Synthesis,Structure And Properties Of Molybdenum Sulfide Cluster Compounds

Sulfur-molybdenum cluster compounds are a class of excellent metal sulfides.Due to its wide molecular composition and unique redox characteristics,it has a wide range of applications in the fields of electrocatalysis,medicine,magnetism or supramolecular chemistry,which has attracted the attention of many scientific researchers.Although it has been reported that many sulfur-molybdenum cluster compounds with novel structures have been synthesized,but its types and development are far behind other sulfur-containing metal cluster compounds.At the same time,the self-assembly synthesis method is adopted in the reaction process,and the product can not be effectively controlled.The directional design and synthesis of thiomolybdenum cluster compounds has also become the focus and difficulty in this field.In order to obtain controllable structure of thiomolybdenum cluster compounds,we have made many attempts.This article mainly used ammonium dithiomolybdate and ammonium tetrathiomolybdate as the precursors,adding some solvent-like ligands（methylimidazole,ethylimidazole,）by adjusting the metering ratio of the reactants and the reaction temperature,the self-assembly under solvothermal conditions resulted in several novel thiomolybdenum cluster compounds.Through single crystal diffraction analysis,X-ray powder diffraction spectrum analysis,thermogravimetric analysis,infrared spectroscopy and ultraviolet spectroscopy,the structure of the prepared crystals was characterized,and their structure was determined.At the same time,the in-depth study of the electrochemical and fluorescence properties of the compound.The main work is divided into the following four parts:1.We used ammonium dithiomolybdate as the precursor and N-methylimidazole as the ligand.Under solvothermal conditions,we successfully synthesized a high-yield thiomolybdenum cluster compound[（Mo₂O₃S）（C₄N₂H₆）₄(SO₄)])（referred to as compound 1 for short）by the self-assembly method.The molybdenum atoms in compound 1 are all six-coordinated.In this work,we introduced the synthesis method and crystal structure of the compound.At the same time,we studied the electrocatalytic activity of compound 1.2.We used ammonium dithiomolybdate as the precursor,and N-methylimidazole as the main ligand,and 3-mercapto-1,2,4-triazole as the auxiliary ligand.Under solvothermal conditions,we successfully synthesizedmolybdenumsulfideclustercompound[（Mo₂O₂S₂）（C₄N₂H₆）₄（Mo O₄）]（referred to as compound 2 for short）by the self-assembly method.In addition,directly loading compound 2 into carbon paper as working electrode exhibited efficient oxygen evolution reaction（OER）catalytic performance.In 1 M KOH,compound 2 has a catalytic reaction overpotential of 389 m V at a current density of 10.0m A/cm~2,a tafel slope of 71.8 m V/dec,and catalytic stability for 12 h.3.We used ammonium dithiomolybdate as the precursor and ethylimidazole as the main ligand.Under solvothermal conditions,we successfully synthesized a thiomolybdenum cluster compound[（Mo₂O₃S）（C₅N₂H₈）₄SO₄)]（referred to as compound 3 for short）We studied its electrochemical properties,and the compound 3 has excellent luminescence properties.4.The compound[（Mo₂O₂S₆）（DMF）₂]（referred to as compound 4 for short）was successfully synthesized using ammonium tetrathiomolybdate as the precursor under the solvothermal conditions of chloroform and N,N-dimethylformamide.In this work,we described its synthesis method and crystal structure,and studied its electrochemical properties.