Syntheses, Structures, And Gas Storage Properties Of Metal-Organic Framework Materials

In this thesis, primary ligand carboxylate acid of terephthalic acid,1,3,5-benzenetricarboxylic acid,2,6-naphthalene dicarboxylic acid and auxiliary ligand N-containingneutral ligand such as4,4′-AZPY,4,4′-bipyridine and pyrazine were used to synthesizeseries of novel metal-organic coordination polymers with transition metal ion （Co, Zn, Mn,Pb） by intermolecular self-assembly under solvothermal condition. Charcterization aboutstructures and gas-storing properties have been processed.Three-dimensional metal-organic coordination polymer Co₂[（NDC）（AZPY）]2·2H₂O·DMF （1） with Co metal matrix by intermolecular self-assembly were synthesizedby using primary ligand2,6-naphthalene dicarboxylic acid and nitrogenous ligands4,4′-AZPY. The single crystal X-ray result shows that polymer （1） crystallizes in themonoclinic system, space group C2/c. In compound （1） the AZPY bends to the gauche isomer structure and hydrogen adsorption experimental result shows that polymer （1） can store hydrogen with2.87mmol/g.1,3,5-benzene tricarboxylic acid and another ligand glycolic acid were used tosynthesize three-dimensional metal-organic coordination polymer Co₂Cl（BTC）（DMA）₃（2）with Co metal matrix by intermolecular self-assembly. The polymer （2） belongs to theorthorhombic system, space group P2₁2₁2₁.1,3,5-benzene tricarboxylic acid and4,4′-bipyridine were selected to synthesize the three-dimensional metal-organiccoordination polymer Co₂（BTC）₃（DMF）₃（CH₃O）·（DMF）₂·（H₂O）2·（C₂H₃N）（3） with Cometal matrix by intermolecular self-assembly. The polymer （3） crystallizes in themonoclinic system, space group C2/c.1,3,5-benzene tricarboxylic acid is used tosynthesize the three-dimensional metal-organic coordination polymer Co₃（BTC）ph·9H₂O （4）with Co metal matrix by intermolecular self-assembly. The polymer （4） belongs to thehexagonal system, space group P6（3）/m.1,3,5-benzene tricarboxylic acid was used to synthesize the three-dimensionalmetal-organic coordination polymer Zn（BTC）·DMA·[N（CH₃）₂]（5） and Zn（BTC）·DMF·（C₂H₈N）（6） with Zn metal matrix by intermolecular self-assembly. Polymer （5） andpolymer （6） have the same coordination environment, and only differ in the size and shapeof cavities and the solvents in cavities, which belong to the monoclinic system, space groupP2₁/c. The nitrogen adsorption experimental result of polymer （5） indicates that the nitrogen uptake is only0.50mmol/g.1,3,5-benzene tricarboxylic acid was used to synthesize the three-dimensionalmetal-organic coordination polymer Mn₃（BTC）₂（DMF）₄（7） with Mn metal matrix byintermolecular self-assembly. Polymer （7） belongs to the orthorhombic system, space groupP2₁/c The hydrogen adsorption experimental result of polymer （7） indicates that thehydrogen uptake is only0.03mmol/g.Terephthalic acid was used to synthesize the three-dimensional metal-organiccoordination polymer Pb₂O·（BDC）·（DMF）（8） with Pb metal matrix by intermolecularself-assembly. Polymer （8） crystallizes in the orthorhombic system, space group P2₁2₁2₁.The polymer （8） was characterized by XRD, IR, TG. The hydrogen adsorption experimentalresult of polymer （8） indicates that the hydrogen uptake is1.06mmol/g.