以催化为导向的功能化金属有机配位聚合物的合成及性质研究

发布时间：2018-03-26 17:08

  本文选题：金属有机配位聚合物　切入点：原位组装　出处：《山东师范大学》2017年硕士论文

【摘要】：金属机配位聚合物新颖的结构和独特的性质,使其在非均相催化领域具有广泛地应用。本文分别通过原位组装、负载活性客体分子和后合成修饰这三种方式合成了基于金属有机配位聚合物的非均相催化剂,并分别对其多功能催化、催化串联反应和协同催化的性质进行了研究。I.从课题组前期工作中筛选出两例基于Cu(I)的金属有机配位聚合物,其中化合物1是1D锯齿形结构,两种Cu金属中心间存在弱的Cu···Cu相互作用,[Cu Br2]-作为反荷阴离子悬挂在1D链的外面。化合物2是1D梯形链状结构,[Cu2Br4]2-作为反荷阴离子,位于两条链中间,连接两条相邻的1D链。将这两例化合物分别作为非均相催化剂催化了酚乙酰化反应和A3(炔+醛+胺)偶联反应。经研究发现化合物1均可以高效催化这两类反应,催化剂可循环使用至少五次,并且其催化效率远远高于化合物2的催化效率,证明了化合物1结构中裸露的[Cu Br2]-作为催化活性中心,减小了反应的位阻,有利于反应的进行。II.利用已知结构的3D Cu4I4-MOF实现了对I2的可逆吸附,得到了负载非金属单质的多孔复合材料0.75I2@Cu4I4-MOF。0.75I2@Cu4I4-MOF不仅可以高效催化缩醛脱保护反应和醛与吲哚的傅-克烷基化反应,还可催化缩醛与吲哚的傅-克烷基化串联反应,并取得了很好的催化效果,催化剂循环使用五次后催化活性并无大幅度降低且仍保持自身结构和形貌稳定,首次实现了非金属@MOF高效催化有机串联反应。III.以结构和性质稳定的Ui O-66-NH2为基质,通过后合成修饰的方式引入硫脲官能团得到Ui O-66-Thiourea,转化率为38.4%,并通过红外、质谱、PXRD等对其性质进行了表征。UiO-66-Thiourea被应用于催化芳醛的硅氰化反应,转化率均在95%以上,催化剂在重复使用五次后催化效率并无明显降低,实现了MOF与有机小分子间的协同催化。研究表明,通过原位组装、负载活性客体分子以及后合成修饰得到的金属有机配位聚合物催化剂均可以对有机合成反应实现高效催化,丰富了催化剂的种类,为合成新型高效的非均相催化剂提供了新思路。
[Abstract]:Metal coordination polymers are widely used in heterogeneous catalysis due to their novel structure and unique properties. Heterogeneous catalysts based on metal-organic coordination polymers were synthesized by supported active guest molecules and post-synthetic modification. The properties of catalytic series reaction and synergistic catalysis were studied. I. two metal-organic coordination polymers based on Cui were selected from the previous work of our group, in which compound 1 was a 1D zigzag structure. There is a weak Cu Cu interaction between the centers of two Cu metals. [Cu Br2]-is suspended outside the 1D chain as countercharge anions. Compound 2 is a 1D trapezoidal chain structure, and [Cu2Br4] 2- is a reverse charge anion located between the two chains. The two compounds were used as heterogeneous catalysts to catalyze the acetylation of phenol and the coupling reaction of A _ 3 (acetylaldehyde amine). It was found that compound 1 could efficiently catalyze these two reactions. The catalyst can be reused for at least five times, and its catalytic efficiency is much higher than that of compound 2. It is proved that the exposed [Cu Br2]-in compound 1 structure acts as the catalytic active center and reduces the steric resistance of the reaction. The reversible adsorption of I _ 2 was achieved by using 3D Cu4I4-MOF with known structure. The porous composite 0.75I2@Cu4I4-MOF.0.75I2@Cu4I4-MOF supported on non-metallic materials could not only catalyze the deprotection reaction of acetal and the Friede-gram alkylation of aldehyde with indole, but also could effectively catalyze the deprotection of acetal and the alkylation of aldehyde with indole. It can also catalyze the Friede-gram alkylation of acetal and indole in series, and obtain a good catalytic effect. The catalytic activity does not decrease significantly and the structure and morphology of the catalyst remain stable after five cycles. For the first time, the high performance organic series reaction of non-metallic @ MOF was realized. The Ui O-66-NH2 with stable structure and properties was used as the substrate. The Ui O-66-Thioureawas obtained by introducing thiourea functional group by post-synthesis modification. The conversion was 38.4% and the conversion was 38.4%, and the Ui O-66-Thioureawas obtained by IR. Its properties were characterized by PXRD. UiO-66-Thiourea was used to catalyze the silicocyanic reaction of aromatic aldehydes. The conversion rate was above 95%. The catalytic efficiency of the catalyst was not significantly decreased after the repeated use of the catalyst for five times. The synergistic catalysis between MOF and small organic molecules has been realized. The results show that the organometallic coordination polymer catalysts can efficiently catalyze the organic synthesis by in situ assembly, loading of active guest molecules and modification of organometallic coordination polymers. It enriches the kinds of catalysts and provides a new idea for the synthesis of new and efficient heterogeneous catalysts.
【学位授予单位】：山东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O643.36
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本文编号：1668779