Synthesis,Structures And Properties Of Keggin Heteropoly Blue-embedded Metal-organic Frameworks

This thesis reports 4 compounds based on heteropoly blue-metal organic framework synthesized by hydrothermal synthesis technology and conventional synthesis methods of aqueous solution. By hydrothermal synthesis technology, Keggin type heteropoly blue [(CH3)4N]5[SiW11MovO40]·6H2O and [(CH3)4N]6[GeW10Mov2O40]·6H2O have been introduced into the metal organic framework as materials, successfully synthesized two cases of heteropoly blue-embedded metal organic frameworks. Through conventional synthesis methods of aqueous solution, using V2O5 as materials, we synthesized two mixed metal vanadium oxide clusters. The structure characterizations and other properties of these new compounds have been characterized.1.By hydrothermal synthesis technology, [(CH3)4N]5[SiW11MovO40]·6H2O, organic ligand 1,3,5-benzentricaboxylate and transition metal salt CuCl2 as raw materials, successfully synthesized a heteropoly blue-embedded metal organic framework. Formula is as follow:[Cu3(BTC)2(H2O)3]4[SiW11MovO40](C4H12N)5·30H2O(BTC=1,3,5-benzentricaboxylate)(1)In the crystal structure of compound 1, free [SiW11MovO40]5- heteropoly blues as guests introduced into an open porous system which is the famous metal-organic framework HKUST-1. Proton conduction test for compound 1, study has shown that compounds 1 change from nonconductor to proton conductor with the increase of humidity.2. By hydrothermal synthesis technology, [(CH3)4N]6[GeW10Mov2O40]·6H2O, organic ligand 1,3,5-benzentricaboxylate and transition metal salt CuCl2 as raw materials, successfully synthesized a heteropoly blue-embedded metal organic framework. Formula is as follow:[Cu3(BTC)2(H2O)3]4[GeW10Mov2O40](C4H12N)6·30H2O(BTC=1,3,5-benzentricaboxylate)(2)In the crystal structure of compound 2, free [GeW10Mov2O40]6- heteropoly blues as guests introduced into an open porous system which is the famous metal-organic framework HKUST-1. Gas sensing test for compound 2, studies have shown that compound 2 with acetone and ethanol sensing function.3. In aqueous solution, with V2O5 and LiOH·H2O, NH2·NH2·H2SO4, NiSO4·6H2O and CoSO4·6H2O as raw materials, by adjusting the reaction temperature and reaction time,2 mixed metal vanadium oxide clusters have been successfully synthesized. Formulas are as follows:(N2H5)2[Ni3VIV12Vv6O42(SO4)(H2O)12]·22H2O(3)(N2H5)2[Co3VIV12Vv6O42(SO4)(H2O)12]·22H2O(4)In compounds 3 and 4, the vanadium oxides are connected by transition metal Ni and Co into three dimensional networks, and we find that 3 and 4 exist antiferromagnetic interactions.