钌—邻菲罗啉基配位聚合物的制备及性能研究

发布时间：2018-01-01 22:33

本文关键词：钌—邻菲罗啉基配位聚合物的制备及性能研究　出处：《太原理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：金属有机高分子材料是将无机金属与有机高分子相结合的有机-无机复合材料,相比于纯粹的有机高分子材料,金属有机高分子拥有更为丰富的物理化学特征和广阔的应用前景,在催化剂、传感器、光电材料、储能等方面都具有非常重要的应用。本研究合成了三种具有多向配位能力的螯合配体,并使配体与钌离子配位聚合制备了三种金属有机聚合物材料,主要研究内容如下:1.配体TBI-phen及其配位聚合物Ru-PBI-1的制备和性能研究。以5,6-二氨基-1,10-菲罗啉和1,3,5-苯三甲酸的咪唑化反应合成了配体TBI-phen,通过红外、核磁、元素分析等表征,确定配体结构由邻菲罗啉基团通过咪唑环连接在苯环上,具有三向螯合配位能力。TBI-phen作为结构配体,与钌离子通过配位自组装作用形成具有空间网状结构的配位聚合物Ru-PBI-1。Ru-PBI-1的热分解温度在400°C以上,具有良好的热稳定性,而且聚合物432 m~2/g的比表面积说明该材料在吸附、催化等方面有潜在应用。此外,Ru-PBI-1在光激发下还能够发射出586nm波长的红色荧光,表明该材料可以用作耐高温固体荧光材料。2.配体TPI-phen及其配位聚合物Ru-PBI-2的制备和性能研究。以1,3,5-(4-羧基苯基)苯和5,6-二氨基-1,10-菲罗啉合成了分子尺寸较大的三向配体TPI-phen,TPI-phen分子结构和TBI-phen类似,但不同的是在每个支化方向上都比后者多出一个苯环。配体TPI-phen与钌离子经过配位聚合,形成具有较大孔径的聚合物Ru-PBI-2,随后通过核磁、XPS、XRD、SEM、TEM等对聚合物结构、形貌进行表征。聚合物Ru-PBI-2的热稳定性优异,并且具有308 m~2/g的比表面积,在453 nm光激发下能够产生589 nm波长的红色荧光。3.配体BBI-phen及其配位聚合物Ru-PBI-3的制备和性能研究。通过1,4-苯二甲酸和5,6-二氨基-1,10-菲罗啉的咪唑化反应合成了双向配体BBI-phen,该配体具有哑铃状结构并且关于苯环对称,BBI-phen与钌离子配位合成了具有更大孔径结构的配位聚合物Ru-PBI-3,该聚合物的结构、形貌分别通过核磁、XPS、XRD、SEM、TEM等表征手段分析。聚合物Ru-PBI-3热稳定高,并且具有227 m~2/g的比表面积,在453 nm光激发下能够产生586 nm波长的红色荧光。
[Abstract]:Metal-organic polymer materials are organic-inorganic composites which combine inorganic metals with organic polymers, compared with pure organic polymer materials. Organometallic polymers have richer physical and chemical characteristics and broad application prospects in catalysts, sensors, and optoelectronic materials. In this study, three kinds of chelating ligands with multidirectional coordination ability were synthesized, and three kinds of organometallic polymers were prepared by coordination polymerization of ruthenium with ligands. The main contents are as follows: 1. Preparation and properties of ligand TBI-phen and its coordination polymer Ru-PBI-1. The ligand TBI-phenin was synthesized by imidazolization of 5-benzoic acid. The ligand was characterized by IR, NMR and elemental analysis. It was confirmed that the ligand structure was connected to benzene ring by imidazole ring by o-phenanthroline group. TBI-phen was used as structural ligand. The thermal decomposition temperature of coordination polymer Ru-PBI-1.Ru-PBI-1 with space network structure is above 400 掳C through coordination self-assembly with ruthenium ion. It has good thermal stability, and the specific surface area of the polymer 432 mg / g shows that the material has potential applications in adsorption, catalysis and so on. Ru-PBI-1 can also emit 586 nm red fluorescence. The results show that this material can be used as high temperature resistant solid fluorescent material. 2. The preparation and properties of ligand TPI-phen and its coordination polymer Ru-PBI-2. TPI-phen with large molecular size has been synthesized from 5-N 4-carboxyphenyl) benzene and 5N 6-diamino -1o 10-phenanthroline. The molecular structure of TPI-phen is similar to that of TBI-phen, but there is a benzene ring in each branching direction. The ligand TPI-phen is coordinated polymerized with ruthenium ion. The polymer Ru-PBI-2 with large pore size was formed, and then the polymer structure was obtained by nuclear magnetic resonance (NMR) XPSN XRDX SEMI-TEM and so on. The morphology of the polymer Ru-PBI-2 was characterized by its excellent thermal stability and specific surface area of 308mg / g. A 589nm red fluorescence was generated under 453 nm excitation. The preparation and properties of ligand BBI-phen and its coordination polymer Ru-PBI-3 were studied. The bidirectional ligands BBI-phenanthroline were synthesized by the imidazolization reaction of 4-phthalic acid and 5o-6-diamino-10-phenanthroline. The ligands have dumbbell-like structure and symmetry of benzene ring. Ru-PBI-3, a coordination polymer with larger pore size, was synthesized by coordination of BBI-phen with ruthenium ion. The structure and morphology of Ru-PBI-3 were characterized by NMR. TEM analysis showed that the polymer Ru-PBI-3 had a high thermal stability and a specific surface area of 227mg / g. The red fluorescence of 586 nm can be produced under 453 nm excitation.
【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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