无机半导体/噻吩及卟啉基层状有机骨架复合材料的合成及光电性能研究

The long-range pi orbital overlap in two dimensional covalent organic framework (COF) gives rise to high exciton and charge mobilities, which make 2D COF an excellent cadidate for organic photoelectric material.On the other hand, the high surface area and large pore size might accommodate complementary semiconductors or other functional guests, which make it possible to fabricate donor-acceptor composite photoelectric materials.This project intends to synthesize high performance donor-acceptor composite materials by employing layered COFs with high intrinsic charge mobility and structural versatility and inorganic semiconductors.We will first synthesize 2D layred COFs with high intrinsic charge mobolities by choosing proper monomers, followed by damaging the non-covalent interactions between different layers by mechano or sonochemical exfoliation or chemical modification of COF surface to achieve solution dispersable COF films since interfacing COF reliably to electrods is necessary to realize their optoelectronic potential.We next will synthesize COF film/inorganic composits, optimize the photoelectronic properties by surface modification, structure optimization and skeleton doping of the COF films and investigate their applicatuons in the field of optoelectronic devices.In summary,this work will establish a series of methods used to construct solution disperable layered COF monolayer films, get different surface modification and skeleton doped COF film, achieve high performance COF/inorganic hybrid materials and initially investigate the relationship between structure and device performance of these materials.

二维层状有机骨架材料（COF）的层间长程pi-pi堆积赋予了这种材料极高的载流子迁移率，使其成为一种优异的有机骨架光电材料。另一方面，层状COF材料高的比表面及孔道结构赋予了其容纳其它光电活性材料的能力，为构筑高性能电子给体-受体复合光电材料提供了可能。本工作拟借助二维层状COF的高本征电荷迁移率及结构的可控性构筑薄膜COF/无机半导体高性能给-受体复合光电材料并用于光电器件的构筑。通过合适的单体选择，获得具有高本征电荷迁移率的二维层状COF，借助机械剥离及化学修饰等手段破坏二维层状COF层间的非共价键相互作用，获得可用于器件构筑的COF薄膜，以克服目前粉末COF材料的分散性差及难以用于器件构筑等方面的限制。通过表面修饰，结构优化及骨架掺杂等手段实现不同薄膜COF与无机纳米材料的有效复合，优化所获得复合材料的光电性能，进而阐述材料结构与器件性能的依赖关系。

本项目主要开展了刚性骨架结构多孔聚合物的设计合成及应用研究。在前期对此类材料（例如共价有机骨架，共轭微孔聚合物等）孔尺寸、孔表面性质及骨架结构进行系统调控的基础上，进一步，通过表面引发聚合的方法，实现了共轭多孔聚合物材料薄膜化，实现了高通量的分子过滤及分离。首次阐明共轭微孔聚合物的全刚性骨架导致材料高的孔隙率及孔道联通性，从而导致极高的物质传输速度。项目执行期间共发表包括Nat. Chem., Adv. Mater., Adv. Energy Mater., J. Mater. Chem. A等在内的第一及通讯作者论文9篇。本项目实现了对刚性骨架结构材料的薄膜化，并用于构筑新型高效纳米过滤膜，展示了通过对此类材料薄膜孔结构的精细调控实现多种重要工业分离体系，如有机溶剂纳滤、共沸物、同系物、异构体等高效分离的可能性，为构筑新一代高性能膜分离材料奠定了理论基础。