High-Stability Ti₃C₂-QDs/ZnIn₂S₄/Ti(IV) Flower-like Heterojunction for Boosted Photocatalytic Hydrogen Evolution

The practical application of photocatalytic H₂-evolution is greatly limited by its sluggish charge separation, insufficient active sites, and stability of photocatalysts. Zero-dimensional (0D) Ti₃C₂ MXene quantum dots (MQDs) and amorphous Ti(IV) have been proven to be potential substitutes for noble co-catalyst to accelerate the separation of photogenerated electron-hole pairs and prevent the self-oxidation of photocatalysts, leading to better photocatalytic H₂-evolution performance with long-term stability. In this study, amorphous Ti(IV) and MQDs co-catalysts were successfully deposited on ZnIn₂S₄ (ZIS) microspheres composed of ultra-thin nanosheets via a simple impregnation and self-assembly method (denoted as MQDs/ZIS/Ti(IV)). As expected, the optimal MQDs/ZIS/Ti(IV) sample exhibited a photocatalytic H₂-evolution rate of 7.52 mmol·g^-1·h^-1 and excellent photostability without metallic Pt as the co-catalyst in the presence of Na₂S/Na₂SO₃ as hole scavenger, about 16, 4.02 and 4.25 times higher than those of ZIS, ZIS/Ti(IV), and MQDs/ZIS, respectively. The significantly enhanced photocatalytic H₂-evolution activity is attributed to the synergistic effect of the three-dimensional (3D) flower-like microsphere structure, the amorphous Ti(IV) hole co-catalyst, and a Schottky junction formed at the ZIS-MQDs interface, which offers more active sites, suppresses self-photocorrosion, and photo-generates the charge recombination of ZIS.