本文關(guān)鍵詞：釕—鄰菲羅啉基配位聚合物的制備及性能研究　出處：《太原理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 金屬有機高分子 多向配體 螯合配位 配位聚合物 熱穩(wěn)定性

【摘要】：金屬有機高分子材料是將無機金屬與有機高分子相結(jié)合的有機-無機復(fù)合材料,相比于純粹的有機高分子材料,金屬有機高分子擁有更為豐富的物理化學(xué)特征和廣闊的應(yīng)用前景,在催化劑、傳感器、光電材料、儲能等方面都具有非常重要的應(yīng)用。本研究合成了三種具有多向配位能力的螯合配體,并使配體與釕離子配位聚合制備了三種金屬有機聚合物材料,主要研究內(nèi)容如下:1.配體TBI-phen及其配位聚合物Ru-PBI-1的制備和性能研究。以5,6-二氨基-1,10-菲羅啉和1,3,5-苯三甲酸的咪唑化反應(yīng)合成了配體TBI-phen,通過紅外、核磁、元素分析等表征,確定配體結(jié)構(gòu)由鄰菲羅啉基團通過咪唑環(huán)連接在苯環(huán)上,具有三向螯合配位能力。TBI-phen作為結(jié)構(gòu)配體,與釕離子通過配位自組裝作用形成具有空間網(wǎng)狀結(jié)構(gòu)的配位聚合物Ru-PBI-1。Ru-PBI-1的熱分解溫度在400°C以上,具有良好的熱穩(wěn)定性,而且聚合物432 m~2/g的比表面積說明該材料在吸附、催化等方面有潛在應(yīng)用。此外,Ru-PBI-1在光激發(fā)下還能夠發(fā)射出586nm波長的紅色熒光,表明該材料可以用作耐高溫固體熒光材料。2.配體TPI-phen及其配位聚合物Ru-PBI-2的制備和性能研究。以1,3,5-(4-羧基苯基)苯和5,6-二氨基-1,10-菲羅啉合成了分子尺寸較大的三向配體TPI-phen,TPI-phen分子結(jié)構(gòu)和TBI-phen類似,但不同的是在每個支化方向上都比后者多出一個苯環(huán)。配體TPI-phen與釕離子經(jīng)過配位聚合,形成具有較大孔徑的聚合物Ru-PBI-2,隨后通過核磁、XPS、XRD、SEM、TEM等對聚合物結(jié)構(gòu)、形貌進行表征。聚合物Ru-PBI-2的熱穩(wěn)定性優(yōu)異,并且具有308 m~2/g的比表面積,在453 nm光激發(fā)下能夠產(chǎn)生589 nm波長的紅色熒光。3.配體BBI-phen及其配位聚合物Ru-PBI-3的制備和性能研究。通過1,4-苯二甲酸和5,6-二氨基-1,10-菲羅啉的咪唑化反應(yīng)合成了雙向配體BBI-phen,該配體具有啞鈴狀結(jié)構(gòu)并且關(guān)于苯環(huán)對稱,BBI-phen與釕離子配位合成了具有更大孔徑結(jié)構(gòu)的配位聚合物Ru-PBI-3,該聚合物的結(jié)構(gòu)、形貌分別通過核磁、XPS、XRD、SEM、TEM等表征手段分析。聚合物Ru-PBI-3熱穩(wěn)定高,并且具有227 m~2/g的比表面積,在453 nm光激發(fā)下能夠產(chǎn)生586 nm波長的紅色熒光。
[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 擄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.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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本文編號：1366514