基于“金属有机骨架体”的生物-化学催化体系的建立和催化串联反应性能研究

High catalytic efficiency, abundant type of catalysts, and synergic catalytic property of bio-chemical catalysts have led to their wide application in “green” cascade reaction. The aim of this project is to develop a general strategy to synthesize novel bio-chemical catalytic systems for cascade reaction, based on the easy chemically functionability and highly ordered and tunable porosity of metal organic frameworks (MOFs). These systems, so called “MOFsome”, will be prepared through preparation of MOF-supported nanocatalysts followed by interfacial nano-assembly. Three different catalysts including bio-metal nanocatalyst, bio-organometallic catalyst, and bio-metal nanocatalyst-organometallic catalyst will be designed for dynamic kinetic resolution, Suzuki-Miyaura coupling-transesterification, and Suzuki-Miyaura coupling-dynamic kinetic resolution, respectively. Recyclability will be improved further by magnetic functionalization and cross-linking; the influence of content of catalysts, ration between oil and water phase, shear condition, content of magnetic particles, and cross-linking degree on the catalytic properties of bio-chemical catalysts will be investigated systematically to ultimately achieve high efficiency, high selectivity, and superior recyclability.

生物-化学催化体系因其催化效率高、催化类型繁多及协同催化性能，广泛应用于催化串联反应。本项目旨在利用金属有机骨架的易化学修饰性和孔径高度有序性，探索通用方法建立生物-化学催化体系并研究其催化串联反应性能。该方法将先制备化学催化剂负载金属有机骨架纳米颗粒，再进行界面纳米组装制得封装有生物酶的“金属有机骨架体”，获得生物-化学催化体系。将基于此法设计多种催化体系，包括生物酶-纳米金属、生物酶-有机金属和生物酶-纳米金属-有机金属催化体系，并分别将其应用于催化动态动力学拆分反应、Suzuki-Miyaura偶联-酯交换反应和Suzuki-Miyaura偶联-动态动力学拆分反应。进一步采用磁功能化和交联稳定提高催化体系循环使用性能；系统研究催化剂含量、油/水比、剪切条件、磁性颗粒含量、交联程度等对催化体系性能的影响，最终获得高效、尺寸选择性、可循环使用的生物-化学催化体系。

生物-化学催化体系因其催化效率高、催化类型繁多及协同催化性能，广泛应用于催化串联反应。本项目旨在利用金属有机骨架的易化学修饰性和孔径高度有序性，探索通用方法建立生物-化学催化体系并研究其催化串联反应性能。该方法将通过先制备化学催化剂负载金属有机骨架纳米颗粒，再进行界面纳米组装制得封装有生物酶的“金属有机骨架体”，获得生物-化学催化体系。将基于此法设计多种催化体系，包括生物酶-纳米金属、生物酶-有机金属和生物酶-纳米金属-有机金属催化体系，并分别将其应用于催化动态动力学拆分反应、Suzuki-Miyaura偶联-酯交换反应和Suzuki-Miyaura偶联-动态动力学拆分反应。进一步采用磁功能化和交联稳定提高催化体系循环使用性能；系统研究催化剂含量、油/水比、剪切条件、磁性颗粒含量、交联程度等对催化体系性能的影响，最终获得高效、尺寸选择性、可循环使用的生物-化学催化体系。