后修饰法制备手性介孔锆基金属-有机骨架材料及其不对称催化研究

The study of chiral metal-organic framework (MOF) catalysts has been the focus of current chemistry, however the application range of chiral MOF catalysts has been severely restricted by the small pore size and the low chemical stability of chiral MOF catalysts reported to date. On the other hand, mesoporous MOFs have attracted considerable attention from scientists. However, the mesoporous MOFs with high chemical stability are still quite uncommon. Therefore, the construction of chiral mesoporous MOF catalysts with high chemical stability is a challenging task with great value. Considering that Zr-based MOFs possess excellent chemical stability, in this project, the mesoporous MOFs with good chemical stability are firstly prepared by controlled chemical etching reaction on the amino-functionalized Zr-MOFs. And then, the chiral mesoporous MOF catalysts possessing excellent chemical stability and high catalytic activity are firstly synthesized by covalent postsynthetic modification of mesoporous Zr-based MOFs with chiral organocatalysts. The modulation rules of the different mesopore sizes, the different structures and types of chiral organocatalysts, and the different original microporous Zr-MOFs on the asymmetric catalytic activity of these chiral mesoporous MOFs will be explored through the comparison, analysis and summarization of the catalytic activity of the obtained chiral mesoporous MOFs. The results of this project will provide a new route for the systematic and controlled synthesis of chiral mesoporous MOF catalysts with excellent chemical stability.

手性MOF催化剂研究已成为化学领域内的一个研究热点，然而当前手性MOF催化剂仍存在孔道较小和化学稳定性不佳两个缺点，严重限制了手性MOF催化剂的应用范围。另一方面，介孔MOFs研究近年来引起了科学家的广泛关注，但化学稳定的介孔MOFs还罕见报道。因此，构建化学稳定的手性介孔MOF催化剂是一个极具价值和挑战性的课题。考虑到锆基MOFs的优异化学稳定性，本项目拟首次对氨基功能化锆基MOFs进行可控化学刻蚀制备化学稳定的介孔MOFs；然后再首次用共价后修饰法在介孔锆基MOFs中嫁接手性有机催化剂，构筑催化活性高和化学稳定性优异的手性介孔MOF催化剂。通过对所得手性介孔MOFs的催化活性进行比较、分析和总结，探索不对称催化活性随手性介孔MOFs的介孔孔径、嫁接的手性有机催化剂的种类和结构、以及母体微孔MOFs结构类型的调控规律。相关研究结果为系统可控制备化学稳定的手性介孔MOF催化剂提供了新思路。

金属-有机骨架(MOF)材料研究已经成为化学领域内的一个研究热点，然而当前MOF材料仍然存在孔道较小和化学稳定性不佳两个缺点，从而严重限制了MOF材料的应用范围。因此，构建化学稳定的介孔、多级孔及中空MOF材料是一个极具价值和挑战性的课题，近年来也已经引起了科学家的广泛关注。在本项目中，我们首先通过选择具有优异化学稳定性的微孔锆基MOFs进行可控化学刻蚀，已成功制备了多个系列的高稳定介孔、多级孔、中空以及具有蛋黄-蛋壳(yolk-shell)结构的锆基MOFs，从而为可控制备化学稳定的介孔、多级孔、中空及yolk-shell MOFs提供了一条新的可行性路线。然后我们采用后修饰法在介孔、多级孔、中空以及yolk-shell锆基MOFs中嫁接手性有机催化剂及功能分子，成功实现了上述锆基MOFs的后修饰功能化，并对所得功能化锆基MOFs进行了不对称催化活性及其在生物分析方面的应用研究；这些工作为拓展锆基MOFs的应用范围提供了新的思路。