含卟啉基团的多孔芳香骨架材料的设计、合成及其性质研究

发布时间：2018-05-03 07:15

本文选题：多孔芳香骨架材料 + 卟啉　；参考：《吉林大学》2017年博士论文

【摘要】：有机多孔材料(Porous Organic Frameworks,POFs)是一类利用有机基块通过共价键连接构筑而成的新型多孔材料,近年来发展尤为迅速。它具有超高的比表面积、超高的稳定性、孔道的可控性和官能团可修饰性,优异的性质使它们在气体的储存与分离,有机催化,能源存储与传递等领域有巨大的应用前景。卟啉作为一类重要的仿生原料也有非常优异的性质,人们对其在仿生领域、光电领域的优秀性能一直有着浓厚的兴趣。本论文立足于含有卟啉基团的多孔芳香骨架材料的设计合成,研究材料在小分子烷烃存储与分离、有机催化及电催化析氧性能方面具有潜在的应用价值。首先,利用AlCl_3催化的肖尔反应,以四苯基卟啉为单体合成了PAF-40,以四苯基卟啉-Fe和四苯基卟啉-Mn为单体合成了PAF-40-Fe和PAF-40-Mn,探究金属离子的引入对材料比表面积和气体吸附分离性质的影响。我们测试了这三个材料的小分子烷烃吸附性能,并用IAST计算了C2和C3小分子烷烃对于CH4的分离比。结果显示,PAF-40s材料具有较高的气体吸附量,PAF-40-Fe提高了小分子烷烃的吸附焓,PAF-40-Mn大大提高了C2和C3小分子烷烃对CH4的分离比。其次,利用Suzuki偶联反应,以四苯甲烷四硼脂和四溴四苯基卟啉为单体合成了PAF-76,以四溴四苯基卟啉-Fe、四溴四苯基卟啉-Mn和四溴四苯基卟啉-Zn代替四溴四苯卟啉,分别合成了PAF-76-Fe、PAF-76-Mn和PAF-76-Zn。我们对上述材料进行了苯乙烯催化氧化的性质测试,催化结果表明,PAF-76s有优异的催化性能,其中PAF-76-Mn在苯乙烯的高转化率,对苯乙醛产物的高选择性方面具有最好催化性能,这是由于框架中的单一和高度密集的金属位点在微孔骨架的富集。合成的PAF-76s催化剂显示出高的热稳定性,良好的再循环性和对溶剂的优异的耐用性都证明了其优异的异相催化能力。最后,利用席夫碱反应,以四氨基四苯基卟啉和5,10-二(4-氨基苯基)-10,20-二苯基卟啉的氨基与1,3,5-三甲酰基间苯三酚分别合成了PAF-77和PAF-78。此外,我们后修饰Co离子合成了PAF-77-Co和PAF-78-Co,探究了这些具有不同结构材料的电催化水析氧性质。骨架孔容、孔径差异和金属离子引入将影响材料析氧性质。通过比较电化学性质,我们发现从过电势、塔菲尔斜率方面性质优异趋势为PAF-78-CoPAF-77-CoPAF-78PAF-77。合成的PAF-77s和PAF-78s催化剂均显示出在强酸强碱溶液中的高稳定性。
[Abstract]:Porous Organic Frameworks (POFs) is a new type of porous material made of covalent bonds by organic base blocks. It has developed rapidly in recent years. It has super high specific surface area, high stability, the controllability of the channel and the functional group modifiability. The excellent properties make them in the storage and storage of gas. Separation, organic catalysis, energy storage and transmission have great potential applications. Porphyrin as an important kind of biomimetic raw material also has very excellent properties. People have been interested in its excellent performance in the field of bionics and photoelectric field. This paper is based on the design of porous aromatic skeleton materials containing porphyrin groups. Synthesis, research materials have potential applications in the storage and separation of small molecular alkanes, organic catalysis and the performance of electrocatalytic oxygen evolution. First, using the Shaw reaction catalyzed by AlCl_3, four phenyl porphyrin is synthesized by PAF-40, and PAF-40-Fe and PAF-40-Mn are synthesized with four phenyl porphyrin -Fe and four phenyl porphyrin -Mn as monomers. The influence of the introduction of ions on the specific surface area and gas adsorption separation properties. We tested the adsorption properties of small molecular alkanes in these three materials and calculated the separation ratio of C2 and C3 small molecules of alkanes to CH4 by IAST. The results showed that the PAF-40s material had higher gas absorption and PAF-40-Fe increased the adsorption of small molecular alkanes. Enthalpy, PAF-40-Mn greatly enhanced the separation ratio of C2 and C3 small molecular alkanes to CH4. Secondly, PAF-76 was synthesized by Suzuki coupling reaction with four benzyl methane four boron grease and four bromine four phenyl porphyrin, with four bromo four phenyl porphyrin -Fe, four bromine four phenyl porphyrin -Mn and four bromo four phenyl porphyrin -Zn instead four bromine four phenyl porphyrin, and PAF-76 respectively synthesized PAF-76. -Fe, PAF-76-Mn and PAF-76-Zn. have been tested for the catalytic oxidation of styrene. The catalytic results show that PAF-76s has excellent catalytic properties. The high conversion of PAF-76-Mn in styrene has the best catalytic performance for the high selectivity of phenylacetaldehyde products, which is due to the single and high density of the framework. The concentration of the metal site in the microporous skeleton. The synthesized PAF-76s catalyst showed high thermal stability, good recirculation and excellent durability to the solvent, which proved its excellent heterogeneous catalytic ability. Finally, the Schiff base reaction was made with four amino four phenyl porphyrin and 5,10- two (4- amino phenyl) -10,20- two phenyl porphyrin. PAF-77 and PAF-78. were synthesized between the base and 1,3,5- Triamyl benzoyl, respectively. PAF-77-Co and PAF-78-Co were synthesized by modified Co ions. The properties of the electrocatalytic water evolution of these different structural materials were investigated, the pore volume of the skeleton, the difference of pore size and the oxygen evolution properties of the material were introduced by metal ions. By comparing the electrochemical properties, We found that the high stability of PAF-77s and PAF-78s catalysts for PAF-78-CoPAF-77-CoPAF-78PAF-77. synthesis showed high stability in strong acid and strong alkali solutions from the potential of over electric potential and Tafel slope.

【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB383.4

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