.5 M) and KOH (1.0 M), respectively. The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques. This study has shown that phase engineering is a promising strategy for enhancing the H* adsorption of metal sulfides.