介孔分子筛复合固载NHPI/Cosalen催化剂的构建及其在无溶剂甲苯液相分子氧氧化反应中的性能研究

本项目将碳自由基生成催化剂NHPI与具有活化分子氧功能的Cosalen配合物通过共价接枝的方法复合固载到介孔分子筛SBA-15上，用于催化甲苯的液相分子氧氧化反应，在无溶剂条件下，将反应场所转移到介孔分子筛的空腔中，借助分子筛孔道的尺寸效应和载体的疏水性能以及NHPI侧链的电子环境，在温和的条件下选择性生成附加值更高的产物苯甲醛和苯甲醇，避免深度氧化反应生成苯甲酸。复合固载的催化剂将易于与反应液分离，能够重复使用。拟对复合固载催化剂的制备条件进行详细考察，采用多种手段对催化剂结构进行表征，对比评价SBA-15-NHPI/Cosalen在甲苯氧化反应中的催化性能及重复使用性，通过构效关系的考察，探寻NHPI体系甲苯氧化反应选择性调控的普遍规律以及保持NHPI稳定性的关键因素，为烃类的选择性氧化提供技术积累和理论支持。

The carbon free radical generation catalyst NHPI and Cosalen complex with activation of molecular oxygen will be immobilized on the mesoporous molecular sieve SBA-15 as carrier through the covalent grafting, which is used as catalyst in the liquid aerobic oxidation of toluene under the condition of no solvent, the place of reaction is transferred into the hollow mesoporous pore of zeolite, by the size effect of sieve channel, the hydrophobic properties of carrier and the electronic enviroment of NHPI with side chain derivatives, toluene will be selectively converted into benzaldehyde and benzylalcohol with high added value, avoiding the happen of deep oxidation to benzoic acid. The composite catalyst is easy to separate from the reaction mixture for repeated use. The preparation conditions of the composite catalyst will be investigated and various means are used to characterize the structure of catalyst. The catalytic and reuse performance of catalysts SBA-15-NHPI/Cosalen will be evaluated by contrast.Through the study of the structure-activity relationship, the universal rule of the selectivity regulate and control of the toluene oxidation would be seeked，the key factors of keeping the stability of the NHPI are espected to be observed. The study work will provide the technology accumulation and theoretical support for the selective oxidation of hydrocarbons.