多酸基高维杂化材料的设计与制备
发布时间：2018-10-16 16:59
【摘要】：多酸基金属有机无机高维杂化材料协同多酸(POMs)与金属有机配合物(MOFs)的优点,具有新颖的结构和优异的催化、电化学、磁性等性能,因此设计合成多酸基金属高维杂化材料已成为近年来多酸方向的研究热点之一。本论文在水热条件下,通过改变配体的种类,增加配体的位阻,多酸阴离子的种类,反应体系的温度制备了4个以d金属、柔性乙二胺配体/刚性氮唑配体/柔性双氮唑配体修饰的多酸基高维杂化材料。通过单晶X-射线衍射,红外测试(IR),粉末X-射线衍射(PXRD),元素分析(EA)等多种手段对所得晶体材料进行了结构表征,初步研究了其电化学性质。制备材料过程中,考察了反应体系的温度、多酸阴离子种类与金属的连接方式、有机配体的构型及位阻等多种影响因素对多酸杂化材料产物结构的影响,探究了配体的配位点个数及增加柔性间隔子对产物结构的影响。主要研究结果如下:1.采用水热合成技术,向[Cu2(en)2(ox)]2+双核铜反应体系中,引入BW12Keggin多酸阴离子,设计制备了Cu-en/ox片段修饰的BW12一维杂化材料,该化合物代表首例由柔性有机胺-草酸双核铜构筑的多酸基扩展结构。2.Ag-trz修饰[SiW12O40]4-(SiW12)构筑的新颖三维POMOFs杂化材料。水热反应条件下,固定多酸为SiW12,选用1H-1,2,4-triazole-3-carboxylic acid配体(1H-1,2,4-三氮唑-3-羧酸配体,简称为tda),通过tda原位脱羧生成triazole配体(1H-1,2,4-三氮唑,简称为trz),设计制备了Ag-trz修饰[SiW12O40]4-(SiW12)构筑的新颖三维POMOFs杂化材料化合物2和3。此外,初步的电化学行为研究结果表明化合物2的循环伏安曲线中的峰电流与其扫速呈线性关系,从而说明该化合物电化学行为是表面控制过程,电子传输速率较快。3.Cu-bpte修饰的[β-Mo8O26]4-(Mo8)三维杂化材料。通过选用位阻较小的Mo8簇、配位模式丰富的Cu离子及多种构象的双三氮唑柔性配体bpte,水热条件下制备出Cu-bpte修饰的β-Mo8O26多酸基扩展结构4。化合物4为首例由bpte-Cu-Mo8构筑的三维POMOF结构。
[Abstract]:Polyacid-base metal-organic-inorganic high-dimensional hybrid materials have the advantages of coordination of polyacid (POMs) with organometallic complex (MOFs), with novel structure and excellent catalytic, electrochemical and magnetic properties. Therefore, the design and synthesis of polyacid-based metals with high dimensional hybrid materials has become one of the research focuses in the direction of polyacid in recent years. In this paper, four d metals were prepared by changing the type of ligands, increasing the steric resistance of ligands, the kinds of polyacid anions, and the temperature of the reaction system under hydrothermal conditions. Flexible ethylenediamine ligands / rigid azazole ligands / flexible diazazole ligands modified polyacid high dimensional hybrid materials. The structure of the crystal was characterized by single crystal X-ray diffraction and X-ray diffraction of (IR), powder by (PXRD), elemental analysis of (EA). The electrochemical properties of the crystal were preliminarily studied. In the process of preparation, the effects of reaction temperature, the type of polyacid anions and metal, the configuration and steric resistance of organic ligands on the structure of polyacid hybrid materials were investigated. The effects of the number of ligand coordination points and the increase of flexible spacers on the structure of the product were investigated. The main results are as follows: 1. The one-dimensional BW12 hybrid material modified by Cu-en/ox fragment was designed and prepared by introducing BW12Keggin polyacid anions into [Cu2 (en) _ 2 (ox)] _ 2 binuclear copper reaction system by hydrothermal synthesis technique. The compound represents the first polyacid-group expanded structure constructed from flexible organoamine-oxalate binuclear copper. 2.Ag-trz modified [SiW12O40] 4- (SiW12) as a novel three-dimensional POMOFs hybrid material. Under hydrothermal reaction conditions, the fixed polyacids were used as SiW12, ligands (1H-1O2-triazole-3-carboxylic acid ligands) (1H-1O2A4-triazole-3-carboxylic acid ligands), which were called tda), in situ decarboxylation via tda to produce triazole ligands (1H-1O2C2-triazole-3-carboxylic ligands). Ag-trz modified [SiW12O40] 4- (SiW12) novel three dimensional POMOFs hybrid compounds 2 and 3 were designed and prepared by trz), for short. In addition, the preliminary study of electrochemical behavior shows that the peak current in cyclic voltammetry curve of compound 2 is linearly related to its sweep speed, which indicates that the electrochemical behavior of compound is a surface controlled process. 3.Cu-bpte modified [尾-Mo8O26] 4-(Mo8) three-dimensional hybrid materials. The 尾-Mo8O26 polyacid extension structure modified by Cu-bpte was prepared under hydrothermal conditions by using Mo8 clusters with low steric resistance, rich coordination mode Cu ions and a variety of conformational ditriazole flexible ligands, bpte,. Compound 4 is the first three-dimensional POMOF structure constructed by bpte-Cu-Mo8.
【学位授予单位】：哈尔滨理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2275041
[Abstract]:Polyacid-base metal-organic-inorganic high-dimensional hybrid materials have the advantages of coordination of polyacid (POMs) with organometallic complex (MOFs), with novel structure and excellent catalytic, electrochemical and magnetic properties. Therefore, the design and synthesis of polyacid-based metals with high dimensional hybrid materials has become one of the research focuses in the direction of polyacid in recent years. In this paper, four d metals were prepared by changing the type of ligands, increasing the steric resistance of ligands, the kinds of polyacid anions, and the temperature of the reaction system under hydrothermal conditions. Flexible ethylenediamine ligands / rigid azazole ligands / flexible diazazole ligands modified polyacid high dimensional hybrid materials. The structure of the crystal was characterized by single crystal X-ray diffraction and X-ray diffraction of (IR), powder by (PXRD), elemental analysis of (EA). The electrochemical properties of the crystal were preliminarily studied. In the process of preparation, the effects of reaction temperature, the type of polyacid anions and metal, the configuration and steric resistance of organic ligands on the structure of polyacid hybrid materials were investigated. The effects of the number of ligand coordination points and the increase of flexible spacers on the structure of the product were investigated. The main results are as follows: 1. The one-dimensional BW12 hybrid material modified by Cu-en/ox fragment was designed and prepared by introducing BW12Keggin polyacid anions into [Cu2 (en) _ 2 (ox)] _ 2 binuclear copper reaction system by hydrothermal synthesis technique. The compound represents the first polyacid-group expanded structure constructed from flexible organoamine-oxalate binuclear copper. 2.Ag-trz modified [SiW12O40] 4- (SiW12) as a novel three-dimensional POMOFs hybrid material. Under hydrothermal reaction conditions, the fixed polyacids were used as SiW12, ligands (1H-1O2-triazole-3-carboxylic acid ligands) (1H-1O2A4-triazole-3-carboxylic acid ligands), which were called tda), in situ decarboxylation via tda to produce triazole ligands (1H-1O2C2-triazole-3-carboxylic ligands). Ag-trz modified [SiW12O40] 4- (SiW12) novel three dimensional POMOFs hybrid compounds 2 and 3 were designed and prepared by trz), for short. In addition, the preliminary study of electrochemical behavior shows that the peak current in cyclic voltammetry curve of compound 2 is linearly related to its sweep speed, which indicates that the electrochemical behavior of compound is a surface controlled process. 3.Cu-bpte modified [尾-Mo8O26] 4-(Mo8) three-dimensional hybrid materials. The 尾-Mo8O26 polyacid extension structure modified by Cu-bpte was prepared under hydrothermal conditions by using Mo8 clusters with low steric resistance, rich coordination mode Cu ions and a variety of conformational ditriazole flexible ligands, bpte,. Compound 4 is the first three-dimensional POMOF structure constructed by bpte-Cu-Mo8.
【学位授予单位】：哈尔滨理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
【参考文献】
相关期刊论文 前1条
1 刘术侠，刘彦勇，王恩波，，曾毅，李泽琳;Keggin结构钨磷酸稀土镨盐杂多蓝的合成及抗艾滋病病毒（HIV－1）活性的研究[J];高等学校化学学报;1996年08期
相关博士学位论文 前1条
1 李小敏;多金属氧酸盐基无机—有机杂化材料的合成、晶体结构和性质研究[D];东北师范大学;2015年
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