过渡金属修饰的Keggin型多酸基有机无机杂化材料的合成及其催化性能研究

发布时间：2018-04-28 19:01

  本文选题：Keggin型多酸 + 有机无机杂化材料　； 参考：《东北师范大学》2017年硕士论文

【摘要】：多金属氧酸盐(Polyoxometalates),简称为多酸(POMs),作为金属氧簇的一个重要组成部分,一直以来都是大量科研工作者的研究热点,这是因为它在催化、电化学、电催化、光催化、磁性和药学等领域都有潜在的应用。本文利用过渡金属银、镍与常见的含氮配体对Keggin型多酸进行修饰,得到了5例多酸基有机无机杂化化合物,并通过单晶X-射线衍射分析、热重、XRD、红外等分析测试,对晶体结构进行相应的表征与分析。在此基础上,对晶体的性质也进行了研究,如氧化脱硫性质、电催化性质等。1.利用Keggin型多酸H5PMo10V2O40、Ag+和混合的有机配体(Htrz、4,4’-bpy)在水热条件下得到化合物1。并对化合物1在氧化脱硫,电催化还原H2O2和Br O3-方面的活性进行了研究。{Ag8O(Htrz)4(4,4’-bpy)2}{Ag PMo12O40}(Htrz=1,2,4-三氮唑)(1)化合物1的结构是由纯无机的1D链和2D有机层Ag-Htrz-4,4’-bpy构成的,Keggin型多阴离子和Ag+构成了纯无机1D链,并且它贯穿在2D的Ag-Htrz-4,4’-bpy有机层中。另外,混合配体的比率在这个化合物的合成上扮演着重要角色。2.利用Keggin型多酸阴离子[PW11Ni O39(H2O)]5-,[BW12O40]5-,[Ge W12O40]4-和[PW12O40]3-分别与Ni2+和2,2’-bpy在水热条件下得到化合物2-5,并对化合物2-5的水氧化和还原亚硝酸盐的电催化活性进行了研究。[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)在化合物2中,两个单取代的[PW11Ni O39(H2O)]5-阴离子通过氢键作用形成一个二聚的多阴离子[PW11Ni O39(H2O)]210-,它被Ni-bpy阳离子单元包围形成复合分子结构。化合物3-5分别是由饱和的Keggin型多阴离子[BW12O40]5-,[Ge W12O40]4-和[PW12O40]3-构成的,这些饱和的阴离子被[Ni(2,2-bpy)3]2+和[Ni(2,2-bpy)2(H2O)]2+阳离子单元包围形成同构的有机无机杂化材料。
[Abstract]:Polyoxometalates polyoxometalates (POMsN), as an important component of metal oxygen clusters, has been a hot research topic for a large number of researchers because of its catalysis, electrochemistry, electrocatalysis and photocatalysis. Magnetic and pharmaceutical fields have potential applications. In this paper, Keggin polyacids were modified with transition metal silver, nickel and nitrogen-containing ligands. Five polyacid-base organic-inorganic hybrid compounds were obtained. The results were analyzed by single crystal X-ray diffraction, thermogravimetric analysis and IR. The crystal structure was characterized and analyzed. On this basis, the properties of the crystal are also studied, such as oxidation desulfurization, electrocatalytic properties and so on. Compound 1 was synthesized by using Keggin polyacid H 5PMo 10 V 2O 40 Ag and a mixed organic ligand, Htrzf4 Htrzan4B pyre, under hydrothermal conditions. Compound 1 was oxidized and desulphurized. The activity of electrocatalytic reduction of H2O2 and Br O 3- was studied. The structure of compound 1 is composed of pure inorganic 1D chain and 2D organic layer Ag-Htrzz-4N 4N -bpy. The structure of compound 1 is composed of pure inorganic 1D chain and Ag pure inorganic 1D chain. And it runs through the 2 D Ag-Htrz-4N 4N-BPY organic layer. In addition, the ratio of mixed ligands plays an important role in the synthesis of this compound. 鍒╃敤Keggin鍨嬪�氶吀闃寸�诲瓙[PW11Ni O39(H2O)]5-,[BW12O40]5-,[Ge W12O40]4-鍜孾PW12O40]3-鍒嗗埆涓嶯i2 鍜，

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