多酸基晶态无机—有机杂化材料的合成、结构与性质研究

发布时间：2018-06-25 16:58

本文选题：多酸 + 无机-有机杂化物　；参考：《东北师范大学》2016年硕士论文

【摘要】：多酸(多金属氧酸盐)作为一类重要的阴离子建筑块,广泛地被应用于构筑结构新颖的以及功能型的晶态无机有机杂化物。其具有丰富并且确定的结构,如经典的Keggin型、Dawson型等,并在催化、医药、电化学、光致变色到磁性等众多的领域有巨大的应用前景。基于多酸的无机有机杂化物的研究在近年来引起了很多化学及材料研究者的青睐,特别是在催化方面。多酸阴离子代表了一类已知的有路易斯和布朗特酸性的无机建筑块,常被用来构建有效的固态酸催化剂来催化一系列的化学反应。本文用Keggin型多酸阴离子作为基本建筑块之一,与有机配体和金属盐在水热条件下构建了12例化合物,并对他们的结构进行了表征,催化或抗菌性质进行了初步的探究。1.我们选用了Keggin型{PW12),AgN03和刚性含氮配体4,4’-联吡啶,2,2’-联眯唑和4-(1H-四唑-5-基)吡啶合成了三例晶态杂化物(1,2,3),均具有光驱动降解有机染料和抗菌的性质。此外为了验证化合物2中配体上发生的硝化作用,用联咪唑配体又合成了化合物4。{Ag3(bpy)6[PW12040]} (1) {Ag5(H2biim)2(Hbiim-N02)2[PW12040]) (2) {Ag7(pytz)4[PW12040]} (3) {CU2.5(H2biim)5(H20)[BW12040]}·3H20 (4)对化合物1-3的结构分析和表征表明配体从单齿螯合配位到多齿螯合配位促使了化合物的结构从低维度到高纬度的递进,结构也越来越复杂有趣。此外,化合物2的合成中还出现了罕见的水热条件下的硝化反应。光催化降解有机染料和抗菌活性测试表明化合物1-3都具有双功能特性,不仅可以在紫外光下催化降解RhB,MB和AR,而且可以同时抑制革兰氏阴性菌E.coli和阳性菌S.agalactiae的生长。2.我们合成了对位苯并双甲基三唑(1,4-BBTZ)和间位苯并双甲基三唑(1,3-BBTZ) (BBTZ=bis(1,2,4-triazol-1-lmethyl)benzene)以及苯并双氧甲基吡啶(L)配体。此外,我们选择了Keggin型的{BW12}阴离子,主要考虑其有更高的负电荷易于与金属离子配位,其次制备容易且用来构建无机有机杂化物的研究较少。基于温度的调控,我们在水热条件下获得了四例基于{BW12}和BBTZ-Cu的化合物(5,6,7,8),另外利用配体L和{SiW12}合成了化合物9。{CuⅡ3C1(1,4-BBTZ)5[BW12040](H20)2}·6H20 (5) {CuⅠ3CⅡ(1,4-BBTZ)5[BW12040](H20))·H2O (6) {CuⅡ2CuⅠ(1,3-BBTZ)5[BW12040]}·H20 (7) {CuⅠ5(1,3-BBTZ)4[BW12040]}·4H2O (8) {CuⅡ2(L)4[SiW12040]}·6H2O (9)晶体衍射数据表明化合物5-7是3D结构,8和9是2D结构。通过配体和温度的调控,我们分析了获得的化合物结构,并根据结构特性推测了光催化的性能,着重对化合物5和6进行了一系列光催化性质探索。结果表明更高温度下的化合物6具有更窄的能带尺寸,可以在可见光下被激发,与H202共同作用有效的降解有机染料。3.我们继续使用高温合成的策略,采用了易于配位且配位点多的1,2,4-三氮唑与CuCl2,Keggin多酸在190-195℃下自组装了三例同构的无机有机杂化物10,11,12。{CuⅠ12Cl(trz)8[PW12O40]} (10) {CuⅠ12Cl(trz)8[PMo12O40]} (11) {CuⅠ12Cl(trz)8[HSiW12O40]} (12)三个化合物中所有的铜离子均是一价的,均可以在可见光驱动下催化降解染料,我们对化合物的催化机理也进行了一些巧妙的探讨和分析。此外,三个化合物都比较稳定,具有较好的抗酸碱稳定性。
[Abstract]:Polyoxometalates (polyoxometalates), as an important class of anionic building blocks, are widely used in the construction of novel and functional crystalline inorganic organic hybrids. They have rich and definite structures, such as the classic Keggin type, Dawson type, etc., and are in the fields of catalysis, medicine, electrochemistry, photochromism and magnetism. The study of inorganic organic Hybrids Based on polyacid has attracted many researchers in recent years, especially in catalysis. Polyanic anions represent a class of known inorganic building blocks with Lewis and Blount acidity, which are often used to build effective solid acid catalysts to catalyze a catalyst. A series of chemical reactions. In this paper, Keggin polyanic anions were used as one of the basic building blocks. 12 compounds were constructed with organic ligands and metal salts under hydrothermal conditions. Their structures were characterized. The catalytic or antibacterial properties were preliminarily explored..1. we chose Keggin {PW12), AgN03 and rigid nitrogen ligand 4,4. "- bipyridine, 2,2 '- biolazole and 4- (1H- four azole -5-) pyridine have synthesized three crystalline hybrids (1,2,3), all with light driven degradation of organic dyes and antibacterial properties. In addition, in order to verify the nitrification of ligands in compound 2, a compound of 4.{Ag3 (bpy) 6[PW12040]} (1) {Ag5 (H2biim) 2 (Hbiim-) (Hbiim-) was synthesized by the ligands of the ligands. N02) 2[PW12040]) (2) the structural analysis and characterization of {Ag7 (pytz) 4[PW12040]} (pytz) 4[PW12040]} (3) {CU2.5 (H2biim) 5 (H20) [BW12040]} 3H20 (4) on compound 1-3 shows that ligands from one tooth chelating coordination to multi tooth chelating coordination promote the structure of the compound from low to high latitudes, and the structure is becoming more and more complex and interesting. In addition, compound 2 synthesis There is also a rare nitrification reaction under hydrothermal conditions. The test of photocatalytic degradation of organic dyes and antibacterial activity shows that compounds 1-3 have dual functional properties, which can not only catalyze the degradation of RhB, MB and AR under ultraviolet light, but also inhibit the growth of Gram-negative bacteria E.coli and the growth.2. of positive bacteria S.agalactiae at the same time. Benzo dimethyl three azole (1,4-BBTZ) and interposition benzo dimethyl three azole (1,3-BBTZ) (BBTZ=bis (1,2,4-triazol-1-lmethyl) benzene) and benzo dioxomethyl pyridine (L) ligands. In addition, we choose the {BW12} anion of the Keggin type, mainly considering that it has higher negative charge and is easy to coordinate with metal ions. Second preparation is easy and used. There are few studies on the construction of inorganic organic hybrids. Based on the temperature control, we have obtained four {BW12} and BBTZ-Cu based compounds (5,6,7,8) under the hydrothermal condition, and the synthesis of 9.{Cu II 3C1 (1,4-BBTZ) 5[BW12040] (H20) 2} 6H20 (5) (6). The diffraction data of U I (1,3-BBTZ) 5[BW12040]}. H20 (7) {Cu I 5 (1,3-BBTZ) 4[BW12040]}. 4H2O (8) {Cu II 2 (L) 4[SiW12040]} 6H2O (9) shows that compound 5-7 is a structure, 8 and 9 is a structure. A series of photocatalytic properties of compound 5 and 6 have been explored. The results show that the compound 6 at higher temperature has a narrower band size and can be excited under visible light. The effective degradation of organic dye.3. with H202 can continue to use the strategy of high temperature synthesis, and the 1,2,4- three azoles, which are easy to coordinate and have more loci, are used. With CuCl2, Keggin polyacid at 190-195, three isomorphic inorganic organic hybrids 10,11,12.{Cu I 12Cl (Trz) 8[PW12O40]} (10) {Cu I 12Cl (Trz) 8[PMo12O40]} (11) {Cu I (11) {Cu 12Cl (12) three compounds are all monovalent, all of which can catalyze the degradation of dyes under visible light. The catalytic mechanism of the compound has also been discussed and analyzed in detail. In addition, the three compounds are relatively stable and have good acid and alkali stability.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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