本文關(guān)鍵詞： 金屬有機(jī)框架化合物 共價有機(jī)框架化合物 卟啉 催化 染料吸附　出處：《北京科技大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：在過去的二十多年里,關(guān)于有機(jī)多孔材料的研究發(fā)展迅速,由于其具有優(yōu)越的性能而被廣泛應(yīng)用在氣體的儲存與分離、超疏水界面、催化、能量的轉(zhuǎn)移及儲存和光電器件等方面。盡管科學(xué)家們已經(jīng)合成了各種各樣的孔材料,但是利用網(wǎng)狀化學(xué)設(shè)計合成具有特定孔尺寸及一定拓?fù)浣Y(jié)構(gòu)的孔材料還具有一定的難度。金屬有機(jī)框架化合物(Metal Organic Frameworks,MOFs)是第一類利用拓?fù)湓碓O(shè)計合成的具有一定網(wǎng)格結(jié)構(gòu)的有機(jī)多孔材料;共價有機(jī)框架化合物(Covalent Organic Frameworks,COFs)是另外一類利用拓?fù)湓碓O(shè)計合成的具有精確拓?fù)浣Y(jié)構(gòu)、明確孔徑分布的晶型多孔材料。卟啉是由四個吡咯通過亞甲基相連而形成的共軛大環(huán)化合物,其特有的結(jié)構(gòu)穩(wěn)定性和功能多樣性使其表現(xiàn)出超乎尋常的光、電、磁等性能,因此基于卟啉的多孔材料也可能具備這些優(yōu)異的特性,在生命、信息、材料科學(xué)等不同領(lǐng)域均有潛在的應(yīng)用前景。本論文主要以卟啉為基本構(gòu)筑單元，，研究其與不同的構(gòu)筑基元或者金屬節(jié)點形成的具有一定拓?fù)浣Y(jié)構(gòu)的COFs和MOFs材料,并詳細(xì)研究了其在催化和染料吸附方面的應(yīng)用。具體研究內(nèi)容如下:1本章工作用含氮豐富的四-(對氨基苯基)卟啉和4,4-聯(lián)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材料上負(fù)載鈀催化劑,通過透射電鏡發(fā)現(xiàn)該材料負(fù)載的鈀催化劑分散性很好,因此對Suzuki-偶聯(lián)反應(yīng)具有很高的催化活性,產(chǎn)率達(dá)到97.1-98.5%。并且該催化劑具有可回收性,重復(fù)使用四次后其催化效果和選擇性基本不變。2本章工作通過5,10,15,20-四-(對氨基苯)卟啉Cu(Ⅱ)和2.6-二甲氧基萘-1,5-二醛縮合反應(yīng),合成了一例新的亞胺鍵連接的卟啉基COF材料CuP-DMNDA-COF,在三氯化鐵的丙酮溶液中簡單處理后得到鐵配位的復(fù)合村料CuP-DMNDA-COF/Fe,該材料對染料RhB具有較好的吸附能力且能循環(huán)使用七次吸附性能基本保持不變,該研究結(jié)果顯示COFs材料在廢水處理方面具有很好地應(yīng)用潛力。3本章工作首次用5.15-(4-羧基苯)卟啉(H2DCPP)和堿土金屬離子(Mg2+,(Ca2+、Sr2+,Ba2+)通過溶劑熱方法合成了一系列四個卟啉基堿土MOFs 1-4。單晶X-射線衍射分析顯示這四個化合物具有周期性納米尺寸孔的網(wǎng)絡(luò)結(jié)構(gòu)。這四個堿土MOFs對亞甲基藍(lán)均具有很好地選擇性吸附性能。其中Ca-MOF 2是目前吸附亞甲基藍(lán)(MB)量最大的MOF材料,吸附量達(dá)到了952 mg/g。這樣的結(jié)果不僅代表了第·例堿土金屬MOF用于染料的吸附性能研究,而且更重要的是為主族MOF的應(yīng)用開辟了一個新的方向。
[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

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