大孔-微孔结构手性金属有机骨架复合材料的制备及不对称催化性能研究

项目名称： 大孔-微孔结构手性金属有机骨架复合材料的制备及不对称催化性能研究

项目编号： No.51503062

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 一般工业技术

项目作者： 霍甲

作者单位： 湖南大学

项目金额： 23万元

中文摘要： 本项目针对目前手性金属有机骨架多为微孔材料，底物扩散阻力大，且缺乏通用制备多级孔金属有机骨架的方法等问题，拟通过先制备手性金属有机骨架纳米颗粒稳定的乳液体系，再聚合交联连续相，即界面纳米组装/聚合法获得兼具大孔结构和金属有机骨架特征微孔结构的手性金属有机骨架/聚苯乙烯复合材料。将设计合适的乳液体系制备包含不同手性配体（包括对空气敏感的Ti-BINOL配体、稳定的Fe-Salen型配体和有机手性配体）的大孔-微孔复合材料，并分别将其应用于催化芳香醛立体选择性加成反应、硫醚不对称氧化反应和羟醛不对称缩合反应。研究纳米颗粒粒径、物料比、剪切作用及连续相溶剂等对复合材料孔结构和不对称催化性能的影响。最终获得高效、低成本且有尺寸选择性能的手性催化剂以及通用的制备方法，推进不对称催化反应生产光学纯手性物质的工业化步伐。

中文关键词： 界面纳米组装；手性金属有机骨架；聚合物复合材料；大孔-微孔；不对称催化

英文摘要： The aim of this project is to synthesize macro-microporous homochiral metal-organic framework (MOF)/polystyrene composites to find a solution of the higher diffusion resistance of microporous MOFs and shortage of a general synthetic route. The composites will possess the macroporous structure and retain the microporous feature of MOFs, which will be prepared through interfacial nano-assembly for the formation of the homochiral MOF nanoparticles-stabilized emulsion droplets followed by polymerization and cross-linking of continuous phase. Optimized emulsion systems will be designed to synthesize the macro-microporous composites separately incorporating air-sensitive Ti-BINOL complex, stable Fe-Salen complex, and chiral organocatalyst, which will be applied for asymmetric heterogeneous catalysis of alkyl addition to benzyl aldehyde, sulfide oxidation, and aldol reaction, respectively. The influence of size of nanoparticles, ration between reactants, shear force, and solvents of continuous phase on the asymmetric catalytic properties will be investigated systematically. Ultimately, highly efficient, inexpensive homochiral metal-organic framework catalysts with the size-selective property and their general synthetic strategy will be developed for pushing their industrial application for the production of chiral compounds.

英文关键词： Interfacial nano-assembly;homochiral metal-organic framework;polymeric composite;macro-microporoe;asymmetric catalysis