卟吩和细菌卟吩基MOFs的设计合成及其光催化降解有机污染物的性能研究

Porphyrinic metal-organic frameworks (porph-MOFs) have wide potential application in photocatalysis due to their photosensitive properties and tunable functionalities. Compared to porphyrin, their derivatives chlorin and bacteriochlorin showed much improved photophysical properties due to their red-shifted Q band and enhanced extinction coefficient. This project will design and synthesize chlorin and bacteriochlorin based MOFs with different type structure (PCN and UiO family) and their composites (MOFs@TiO2) which TiO2 NPs anchored onto the surface through axially bond. The resulting materials will achieve a wide photo response range in the whole visible (or near-infrared) light region to improve the photocatalytic activities significantly. The photocatalytic activity and the mechanism of photocatalytic degradation of organic contaminants under visible light irradiation based on the corresponding MOFs and composites was systematically investigated. The aim of this project is to fabricate the chlorin and bacteriochlorin-based MOFs and establish the research system of their application for photocatalytic activities and elucidate their relationship and influencing factors. This project provides a new strategy to improve the light harvesting efficiency and the photocatalytic activities of porphyrin-based MOFs materials and has a significant scientific value to promote the development of porphyrin derivatives-based MOFs for photocatalytic degradation of organic pollutants.

卟啉基金属有机框架材料结合了卟啉染料的光敏性质和MOFs的结构可控性而在光催化领域具有广阔的应用前景。与卟啉相比，其衍生物卟吩和细菌卟吩具有更红的Q带吸收和更高的摩尔消光系数，表现出更好的光学性质。本项目拟设计合成以卟吩和细菌卟吩为有机配体的MOFs材料（PCN和UiO系列）以及TiO2通过轴向配位固定在MOFs表面的复合材料（MOFs@TiO2），实现该MOFs在整个可见光甚至近红外光区光催化，提高其光催化活性。考察其在可见光照射下降解有机污染物的光催化性能和光催化机理，建立卟啉，卟吩和细菌卟吩基MOFs光催化降解有机污染物的催化活性的研究体系，阐明两者之间的关系和影响因素。本项目的实施为进一步提高卟啉基MOFs光催化剂的光捕获效率和光催化性能提供了新思路，对推进卟啉类衍生物基MOFs材料在光催化降解有机污染物领域的应用具有重要的科学意义。

与卟啉基金属有机框架材料相比，其衍生物卟吩和细菌卟吩基MOFs具有更红的Q带吸收,更高的摩尔消光系数和更强的荧光发射，表现出更好的光学性质。本项目合成了两个卟吩基MOFs材料（TCPC-Zr和TBC-Zr），用于降解和吸附有机染料罗丹明B，降解效率达到77%，吸附量达到498 mg·g-1；另外卟吩基优异的荧光性能使其在F-和PO43-的传感方向得到了很好的应用，其检出限分别为和1.06×10-8 mol·L-1和1.2×10-8 mol·L-1；设计并制备一种新的细菌卟吩基MOFs，相对于已本报道的细菌卟吩基MOFs，材料更加稳定，应用也更加广泛。本项目的结果对卟啉类衍生物类MOFs材料在光催化，传感等领域具有重要的指导意义和科学价值。