Enhancing photocatalytic activity by changing the electronic structure of the catalyst is an effective strategy. 2H‐MoS2 has semiconductor properties, and its unsaturated side S atom is the main active site for its photocatalytic activity. However, due to the weak S‐H bond energy, its hydrogen adsorption capacity is weak. In this work, the electronic structure of MoS2 is adjusted by S‐rich treatment, resulting in the formation of Mo vacancy (MoS2‐VMo). The level of Mo vacancies was assessed using UV‐visible diffuse reflectance spectroscopy (UV‐vis DRS). As these vacancies can capture certain photogenerated electrons, thereby reducing the recombination of electron‐hole pairs. Through DFT calculation, it is found that the anti‐bonding orbital electron filling of MoS2‐VMo is weakened, the bond energy of S‐Mo bond is weakened, and the bond energy between S‐H bond is enhanced, which is more conducive to proton adsorption. The photocatalytic activity for hydrogen evolution of MoS2‐3, which underwent the optimal S‐rich treatment, achieved a remarkable rate of 2404.6 μmol g‐1 h‐1 in dye eosin Y (EY) sensitization system, significantly surpassing that of MoS2 lacking the S‐enriched treatment. This study introduces a novel concept for enhancing the photocatalytic hydrogen evolution performance of metal sulfides via defect engineering.
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