高量子效率固态发光共轭多孔聚合物的合成与应用研究

Conjugated micro/mesoporous polymers (CMPs) have boost fast development during the past years. However, the control of polymer structure and functions is usually random and uncertain. Furthermore, their major applications are usually limited in gas adsorption and separation. It is worthwhile to explore other new application in optoelectronics, catalysis etc. In this proposal, we try to propose a simple but effective approach to induce and tune the optical and photo-catalytic properties of CMPs. Thus, our research work will be focused on the following three aspects: i) The construction of novel solid-state emitting CMPs based on AIE molecules like cyano-stilbenes using new preparation protocols. ii) Tuning the properties of the CMPs (especially the photochemical properties) via variation of monomer structures, polymerization methods and reaction conditions; Investigation on the relationship between different building blocks, aggregated states, and properties of CMPs; iii) Further construction of an inter-penetrating network based on the solid-state emitting CMPs and another photo-catalytic framework via in-situ polymerization of organic photo-catalysts. Then, the exploration of their application in energy transfer and photo-catalysis will be carried out and try to build up multifunctional modules of CMPs. This research will shine light on further preparation of cost-effective, efficient and green photo-catalyst based on conjugated porous polymers.

共轭多孔聚合物(CMPs)在过去几年得到了较快发展，但对其结构和功能的控制往往带有随机性和不确定性，且其应用领域还主要集中在气体吸附与分离。在其他诸如光电、催化领域的应用还有待进一步拓展。因此，申请人在本项目中拟发展一种简单有效的方法，来导入和调控CMPs的光学及光催化性能。基于此，我们将开展以下三方面具体工作：1. 筛选氰基苯乙烯类分子并采用新的制备方法构筑新型固态发光多孔聚合物；2. 研究不同结构单元，不同聚合方法及反应条件对材料光化学性能的调控机制，建立起分子结构、聚集态结构与多孔聚合物性能三者之间的联系；3. 将光催化剂分子在固态发光共轭多孔聚合物孔道内聚合形成互穿双网络，拓展其在能量传递、光催化功能材料等领域的应用，实现多种功能的集成模块化，为制备廉价、高效、绿色的多孔聚合物光催化剂提供参考。

本项目主要通过分子设计、电子态调控及聚合物刚性骨架控制等方法构建具有协同机制和增强放大效应的多功能共轭多孔聚合物。研究共轭多孔聚合物刚性骨架对电子、质子和能量迁移的增强作用；集中研究单体分子大小、对称性、拓扑结构以及反应条件对共轭多孔聚合物形貌、结构及性质的影响；构建出具有高效能量转移、有机光催化活性的功能复合材料体系。为后续优化多孔聚合物性能，进一步设计新型高性能多孔聚合物提供参考。主要包括以下四个方面的研究内容: 1. 具有聚集发光、光催化活性功能性结构单元的合成; 2.功能性多孔聚合物及互穿双功能网络的构筑; 3.功能性多孔聚合物材料光物理性质的表征和调控; 4功能性多孔聚合物光催化有机反应的性能研究。. 基于以上研究成果，发表论文19篇，其中包括J. Mater. Chem. A 5篇，Macromolecules 2篇，Chem. Eur. J. 3篇.项目承担者做国际国内学术会议邀请报告6次，培养博士学位获得者3人，期间获得天津市杰出青年项目资助。