Composites Based Metal-Organic Frameworks (HKUST-1):Preparation And Properties Of Degrading HD

Sulfur mustard (HD), also called mustard gas, is a kind of erosive agents, which is used generally in the current society, and it was ever called " the king of the agents". The materials, which can rapidly degrade HD, are hot spots in the current scientific studies. The main results of this work are as follows:1. Four catalysts of degrading HD were prepared through hydrothermal method, ion exchange method, and calcined method, their structures were charactered and their properties of degrading HD were studied systematically.(1) Preparation and characterization of catalysts? Preparation of catalyst 1: [(CH3)4N]5PMo10V2O40[Cu2(C9H3O6)4/3(H2O)2]6·36H2O ([(CH3)4N]5PMo10V2O40@HKUST-1) was designed and prepared with H5PMo10V2O40 and the initial materials (trimesic acid and Cu(NO3)2·3H2O) making up HKUST-1 by hydrothermal method.(2) Preparation of catalyst 2: [(CH3)4N]4AgPMo10V2O40[Cu2(C9H3O6)4/3(H2O)2]6·36H2O ([(CH3)4N]4AgPMo10V2O40@HKUST-l) was perpared by dipping 1 in silver nitrate solution, partial (CH3)4 N+in catalyst 1 were replaced by silver ions as a result..(3) Preparation of catalysts 1'and 2' Catalysts 1' and 2' were prepared by calcinating 1 and 2 in muffle furnace for 120?, respectively.(2) Charaterization of catalysts 1,2, 1' and 2':catalysts 1,2, 1' and 2' were characterized by Infrared spectroscopy(IR), Thermogravimetric Analysis(TG), powder X-ray diffraction pattern(XRD), Elemental Analysis, Scanning Electron croscope(SEM), specific surface area (BET). The structure of catalyst 1 was desolved by single crystal X-ray diffraction.(3) The investigation on degrading HD performance of catalysts:the influence of catalysts dosage, degradation time on degrading HD and the recycling use of catalysts were investigated. Otherwise the analysis of degradation products by GC-MS were studied.The experimental results showed that the degradation effects:2'> 2> 1'> 1. The catalytic kinetic study found that the degradation of HD with 1 'and 2'met the first order kinetics and the half-life of 1'and 2'were 66.44 min and 45.35 min, respectively. The GC/MS analysis results of the degradation products showed catalysts 1'and 2'degraded HD through hydrolysis and oxidation double degration mechanism.2. Preparation and characterization of (HKUST-1)n@TiO2(n=cycle times) catalysts and their properties of degrading HD performance:(1) Preparation and characterization of (HKUST-1)n@TiO2(n=cycle times) catalysts:carboxylated TiO2 nanoparticles was prepared by the reaction between TiO2 nanoparticles and trimesic acid through solvothermal method. The different loadings of HKUST-1 on TiO2 nanoparticles, named as (HKUST-1)n@TiO2 (n=cycle times) were successfully prepared through layer by layer method. The carboxylated TiO2 nanoparticles were dipped alternately in the ethanol solution of copper acetate and ethanol solution of trimesic acid.(2) Characterization of (HKUST-1)n@TiO2 catalysts:(HKUST-1)n@TiO2 were characterized by Infrared spectroscopy(IR), Thermogravimetric Analysis(TG), powder X-ray diffraction pattern(XRD), Elemental Analysis, Scanning Electron croscope(SEM), specific surface area analysis(BET).(3) The investigation on degrading HD performance of catalysts:the properties of degrading HD of (HKUST-1)n@TiO2 catalysts were studied systematically. The results showed that the degradation rate increased with n increased until n was 8, then the degradation rate was kept. The optimal conditions of degrading HD with (HKUST-1)8@TiO2 are as follows:catalyst amount:40mg; the degradation time:2h,HD concentration:0.115g/ml petroleum ether. The catalytic kinetic study found that the degradation of HD with (HKUST-1)8@TiO2 met the first order kinetics, and the rate constant and the half-life of (HKUST-1)8@TiO2 were 0.018 min-1 and 38.5 min, respectively.