稳定型金属-有机框架中定向合成石墨烯片段及光催化性能研究

This project aims to combine graphene materials with metal-organic frameworks (MOFs) crystalline materials and obtain the porous crystalline materials with tunable pore size by using organic moieties with good solubility and facilely converted into well-defined graphene fragments, which can be realized by stereospecific synthesis using a mild postsynthetic annulation reaction to create long-range ordered graphene fragments inside a single crystal. Simultaneously, a biomimetic metal-porphyrin unit can be introduced into the organic synthon to realize the dispersion and immobilization of the biomimetic unit and the graphene fragments in the MOFs materials at the molecular level. These materials not only possess isolated functional sites and dynamic host-guest responses, but also combine the properties of graphene and MOFs materials, expecting to produce surprising synergies. We will study the photocatalytic reactivity of such materials and hope to solve the problems like easy agglomeration and stacking of three-dimensional graphene materials, as well as wrinkles. The effects of synthesis methods, sizes of graphene fragments, polyoxometalate species and structure-property relationships on the photocatalytic performance of these catalysts will be investigated. Furthermore, the optimal combination of these catalysts showing the best catalytic activity, and the catalytic mechanism will be investigated by means of molecular dynamics simulations and other computational methods. This project would seek a rapid synthesis of three-dimensional graphene-based porous crystalline materials under mild conditions, and provide a theoretical and experimental basis for the development and application of three-dimensional graphene materials and optical-functionalized MOFs materials.

本项目拟将石墨烯材料与MOFs晶体材料结合，利用溶解性好且可转换成石墨烯片段的有机单元制备出孔尺寸可调的多孔材料，再通过单晶内部温和的环化反应，定向合成长程有序石墨烯片段的多孔催化剂。有机基元方面可同时引入仿生型金属卟啉，实现MOFs材料中仿生单元和石墨烯片段在分子水平上的分散与固载。这类材料不仅具有孤立的功能位点及动力学主客体响应，还将兼具石墨烯和MOFs材料共同的特性，可产生令人惊喜的协同作用。我们将研究这类材料在光催化的反应活性，期望解决三维石墨烯材料易团聚和堆叠，以及褶皱现象等问题。探讨这类催化剂的合成方法、石墨烯片段尺寸、多金属氧簇种类、构效关系对其光催化性能的影响；并利用分子动力学模拟等计算手段寻找这类催化剂的最佳活性组合，研究其催化机理。本项目可寻求一种在温和条件下快速合成三维石墨烯基多孔晶体催化剂，为三维石墨烯材料和光功能MOFs材料的开发应用提供理论和实验依据。

将大共轭类石墨烯片段与多孔晶体材料结合，利用溶解性好的类石墨烯片段的有机单元制备出孔尺寸可调的多孔晶体材料。该晶体材料再通过温和的反应，定向合成具有石墨烯片段的多孔晶体催化剂。有机基元方面可同时引入仿生型金属基元，实现MOFs材料中仿生单元以及大共轭类石墨烯片段在分子水平上的分散与固载。这类材料不仅具有孤立的功能位点及动力学主客体响应，还将兼具石墨烯和MOFs材料共同的特性，可产生令人惊喜的协同作用。我们研究了这类材料在光电催化反应中的反应活性，解决了三维大共轭类石墨烯材料易团聚和堆叠，以及褶皱现象等问题。探讨了这类催化剂的合成方法、大共轭类石墨烯片段尺寸、多金属氧簇种类、构效关系对其光催化性能的影响；并利用分子动力学模拟等计算手段寻找这类催化剂的最佳催化活性组合，研究了其催化机理，为三维石墨烯材料和光电功能多孔材料的开发应用提供理论和实验依据。