ZIF装载含钒杂多酸构建高效苯-O2羟基化制苯酚催化剂

苯一步羟基化制苯酚是至今未得到实际应用的绿色工艺，且原子经济型的无牺牲性还原剂条件下，使用非贵金属催化剂通过O2氧化液相苯制苯酚更极具挑战性。本项目拟基于本人在多酸基分子材料研究中的长期积累，首先设计合成含N的有机配体，然后根据配位化学原理，过渡金属通过配位键与所合成的有机组分构建沸石型ZIF材料，将含V多酸阴离子封装在ZIF材料的孔道中，制备一体式复合催化剂，旨在实现无还原剂苯-O2羟基化制苯酚的高效多相催化新工艺。结合量子化学计算，研究催化剂的设计和制备、组成结构和性质，以及催化活性和稳定性；实现材料中ZIF框架与多酸阴离子组分之间的无缝对接、协同效应、优势互补；通过表征分析深入认识含N的有机配体构建的ZIF骨架活化苯环以及多酸活化分子氧的双活性中心机理，揭示催化剂的电子因素、双活性中心分布与协同对催化性能的影响机制，为构建廉价高效苯-O2羟基化制苯酚绿色多相催化提供新思路和新方法。

The direct oxidation of benzene to phenol is a green chemistry technology that has not been applied in practice so far. Meanwhile, it is a great challenge for the preparation of phenol from liquid-phase benzene catalyzed by oxygen through non noble metal without sacrificial reductant. This project is based on my long-term accumulation in the research of polyoxometalate-based molecular materials. Firstly, N-containing organic ligands are designed and synthesized successfully. Then, according to the principle of coordination chemistry, transition metals and organic components were used to construct ZIF-based materials through the coordination bond, and the V-containing polyoxoanions are encapsulated in the pores of ZIF-based materials to prepare integrated composite catalysts, which aims to realize the efficient heterogeneous catalytic process the oxidation of benzene to phenol without reducing agent. In this work, the design and preparation, the composition structure and properties of the catalyst, as well as the catalytic activity and stability are studied in combination with quantum chemical calculation; to achieve seamless connection, enhanced synergy and complementary advantages between zeolitic imidazolate frameworks and anionic components of polyoxovanadates; through characterization and analysis, to deeply understand the mechanism of the double active center mechanism of zeolitic imidazolate frameworks constructed by N-containing organic ligands to activate benzene ring and polyoxometalates to activate molecular oxygen, reveal the influence mechanism of electronic factors, distribution and coordination of double active centers on the catalytic performance of the catalyst, so as to reveal the influence mechanism of electronic factors, double active center distribution and synergy on the catalytic performance of the catalyst, and provide the new idea and method for the preparation of cheap and efficient green heterogeneous catalyst for benzene hydroxylation.