Syntheses And Properties Of Pore-Adjustable Metal-Organic Framework Materials

Metal–organic frameworks(MOFs), well-known than coordination polymers(CPs), are porous crystalline solids that are three-dimensional and porous inherently. MOF are becoming one of the most rapidly developing fields in chemical and material sciences not only because of their novel structures but also due to their diverse applications such as gas adsorption and separation, catalysis, and sensing, etc. Based on the geometries of the organic linkers and coordination modes of the inorganic metal ions or clusters of metal ions, their structures can be designed according to expected functionality, which have been gained a tremendous amount of attention by the scientist.In this thesis, we have synthesized twenty-six carboxylate-based MOF materials by precursor route or grinding-aiden solvothermal synthesis or multicomponent assembly of more than two kinds of such ligands as formic acid, oxalic acid, isophtalic acid, BTC, ISN, BTB and TATB, or more than two kinds of metal salts, of which most are some functional MOF materials as expected.In chapter one, we summarized the basic conception, the significance of related study, synthetic techniques, as well as a brief introduction of properties and application of the MOF.In chapter two, we have synthesized five coordination polymers by using formic acid as ligands and metal salts(M= Fe3+, Cu2+and Co2+) under solvothermal condition. A kind of polymeric cobalt formate with a topology, in which 8-membered ring is the large ring, was first observed. N2 sorption test showed MF-1, the cubic phase of Feric formate prefers to adsorb the gas of carbon dioxide.In chapter three, we have synthesized seven coordination polymers by multicomponent assembly of isophtalic acid and or isonicotinic acid and BTC and TATB as ligand group and M salt group contain no less than two of Cu2+, Co2+, Zn2+, La3+and Mn2+ as metal source under solvothermal condition. Two kinds of 3D MOF such as AF-3, AF-4 were gotten, and their physical properties were investigated.In chapter four, forteen coordination polymers contain such C3 ligands as BTC, BTB and TATB were prepared by the precursor of HKUST-1 and by the multicomponent assembly of ligand group or metal group or solvent group, of which most are some products with open framework. CF-2, CF-6, CF-7, CF-10 and CF-11 all exihit diversity of novel networks, while another foreign metal ions into the known frameworks result in the change in charge and other physical properties, for example, AF-6 encapsulates chloride ion and [Co(DMF)3(H2O)3]2+. Some physical properties were characterized by mean of x-ray powder diffraction(XRD), thermal gravimetric analysis(TGA), x-ray single crystal diffraction, and N2 sorption.In the last chapter, we have summarized some representative results including the structure and special properties of twenty-six coordination polymers.