Structural Design,Preparation And Application Of [Mo₃S₁₃]^2- Clusters Based On Functional Materials For Hydrogen Evolution

Amorphous materials are one kind of non-equilibrium material and have become one of the most active research fields.Amorphous molybdenum sulfide（a-Mo S_x）,as a representative of amorphous materials,has attracted much attention due to its excellent physical structure and active chemical properties.Researchers found that a-Mo S_x is composed of molybdenum sulfur clusters with definite atomic structure.Although the actual structure is still controversial,the[Mo₃S₁₃]^2-cluster can be used as the basic building blocks to form a-Mo S_x.Nanoclusters are ideal substrates for creating new advanced functional materials and are the ideal model for correlating macroscopic properties and microscopic of matter,which is of great significance for deeply knowledge and understanding of material transformation.[Mo₃S₁₃]^2-clusters have the structural characteristics of regular fragments of Mo S₂ like bulk phase and can be regarded as regular ultra-small"quantum dots".In this paper,based on the existing molybdenum-sulfur clusters with a well-defined structure,[Mo₃S₁₃]^2-clusters are used as the motifs to construct functional catalytic hydrogen precipitator materials with a multi-level structure of clusters.The paper focuses on the catalytic hydrogen precipitation conformational relationships of[Mo₃S₁₃]^2-cluster assemblies and reveal the internal relationship between the microstructure of molybdenum-sulfur clusters,the bonding mode between clusters and the hydrogen evolution performance.The main research contents of this paper include the following:1.NH₄(Mo₃S₁₃)·n H₂O crystals were prepared by chemical wet method,and then[Mo₃S₁₃]^2-solution was obtained by methanol dissolution.The prepared samples were characterized by SEM,HRTEM,XRD and EDX for morphology,structure and elemental composition,respectively.2.The[Mo₃S₁₃]^2-clusters in methanol solution were assembled stepwise without templates using the solvent volatilization self-assembly method to obtain molybdenum sulfide nanowire assemblies.The morphological structure,chemical components and atomic structure of molybdenum sulfide nanowires were characterized by TEM and spherical aberration-corrected electron microscopy,The bonding patterns between clusters of molybdenum sulfide nanowires were probed,revealing the transformation pattern of clusters to metamaterial structures or assemblies,providing new ideas for the precise construction and optimal reorganization of cluster structural units in a hierarchical,modular and intelligent manner.3.Using the EY/TEOA photocatalytic hydrogen precipitation system,the photocatalytic hydrogen precipitation performance of[Mo₃S₁₃]^2-cluster assemblies were evaluated,and the maximum H₂ production rate was 38 mmol g^-1 h^-1,which was much higher than the hydrogen evolution performance of other Mo-S system catalysts.It is shown that the nanowire assemblies of[Mo₃S₁₃]^2-clusters,a-Mo S_x,as catalysts can significantly enhance the photocatalytic hydrogen evolution performance of the corresponding systems.