Rational Design of MIL-68(In) Derived Multiple Sulfides with Well Confined Quantum Dots and the Promoted Photocatalytic Hydrogen Generation.

ABSTRACT

Quantum dots (QDs) of metal sulfides were proven to be excellent cocatalysts in visible-light-driven photocatalytic reactions. Metal organic frameworks (MOFs) possess a 3D porous channel that effectively confines small QDs and preserves their high catalytic activity by preventing their aggregation. In order to precisely construct the ternary metal sulfides of ZnS/ZnIn2S4/In2S3 with well-maintained Zn-AgInS2 (ZAIS) QDs, an in situ sulfurization combining a subsequent Zn(II)-exchange strategy was employed in this work. First, the ZAIS QDs were incorporated into MIL-68(In), which were then used as the precursors to precisely construct the ternary metal sulfides of ZnS/ZnIn2S4/In2S3 with well maintained ZAIS QDs through an in situ sulfurization combining subsequent Zn(II)-exchange strategy. When the optimized nanocomposites (QDs@M-t-Zn, where t is the sulfurization time) were applied in visible light-induced photocatalytic hydrogen generation, the resulting QDs@M-24h-Zn showed a significantly improved hydrogen evolution rate of 448.96 µmol g-1 h-1, which values are clearly higher than those of MIL-68(In), QDs@MIL-68(In), and M-24h-Zn without the presence of ZAIS QDs. To elucidate the increased photocatalytic mechanism, the optical patterns and the batch electrochemical investigations were combined. It has been discovered that the matching band potentials and the close contact heterojunction enhance interface charge transfer, which in turn encourages photocatalytic hydrogen production. This study demonstrates the well-thought-out design of the uniform confinement architecture inherited from MOF QD-assisted multinary metal sulfides photocatalysts.