Aggregation-based phase transition tailored heterophase junctions of AgInS₂ for boosting photocatalytic H₂ evolution

Due to high defect tolerance and multiphase allowance, AgInS₂ (AIS) quantum dots (QDs) provide chances for designing new type junctions via tailoring defects, size, or phase structure. These new type junctions potentially enhance photoelectric performance, such as photocatalytic H2 evolution (PHE). Here, ultra-small AIS QDs (∼1 nm) with well-defined exciton absorption were prepared aqueously via a reverse hot-injection procedure for the first time. A coalescence or fast aggregation-based growth was observed for coarsening at 95 or 135 ℃, respectively. XRD and TEM investigations revealed that the tetragonal-orthorhombic (t-o) phase transition occurred via aggregation-based growth. The studies on phase transition kinetics resulted in fine-tailoring on AIS polymorphs, favoring t-o AIS junctions. UV-vis absorption spectra confirm the double absorption edge of the t-o heterophase junction with enhanced visible absorption. Steady and transient PL spectra suggest improvements in carriers' separation/transfer in this t-o junction. As a result, the optimized t-o AIS shows superior photocatalytic H₂ evolution rates of 1022 μmol. g^-1. h^-1, 51.1 times that of t-AIS or 3.8 times that of o-AIS. This work is expected to provide new insight for designing ternary alloyed QDs with strongly coupled interfaces for effective H₂ generations.