| The metal-organic frameworks(MOFs), also named as coordination Polymers(CPs), have high regular and infinit network structures. The azolate ligand can provide the nitrogen donors, while the carboxylic ligand has the carboxylic oxygen donors. Thus the MOFs constructed from azolate ligand or carboxylic ligand, which can coordinate to the metal ions synergetically, have becoming important functional materials due to their excellent gas adsorption and separation properties, photochemical properties, nonlinear optical properties and ferroelectric properties. In this thesis, the 5-amino-1H-tetrazole or 1,2,4-triazole or 3-amino-1,2,4-triazole and diverse polycarboxylic acid ligands have been used to construct MOFs with the Zn(II) ion. Fortunately, seven MOFs have successfully been obtained under solvothermal conditions. They molecule formula are listed below.{(H3O)0.5[Zn(1,2,4,5-BTBC)0.25(ATZ)1.5]·x(solvent)}n(1){[Zn2(1,2,4-BTC)(ATZ)(H2O)]·DMF }n(2){[Zn5(?3-OH)2(1,3,5-BTC)2(trz)2(DMF)2]·x(solvent)}n(3){[Zn7(5-SIP)2(trz)8(H2O)4]·(H2O)4}n(4){[Zn3(1,2,4-BTC)(3-NH2-trz)3]·x(solvent)}n(5){[Zn2(5-CH3-1,3-BDC)(3-NH2-trz)2]·x(solvent)]}n(6){[Zn2(5-OH-1,3-BDC)(3-NH2-trz)2]·x(solvent)}n(7)These compounds have been characterized by X-ray single crystal diffraction, X-ray powder diffraction, thermogravimetric analysis(TGA) and infrared spectroscopy(IR). The results of the structural analyses showed that the compounds 1-7 all are three-dimensional(3D) networks structure featuring the one-dimensional(1D) channels, which being occupied by the solvent molecules, such as N,N- dimethylformamide(DMF) and/or water molecules. In order to drive out the solvent molecules in the channels for obtaining the porous materials, the low boiling point solvents such as methanol and chloroform have been exchanged with the DMF and water molecules in the channels. The results of the solvent-exchange experiments showed that the solvents molecules in the channels for all compounds except for comppounds 4 and 7 have been successfully exchanged by methanol or chloroform solvent. Therefore, the adsorption of N2, CO2 and some paraffin gases(CH4, C2H6, C3H8, C2H4 and C2H2) of these active metal-organic frameworks have been investigated in detail. These compounds except for compound 2 can take up a certain amount of N2, CO2 and some paraffin gases. Some compounds have a moderate adsorption capacities for CO2 and C2H2, which resulted from the aromatic ? systems and the polar amino group on the surface of the pores. In addition, some reaction factors such as reaction time and temperature, solvent, reaction material ratio on the crystal growth of the metal organic-framework compounds have been summarized.Three parts are divided in this paper:The first chapter is the foreword, which mainly summarized the metal-organic framework compounds, the synthesis methods and the influence factors of metal organic framework compounds, the latest research progress on metal-organic frameworks constructed by azolate and carboxylic ligands, and the research work of this thesis.The second chapter described the syntheses and structures of seven metal-organic frameworks. All metal-organic frameworks are 3D structures with 1D channel. The sorption properties of the compounds 1, 2, 3, 5, and 6 have been tested with the N2, CO2 and some paraffin gases(CH4, C2H6, C3H8, C2H4 and C2H2). These compounds except for compound 2 exhibit a certain amount of these gases.The last chapter is the conclusion and an outlook on this thesis. |
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