Surface functionalization of discrete metal-chalcogenide supertetrahedral clusters and the photocatalytic application

Atomically precise metal-chalcogenide supertetrahedral clusters (MCSCs) are supposed to be more attractive for functionalization than conventional metal-sulfide quantum dots owing to their potential ability to establish precise structure-composition-property relationships. However, the accurate surface functionalization of such cluster-based species remains difficult. In this paper, we present a facile method for synthesizing discrete MCSCs decorated with different functional groups via a one-step solvothermal reaction, which was demonstrated to have better solvent dispersibility compared with ligand-free ones. In addition, the composites were also prepared by combining ligand-free clusters (or ligand-partially protected or amino-modified ones) with two-dimensional MXene nanosheets. The composites derived from amino-modified clusters exhibited optimal performance of photocatalytic hydrogen evolution. Furthermore, the hydrogen bonding interactions between modified amino groups and MXene nanosheets were verified by 1H-NMR spectroscopy. This work provides a facile approach for the surface functionalization of MCSCs, and facilitates the expansion of the functionality of atomically precise nano-species. A facile approach for modifying the surface structure of discrete metal chalcogenide supertetrahedral clusters to improve their contact with MXene nanosheets, thus enhancing their photocatalytic performance.