利用天然色素构建光催化氧化偶联甲基苯丙胺新体系的研究

云南是我国禁毒斗争的最前沿阵地和主战场，目前尚未开展缴获毒品的资源化利用研究。本项目拟利用苝醌、叶绿素等天然色素的模板和敏化双重功能合成TiO2/SiO2气凝胶、羟基磷酸氧铋，再将其用于可见光催化氧化冰毒（甲基苯丙胺）合成亚胺。鉴于甲基苯丙胺结构完全不同于目前所研究的光催化氧化偶联的胺类化合物，项目将为缴获冰毒资源化利用和新亚胺化合物的光催化合成提供新思路，也将色素模板所制光催化材料尚局限于污染物的光催化降解拓展至光催化氧化偶联胺类化合物。兼具模板和敏化功能的色素经焙烧后将被转化为自掺杂在所制材料中的碳化物而非原色素化合物，从而增强所制材料的可见光吸收和扩大所制材料的比表面积。这与传统染料敏化只是吸附，且敏化后的染料仍然是原化合物完全不同。拟研究色素模板及所制光催化剂组成、形貌及结构等特征与催化氧化偶联性能的构效关系，优化光催化反应条件，初步揭示所制材料光催化氧化偶联甲基苯丙胺反应机理。

The abuse of illicit drugs is a major concern in society. While the conventional method such as incineration, could cause a series of emerging, potential, non-traditional environmental risks. It is urgently required to develop methods for the transformation of seizure drugs to some useful or potentially useful compounds. Currently, the photocatalytic oxidative coupling of diverse amines to the corresponding imines has been intensively investigated. However, it is more challenging to oxidize the secondary amines and aliphatic primary amine than the primary amines with benzene ring during amine oxidation. In this project, we will synthesize TiO2/SiO2 and Bi3O(OH)(PO4)2 templated and photosensitized by plant pigments. In sharp contrast to regular photosensitization methods in which the original dyes were always left and acted as photosensitizers after photosensitization, in our study natural pigments such as hypocrellins and chlorophyll, will be directly used a structure-directing agent during the synthesis of thermally stable TiO2/SiO2 aerogels and Bi3O(OH)(PO4)2 and removed by calcinations, rather than external adsorption. In this process, natural pigments will act as both a template and a “photosensitizers” which was transferred to in situ carbon species because no any original pigments or photosensitizers were left but carbon species were produced after this calcination treatment. This seems to be the first production of TiO2/SiO2 aerogels and Bi3O(OH)(PO4)2 with carbon species and visible light photocatalytic activity in this way. This will enhance the visible light photocatalytic activities for the photocatalytic oxidative coupling of methamphetamine due to the enhancement of the absorption in the visible region and surface area of the synthesized materials. The reaction conditions, such as reaction temperatrure and time, solvents, the amount of the photocatalysts will be optimized. A catalyst exhibiting high substrate conversion and good product selectivity is expected to obtained.