高性能卟啉POF多相催化剂的结构调控及其催化植物油脂环氧化研究

多孔有机骨架(POF)材料由于具有更大的孔体积和丰富的孔道结构，尤其在酸碱，湿气，高温等苛刻条件下优异的结构稳定性，在催化领域已成为新兴的热点。仿生催化剂金属卟啉能在温和条件下高活性、高选择性的催化烯烃环氧化，但易发生氧化降解使活性降低，而且不易分离重复利用，为解决上述问题，本项目通过共价键连接金属卟啉合成POF催化剂，以云南省丰富的可再生非食用植物油脂资源为研究对象，进行催化植物油脂环氧化研究。首先进行刚性骨架卟啉单元前驱体的设计选择，然后探索高质量、大尺寸、结构有序的的金属卟啉POF催化剂的制备规律；建立高效的催化体系，阐明卟啉POF催化剂的构效关系及结构调控，筛选出高活性和高选择性的可循环利用的多相催化剂；确立卟啉POF催化植物油脂环氧化反应的最佳工艺条件，探索其催化植物油脂环氧化机理，建立卟啉POF催化剂活性中心结构与催化性能调控机制。本项目研究对植物油脂的高值化利用具有重要意义。

Many advances have been made in the design and synthesis of porous organic frameworks (POF) with good mechanical stability, high surface area, controlled surface functionality in recent years, and their wide applications in field of catalysis. The metalloporphyrin biomimetic catalysts gave higher conversion and selectivity by catalytic oxidation of hydrocarbons. Unfortunately, when used as homogeneous catalysts, they often suffer from quick degradation such as ligand oxidation or m-oxo dimer formation.And some disadvantages which increased the cost of reactions and limited application, such as the difficult recycle of catalysts after reaction. We report here Pyrenees-based porous organic frameworks (POF) catalyst. Based on total preparation and characterization of POF catalysts-based metalloporphyrin, epoxidation of vegetable oil over POF catalysts were investigated. The epoxidation of oil is mainly used in the vegetable oil. It's a green environmental protection type of plasticizer which has excellent performance. The epoxidation of the model over the catalyst was investigated to explain the mechanism of the epoxidation. Effects of the epoxidation conditions, such as time, reaction temperature, catalyst amount, on the conversion, selectivity, epoxided product structure were investigated mainly. Finally, a potential mechanism is also proposed in this research and the epoxided product of vegetable oil with excellent properties would be obtained. Through the project, it will provide new directions for the high-valuable utilization of vegetable oil.