有序多级孔卟啉MOF组装体的可控构筑及苯乙烯催化环氧化性能增强机制研究

The catalytic epoxidation of styrene is of great significance in petrochemical industry, and the core lies in the development of high efficiency catalyst. In this proposal, novel porphyrinic MOF assemblies with ordered macro-meso- micro-porous structure were synthesized. Firstly, meso-micro-porous porphyrin MOF nanosheets were prepared by co-deposition-selective etching method, in which the content and distribution of metal can be well regulated by adjusting the experimental parameters. Subsequently, hierarchical porous porphyrin MOF assemblies were achieved by a template method, which help to solve the key scientific problem that the micro-porous structure of MOF material is not conducive to the diffusion of catalytic substrate. The synthesis mechanism of hierarchical porous porphyrinic MOF assemblies was explored. The precisely control of the pore structure was realized by regulating the synthesis conditions. A systematic investigation is also to be conducted on the formation mechanism of hierarchical porous porphyrinic MOF assemblies. This project is expected to provide a novel and efficient catalyst for the catalytic epoxidation of styrene, and lay a foundation for the development and application of porous heterogeneous catalysts.

苯乙烯的催化环氧化在化工生产中具有重要意义，其核心在于高效催化剂的开发。本项目拟针对这一问题，围绕有序多级孔卟啉MOF组装体的可控构筑及其催化性能研究开展工作。首先，通过共沉积-选择性刻蚀的方法制备介孔-微孔卟啉MOF纳米片。随后，通过模板法实现有序大孔-介孔-微孔卟啉MOF组装体的可控构筑，解决MOF材料微孔结构不利于催化底物扩散的关键科学问题。深入研究多级孔二维卟啉MOF组装体的合成机理，并通过调控合成条件，精确控制其孔道结构。系统考察产物的孔道结构对催化底物扩散的影响规律，研究苯乙烯催化环氧化性能增强机制，并揭示催化剂孔道结构与催化性能之间的构效关系。本项目有望为苯乙烯的催化环氧化提供一种新型、高效的催化剂，并为高效多孔非均相催化剂的开发与应用奠定基础。

开发用于苯乙烯催化环氧化的高效催化剂有重要意义。针对金属有机框架（MOFs）催化剂微孔结构对催化过程中反应物和产物扩散阻力大限制催化效率提高的关键问题，本项目提出利用共沉积-选择性刻蚀构筑分级孔道结构有效提升催化底物扩散效率及苯乙烯催化环氧化性能。此外，通过MOFs原位化学转化构建了纳米片组装体，进一步增加了MOFs催化剂表面活性位点。结合吸附实验、理论计算研究了MOFs催化剂孔道结构、纳米片组装结构与催化性能的内在关联，对高性能非均相催化剂开发提供了一定的实验基础和理论依据。项目相关成果在Angew. Chem. Int. Ed.、Small、Nanoscale等期刊发表SCI论文8篇，申请国家发明专利4项。