0D/2D heterostructure constructed by ultra-small chalcogenide-cluster aggregated quaternary sulfides and g-C3N4 for enhanced photocatalytic H2 evolution

Abstract

The lack of atomically precise models in traditional semiconductor materials impedes further understanding of photocatalytic process at atomic scale. Herein, a series of ultra-small T4-Cd4-xZnxIn16S35 (x: 0 ~ 4) metal chalcogenide supertetrahedral nanoclusters (MCSNs) aggregated quaternary ultra-small sulfide nanoparticles was successfully loaded on g-C3N4 to build 0D/2D heterostructure for photocatalytic H2 evolution. As MCSNs were tailorable at sub-nanometer level with fine-tuned ratio of Cd:Zn, the energy band structure of such models was highly adjustable and owing to the suitable band structure, enhanced photogenerated electron-hole separation efficiency and decreased interfacial charge transfer resistance of the heterojunction, optimized hydrogen production rate of 288 μmol g−1 h−1 was obtained for the T4-Cd1Zn3/g-C3N4 heterostructure, which is about 7 times than that of pristine g-C3N4. This work not only provides a better understanding on energy band modulation of MCSNs-based photocatalysts at the atomic level, but also holds great promise for long-term impacts on creating new-type of photocatalysts based-on MCSNs.