Enhancing built-in electric field via ZnIn2S4 nanosheet decorated with ZnS quantum dots photocatalyst for highly efficient hydrogen evolution

Two dimensional (2D) photocatalytic materials are desirable to achieve synergistic charge transfer and segregation. Here, we have developed 2D ZnIn 2 S 4 nanosheet (3–4 nm) that generates more active sites for excellent photocatalytic activity. Further, we have fabricated ZnS quantum dots (QDs) and ZnS nanoparticles (NPs) embedded with ZnIn 2 S 4 nanosheet in the form of ZnS QDs/ZnIn 2 S 4 and ZnS NPs/ZnIn 2 S 4 heterostructures prepared via one step hydrothermal method. The optimal ZnS QDs/ZnIn 2 S 4 presents the hydrogen evolution rate (HER) of 4.5 mmol g −1 h −1 which was approximately 5 and 34 times higher than that of their counterparts as well as about 3 times more efficient than ZnS NPs/ZnIn 2 S 4 heterostructure. The apparent quantum efficiency (AQE) of 21.2% was observed at 350 nm. The work functions determined through Ultraviolet photoelectron spectroscopy (UPS) elaborate the charge transfer mechanism. In situ KPFM validated the surface potential difference between the ZnS QDs and ZnIn 2 S 4 interfaces estimated about 55 mV which was approximately 2 times higher than ZnS NPs/ZnIn 2 S 4 . Theoretical calculation confirms the significant reduction in Gibbs free energy about −0.6 eV. Electron paramagnetic resonance (EPR) spectra suggest the development of a novel S-scheme mechanism and provides a unique insight into the charge transfer, separation and the surface photovoltage of heterostructure photocatalysts.