Synthesis And Catalytic Study Of Transition-Metal Decorated Keggin-type Polyoxometalate-based Organic Inorganic Hybrid Materials

Polyoxometalates(POMs),as an important component of metal oxides,has always been a hot research for research workers,Because it is in the catalytic,electrocatalytic,photocatalytic,magnetic and medicine fields have potential applications.In this thesis,we chose common N-containing ligands as well as transition metal Ag,Ni to decorate the Keggin-type POMs,five POM-based hybrids have been synthesized,they have been structurally characterized by the single crystal X-ray diffractions,thermogravimetry(TG),Powder X-ray diffraction(XRD)and IR spectra et al.methords,we obtained the crystal structures of these five compounds.And on this basis,we all so studied the propertities of the crystals,such as oxidation of desulfurization and electrocatalysis properties.1.Compound 1 was obtained by reaction of the Ag+,Keggin-type POMs H5PMo10V2O40 and the mixed organic linking ligands(Htrz?4,4'-bpy)under the hydrothermal conditions.And its oxidative desulfurization properties and electrocatalytic activity for reduction of H2O2 and Br O3-have been studied.{Ag8O(Htrz)4(4,4'-bpy)2}{Ag PMo12O40}(Htrz =1,2,4-triazole)(1)In 1,a purely inorganic 1D chain composed of Keggin-type polyoxoanions and the Ag+linkers,interluded into the 2D Ag-organic layers,Moreover,The ratio of the mixed ligands played a crucial role in the synthesis of the title compound.2.Four polyoxometalate-based organic inorganic hybrid materials were synthesized by reaction of the [PW11Ni O39(H2O)]5-,[BW12O40]5-,[Ge W12O40]4-and [PW12O40]3-,Ni2+,2,2'-bpy under the hydrothermal conditions,respectively.And their electrocatalytic activity towards water oxidation and reduction of nitrite have been studied.[Ni(2,2-bpy)3]5[PW11Ni O39(H2O)]2·7H2O(2),[Ni(2,2-bpy)3]3[Ni(2,2-bpy)2(H2O)BW12O40]2·3H2O(3),[Ni(2,2-bpy)3]3[Ni(2,2-bpy)2(H2O)Ge W12O40]2·(OH)2(4),[Ni(2,2-bpy)3]3[Ni(2,2-bpy)2(H2O)PW12O40]2·(OH)4(5),In compound 2,two mono-substituted [PW11Ni O39(H2O)]5-anions were fused together via the H-bonding interactions forming a dimeric polyoxoanion [PW11Ni O39(H2O)]210-,which was surrounded by Ni-bpy cationic units into the molecular structures.Compounds 3?5 were composed of the saturated polyoxoanions [BW12O40]5-,[Ge W12O40]4-and [PW12O40]3-,respectively.These saturated anions were surrounded by the [Ni(2,2-bpy)3]2+and [Ni(2,2-bpy)2(H2O)]2+cationic units forming the isostructural organic-inorganic hybrids materials.