基于卟啉框架化合物的构筑及其性质研究

发布时间：2018-02-22 22:03

  本文关键词： 金属有机框架化合物 共价有机框架化合物 卟啉 催化 染料吸附　出处：《北京科技大学》2017年博士论文　论文类型：学位论文

【摘要】：在过去的二十多年里,关于有机多孔材料的研究发展迅速,由于其具有优越的性能而被广泛应用在气体的储存与分离、超疏水界面、催化、能量的转移及储存和光电器件等方面。尽管科学家们已经合成了各种各样的孔材料,但是利用网状化学设计合成具有特定孔尺寸及一定拓扑结构的孔材料还具有一定的难度。金属有机框架化合物(Metal Organic Frameworks,MOFs)是第一类利用拓扑原理设计合成的具有一定网格结构的有机多孔材料;共价有机框架化合物(Covalent Organic Frameworks,COFs)是另外一类利用拓扑原理设计合成的具有精确拓扑结构、明确孔径分布的晶型多孔材料。卟啉是由四个吡咯通过亚甲基相连而形成的共轭大环化合物,其特有的结构稳定性和功能多样性使其表现出超乎寻常的光、电、磁等性能,因此基于卟啉的多孔材料也可能具备这些优异的特性,在生命、信息、材料科学等不同领域均有潜在的应用前景。本论文主要以卟啉为基本构筑单元，，研究其与不同的构筑基元或者金属节点形成的具有一定拓扑结构的COFs和MOFs材料,并详细研究了其在催化和染料吸附方面的应用。具体研究内容如下:1本章工作用含氮丰富的四-(对氨基苯基)卟啉和4,4-联苯二甲醛合成了一例COF材料H2P-Bph-COF,并采用后合成方法在H2P-Bph-COF材料上负载钯催化剂,通过透射电镜发现该材料负载的钯催化剂分散性很好,因此对Suzuki-偶联反应具有很高的催化活性,产率达到97.1-98.5%。并且该催化剂具有可回收性,重复使用四次后其催化效果和选择性基本不变。2本章工作通过5,10,15,20-四-(对氨基苯)卟啉Cu(Ⅱ)和2.6-二甲氧基萘-1,5-二醛缩合反应,合成了一例新的亚胺键连接的卟啉基COF材料CuP-DMNDA-COF,在三氯化铁的丙酮溶液中简单处理后得到铁配位的复合村料CuP-DMNDA-COF/Fe,该材料对染料RhB具有较好的吸附能力且能循环使用七次吸附性能基本保持不变,该研究结果显示COFs材料在废水处理方面具有很好地应用潜力。3本章工作首次用5.15-(4-羧基苯)卟啉(H2DCPP)和碱土金属离子(Mg2+,(Ca2+、Sr2+,Ba2+)通过溶剂热方法合成了一系列四个卟啉基碱土MOFs 1-4。单晶X-射线衍射分析显示这四个化合物具有周期性纳米尺寸孔的网络结构。这四个碱土MOFs对亚甲基蓝均具有很好地选择性吸附性能。其中Ca-MOF 2是目前吸附亚甲基蓝(MB)量最大的MOF材料,吸附量达到了952 mg/g。这样的结果不仅代表了第·例碱土金属MOF用于染料的吸附性能研究,而且更重要的是为主族MOF的应用开辟了一个新的方向。
[Abstract]:In the past 20 years, the research on organic porous materials has developed rapidly. Due to its superior performance, it has been widely used in gas storage and separation, superhydrophobic interface, catalysis, Energy transfer and storage, optoelectronic devices, etc. Although scientists have synthesized a variety of porous materials, However, it is difficult to synthesize porous materials with specific pore size and certain topological structure by using reticular chemical design. The metal-organic framework compound Organic frameworks is the first kind of porous materials with certain topological principle. Organic porous materials with grid structure; Covalent organic framework compound Covalent Organic frameworks (COFs) is another class of exact topological structures designed and synthesized by using topological principles. Porphyrin is a conjugated macrocyclic compound formed by linking four pyrrole through methylene. Its unique structural stability and functional diversity make it exhibit extraordinary optical, electrical, magnetic and other properties. Therefore, porphyrin-based porous materials may also have these excellent properties and have potential applications in different fields such as life, information, material science, etc. In this paper, porphyrin is used as the basic building unit. The COFs and MOFs materials with certain topological structure formed by different building units or metal joints are studied. The application of H2P-Bph-COF in catalysis and dye adsorption was studied in detail. A case of COF material H2P-Bph-COF was synthesized from nitrogen-rich tetra- (p-aminophenyl) porphyrin and 4- 4- biphenyl diformaldehyde as follows: 1. The palladium catalyst was supported on H2P-Bph-COF material by the method of synthesis. It was found by TEM that the palladium catalyst supported on the material had good dispersion, so it had high catalytic activity for Suzuki-coupling reaction, and the yield reached 97.1-98.5.The catalyst was recoverable. After repeated use for four times, the catalytic effect and selectivity of the catalyst remained basically unchanged in this chapter. 2. In this chapter, the condensation reactions of 5H1010155- (p-aminobenzene) porphyrin Cu (鈪

本文编号：1525420