本文關鍵詞：金屬有機框架材料的設計合成、結構及質子導電性質研究　出處：《鄭州大學》2017年碩士論文　論文類型：學位論文

  更多相關文章： 金屬有機框架 MIL-88B 質子導電 羧酸配體

【摘要】：金屬有機框架(Metal-Organic Frameworks,簡稱MOFs),也稱之為多孔配位聚合物(Porous Coordination Polymers,簡稱PCPs),是由金屬離子/簇(亦稱次級構筑單元,Secondly Building Units,SBUs)和有機配體構筑而成。該材料憑借著結構可設計、孔道尺寸可調節(jié)、孔壁可功能化修飾以及高度晶態(tài)化等特點,在吸附/分離、導電、磁性、催化、熒光、鐵電和生物醫(yī)藥等方面有著很好的應用前景。從MOFs材料被發(fā)現可以作為質子傳輸材料以來,科學家們開啟了對MOFs材料質子導體性能的研究熱潮,近幾年來這一領域得到了飛速發(fā)展,使此應用迅速走向成熟。質子交換膜燃料電池中最為核心的部件就是質子交換膜,它能夠隔開電池中的燃料和氧化劑,而且又允許質子在膜中自由通過,是影響電池壽命和性能的關鍵所在。化學家們通過改變配體種類、反應條件等構筑出了大量的具有優(yōu)良導電性能的MOFs材料,并通過各種修飾方法來改善其導電性能,使這種應用更加趨于成熟,為實際應用打下了堅實的理論基礎。在本文中,我們主要開展了以下主要工作:一、我們以MIL-88B結構為基礎,選擇含有不同官能團的有機配體與鉻離子構筑成同構的Cr-MIL-88B結構,研究不同配體對質子導電性能的影響與改善。另外,通過配體摻雜的策略探究了該結構的無水導電特性。我們選擇對苯二甲酸(H_2BDC)、2-氨基對苯二甲酸(H_2BDC-NH_2)、2-甲基對苯二甲酸(H_2BDC-CH3)、2,5-二甲基對苯二甲酸(H_2BDC-2CH3)等配體分別與金屬鉻鹽合成不同配體的同構MIL-88B結構,并且選用輔助配體tpt裝進晶體結構中將其柔性結構撐開,最后分別研究了Cr-MIL-88B、Cr-MIL-88B-NH_2、Cr-MIL-88B-tpt這三種配合物在不同濕度下的質子導電性能。另外,探究了利用不同配體合成的四種配體摻雜與Cr-MIL-88B同構的配合物,并初步測試了其無水質子導電性。通過測試發(fā)現Cr-MIL-88B結構的配合物具有較好的質子導電性質。二、設計合成了多羧酸配體L_1,5-芐巰基間苯二甲酸和柔性多羧酸配體L_2,1,2-二(2-磺酸基-4-羧酸苯基氧基)乙烷�；诙圄人崤潴wL_1與硝酸銅采用溶劑熱法設計合成了兩個異構的三維配合物1和配合物2。經過X-射線單晶衍射測試可知,配合物1的空間群是P-1,屬于三斜晶系。該結構有兩種銅簇,分別與配體相互連接構成一個沿a軸方向的一維孔道。配合物2的空間群是I4/m,屬于四方晶系。配合物2是在配合物1的合成基礎上通過添加三苯基膦的乙醇溶液而得到的。雙核銅簇通過與配體相互連接構筑成兩種交替排列的籠狀結構�；谂潴wL_2,與硝酸銪和硝酸鋱通過溶劑熱法合成了兩個同構的稀土三維配合物3。經過X-射線單晶衍射測試可知,配合物3的空間群是P-1,屬于三斜晶系。配合物3和4的整個結構中沿a軸方向包含有兩種不同的一維孔道,都是由六個配體和八個金屬中心圍繞而成,并且所有配體上的磺酸基全部分布于孔道中,具有很好的親水性,但可能由于配體中摻雜的金屬鈉離子在配合物合成過程中參與了配位而導致整體骨架的水不穩(wěn)定性,無法進行有水導電測試,由于配體上磺酸基團之間距離過大而無法在無水條件下構建質子通路,所以在無水條件下也不具備導電性能。后續(xù)工作中將探索并合成水穩(wěn)定性較好的質子導體材料。
[Abstract]:Metal organic frameworks (Metal-Organic Frameworks, referred to as MOFs), also known as porous coordination polymer (Porous Coordination Polymers, referred to as PCPs), is made of metal ion / cluster (also known as the secondary building unit, Secondly Building Units, SBUs) and organic ligands. The material and structure can be designed with adjustable pore size. And the hole wall functionalization and highly crystalline characteristics in adsorption / separation, conductive, magnetic, catalytic, fluorescence, has a good application prospect of ferroelectric and biomedicine. Since MOFs materials are found can be used as proton transport materials, scientists have opened a research upsurge of proton conducting properties of MOFs the material, in recent years, this field has been the rapid development of the application of rapidly maturing. Most of the core components of proton exchange membrane fuel cell is the proton exchange membrane, it can separate the battery The fuel and oxidizer, and allow protons in the membrane by free, is the key to affect the battery life and performance. Chemists by changing the ligand type, reaction conditions such as a building with excellent electrical properties of MOFs materials, and to improve the conductivity of modified by various methods, make this application more mature, a solid theoretical foundation for the practical application. In this paper, we mainly carried out the following work: first, we based on the MIL-88B structure, forming the Cr-MIL-88B structure with different functional groups of organic ligands and chromium ions, of different ligands influence on the proton conductivity and improve. In addition, anhydrous conductive properties of the structure were explored by ligand doping strategy. We choose terephthalic acid (H_2BDC), 2- (H_2BDC-NH_2), 2- amino acid methyl Terephthalic acid (H_2BDC-CH3), 2,5- (H_2BDC-2CH3) two methyl terephthalate isomorphic MIL-88B structure respectively with the metal ligand chromate synthesis of different ligands, and the selection of auxiliary ligands TPT into the crystal structure of the flexible structure is opened, Cr-MIL-88B-NH_2 finally Cr-MIL-88B were analyzed, and proton conductivity of Cr-MIL-88B-tpt of these three complexes in different humidity conditions. In addition, to explore the complexes with different ligands of the four ligands with Cr-MIL-88B doping isomorphism, and preliminary test the anhydrous proton conductivity. It is found that the complex Cr-MIL-88B structure has good proton conductivity properties. Two, the design and synthesis of polycarboxylate ligands L_1,5- benzyl thiol isophthalic acid and two flexible multi carboxylate the two ligand L_2,1,2- (2- sulfo -4- carboxylic acid phenyl ethoxy) ethane. Design method by using solvothermal polycarboxylic acid ligands and copper mining based on L_1 Three dimensional complexes 1 and two heterogeneous complexes 2. through X- ray diffraction test shows the synthesis, with 1 of the space group is P-1, three belongs to triclinic. This structure has two kinds of copper clusters, respectively connected with ligand to form a 1D channels along the a axis. The complex space group the 2 is I4/m, belongs to tetragonal. Complex 2 by adding three ethanol solution of triphenylphosphine obtained in the synthesis of complexes 1. On the basis of binuclear copper clusters by connecting with each other to build into two kinds of ligands are arranged alternately. The cage structure based on ligand L_2, nitrate and europium and terbium nitrate by solvent hydrothermal synthesis of rare earth complexes with 3D isomorphism of two and 3. by X- ray diffraction shows that the complex space group is 3 P-1, three belongs to triclinic. Complexes 3 and 4 in the whole structure along the a axis contains two different 1D channels, is made up of six From around the eight ligands and metal centers, and all the sulfonic acid ligand part distributed in pores, have good hydrophilicity, but may be due to sodium metal ion ligand complexes doped in the synthesis process involved in the coordination and overall framework of water lead to instability, not the water conducting test, because between the ligand sulfonic acid groups on the distance is too large it is unable to construct the proton pathway under anhydrous conditions, so under anhydrous conditions do not have electrical properties. The follow-up work will explore and synthesis of water stable proton conductor material.

【學位授予單位】：鄭州大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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