MOFs负载Pd催化剂的制备及其对Heck偶联反应的高效催化

发布时间：2018-06-24 12:59

本文选题：Heck反应 + 多相催化　；参考：《辽宁大学》2017年硕士论文

【摘要】：Heck偶联反应一般是指芳基卤代物与活性烯烃之间的反应,是构建不饱和碳碳双键的重要方法。自1970s以来,通过对其催化剂的不断完善和反应条件的不断优化、对反应底物的不断拓展,Heck反应的应用范围越来越广泛,已被广泛应用于众多有机合成反应中。常应用于合成药物分子、天然产物以及新材料等。对Heck偶联反应催化剂的研究经历了均相催化剂到多相催化剂的发展。均相催化剂经历了需要磷配体和不需要磷配体的发展过程,催化活性有了一定程度的提高,但是由于均相催化剂固有的缺点-难以从反应混合物中分离,不能重复利用等,造成了环境污染和资源浪费。这些缺点限制了Heck偶联反应的发展。为了解决这些问题而发展起来的多相催化剂,即将活性催化位点通过化学键固载到无机或者有机载体中。目前常用的载体有配位聚合物、活性炭、介孔材料、氧化铝等。虽然传统载体负载金属钯纳米粒子在改善均相催化剂易团聚、难分离、难以循环利用的缺点上取得了一定的成效。但是存在操作复杂或者催化效率偏低或者在使用过程中催化剂催化效率变低的问题,限制了Heck偶联反应的工业化。因此开发一种操作简便、催化活性高的新型复合材料来实现Heck反应的工业化是很有必要的。MOFs作为一种新型载体具有一系列的优点,本实验合成了Pd@MIL-101和Pd@HKUST-1两种复合材料催化Heck偶联反应。我的实验开篇介绍了Heck反应催化剂目前存在的问题、MOFs材料的特点、合成方法、发展和应用,论证了MOFs材料作为载体催化Heck反应的可行性。然后我合成了两种MOFs材料—MIL-101和HKUST-1,分别制备了Pd@MIL-101和Pd@HKUST-1两种复合材料。对这四种材料分别进行了表征,说明两种MOFs材料被成功的合成出来,制备的Pd@MOFs复合材料晶体构型保持不变,对催化Heck反应具有一定的潜力。接着研究了Pd@MOFs作为催化剂对Heck反应的催化,其中Pd@MIL-101对Heck反应的各类底物具有相对较高的催化活性,尤其是对于碘苯和丙烯酸酯类的反应,其催化速率高于目前同类反应的数倍最后对本论文的材料合成部分和催化实验部分进行总结,Pd@MIL-101复合材料对于Heck偶联反应的高效催化以及可循环使用有望应用于Heck反应的工业生产。
[Abstract]:Heck coupling reaction usually refers to the reaction between aryl halogenates and active alkenes. It is an important method to construct unsaturated carbon and carbon double bonds. Since 1970, through the continuous improvement of the catalyst and the optimization of reaction conditions, the continuous expansion of the reaction substrate Heck reaction has been widely used in many organic synthesis reactions. It is often used to synthesize drug molecules, natural products and new materials. The study of Heck coupling catalyst has experienced the development of homogeneous catalyst to heterogeneous catalyst. The homogeneous catalyst has experienced the development of phosphorus ligands and does not need phosphorus ligands, and the catalytic activity has been improved to some extent. However, due to the inherent shortcomings of homogeneous catalysts, it is difficult to separate from the reaction mixture and can not be reused, etc. It causes environmental pollution and waste of resources. These shortcomings limit the development of Heck coupling reactions. In order to solve these problems, the active catalytic sites are immobilized into inorganic or organic support by chemical bonding. The commonly used carriers are coordination polymers, activated carbon, mesoporous materials, alumina and so on. Although the traditional supported palladium nanoparticles have achieved some success in improving homogeneous catalyst agglomeration, difficult separation, and difficult to recycle. However, the industrialization of Heck coupling reaction is limited by complex operation, low catalytic efficiency or low catalytic efficiency. Therefore, it is necessary to develop a new composite material with simple operation and high catalytic activity to industrialize the Heck reaction. As a new carrier, MOFs has a series of advantages. In this paper, the Heck coupling reaction catalyzed by PD @ MIL-101 and Pdr HKUST-1 composites was synthesized. At the beginning of my experiment, the problems existing in Heck catalyst are introduced. The characteristics, synthesis method, development and application of MOFs are introduced, and the feasibility of using MOFs as carrier to catalyze Heck reaction is demonstrated. Then I synthesized two kinds of MOFs materials, -MIL-101 and HKUST-1, and prepared two kinds of composite materials, PdBM-MIL-101 and Pd@ HKUST-1, respectively. The results show that the two kinds of MOFs have been successfully synthesized, and the crystal configuration of the prepared PD @ MOFs composites remains unchanged, which has a certain potential for catalytic Heck reaction. Then the catalytic activity of PD @ MOFs for Heck reaction was studied. Pd@ MIL-101 had relatively high catalytic activity for various substrates of Heck reaction, especially for the reaction of iodobenzene with acrylate. Its catalytic rate is several times higher than that of the current similar reactions. Finally, the material synthesis and catalytic experiments of this thesis are summarized. The high efficiency catalysis and recycling of PdR MIL-101 composites for Heck coupling reaction are expected to be applied in Heck reaction. Reactive industrial production
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O621.251

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