可见光响应的非均相多孔高分子光催化剂的制备与应用研究

Photocatalysis under visible light is a rapidly emerging and promising technology coming up with clean, green, energy saving and sustainable innovation in organic reactions. We found that 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (hereafter abbreviated as BODIPY) are highly efficient photocatalysts. Its photocatalytic activities are comparable to organometallic photocatalysts for the selective oxidation reaction of sulfide. In addition, the high internal phase emulsion polymerization has been used to prepare polymeric photocatalyst. But its catalytic reaction velocity is not satisfactory. Therefore, this project will prepare BODIPY-PolyHIPE by combining the BODIPY moieties onto the inner surface of the PolyHIPE porous matrix via the click reaction and study the catalytic efficiency of the BODIPY-PolyHIPE for some important organic reactions, paying special attention to the factors affecting the catalytic efficiency such as the molecular structure of BODIPY and the pore size of PolyHIPE, to obtain more basic knowledge on polymeric visible-light-driven photocatalysts, such as catalytic activity, efficiency, reaction velocity, recovery rate and reuse of the catalysts. Based on these findings, new polymeric heterogeneous porous catalysts which can work under the visible-light irradiation with high efficiency, high stability, and high recyclability can be designed and prepared.

可见光响应的光催化体系具有清洁、环保、节能和可持续发展等优点，在有机合成中得到较多应用。申请者前期实验中发现吡咯甲川-二氟化硼络合物（BODIPY）在硫醚选择性氧化反应中具有与金属钌催化剂相当的催化活性。此外，申请者曾尝试以高内相乳液聚合材料（PolyHIPE）为光催化剂载体，获得了成功，使构建以多孔高分子为载体的非均相可见光催化剂成为可能，但反应速度尚不够理想。所以，本课题拟将BODIPY结合到PolyHIPE表面，形成BODIPY-PolyHIPE复合物。进而探讨BODIPY-PolyHIPE对一些重要有机反应的催化效率；研究BODIPY的分子结构，PolyHIPE的孔径等影响催化效率的因素；研究并解决基于PolyHIPE的非均相高分子光催化剂催化有机化学反应的活性、效率、速率、回收、重复利用等关键科学问题，为获得高效、稳定、可重复多次使用、可见光响应的非均相高分子光催化剂提供新途径。

可见光响应的光催化体系具有清洁、环保、节能和可持续发展等优点，在有机合成中得到较多应用。项目负责人前期实验中发现吡咯甲川-二氟化硼络合物（BODIPY）在硫醚选择性氧化反应中具有与金属钌催化剂相当的催化活性，可以使底物的转化率达到100%。此外，项目负责人曾尝试以高内相乳液聚合材料（PolyHIPE）为光催化剂载体，获得了成功，使构建以多孔高分子为载体的非均相可见光催化剂成为可能，但完成上述硫醚选择性氧化反应（底物转化率接近100%）需要60小时，可见其反应速度尚不够理想。本课题首先制备了多个新颖的BODIPY化合物，并申请了专利保护。制备了一种即含有三键官能团，又具有较高单线态氧生成量子产率的新型BOIDPY化合物，即iodic-BOIDPY。将iodic-BODIPY结合到PolyHIPE表面，形成iodic-BODIPY-PolyHIPE复合物。深入研究了iodic-BODIPY-PolyHIPE对硫醚选择性氧化反应的催化效率和反应速率；研究并解决了基于PolyHIPE的非均相高分子光催化剂催化有机化学反应的活性、效率、速率、回收、重复利用等关键科学问题，为获得高效、稳定、可重复多次使用、可见光响应的非均相高分子光催化剂提供了新途径。