二维共轭有机半导体材料实现高效光催化分解水制氢研究

Photocatalytic hydrogen evolution is an attractive method for the acquisition of clean and sustainable energy with the use of solar power. Compared with inorganic systems, organic semiconductors have a series of advantages such as molecular structure can be synthesized by design, easy to fine tune absorption spectrum and energy levels, and low cost of preparation procedure. It is considered to be an ideal choice towards optoelectronic functional applications for new era and new demands. At present, the organic photocatalysts often have a hydrophobic main chain structure, and most of them are insoluble in conventional solvents, and the phase size is difficult to be effectively controlled by manual intervention, which may cause batch to batch differences and difficulty in forming uniform dispersion in an aqueous solution. This project aims to develop a series of organic semiconductor material systems with two-dimensional conjugate properties and uniformed phase sizes through structural design and synthesis method development. On one hand, the hydrophilic side chain is introduced into the main chain structure through structural design, so that the obtained material can be uniformly dispersed in water, and on the other hand, a synthetic method capable of controlling the phase size of the obtained material is developed to ensure the material has good repeatability. At the same time, it is also convenient to further study the relationship between materials structure and their optoelectronic application performance.

光催化分解水制氢是一种理想的获取清洁能源手段，因此高效光催化剂的发展在近年的研究工作中备受关注。相比于无机体系，有机半导体材料具有分子结构高度可调，吸收光谱、能级易于进行精准剪裁修饰以及制备成本低廉等一系列优势，被认为是发展面向新时代、新需求的光电功能化应用材料体系的理想选择。目前所报道的有机光催化剂往往具有疏水性主链结构，同时大都不能溶于常规溶剂，相尺寸难以通过人工干预进行有效控制，会造成批次差异以及难以在水溶液中形成均匀分散等问题。本项目旨在通过结构设计与合成方法上的研究发展一系列具有二维共轭特性的有机半导体材料体系。一方面通过结构设计在主链结构中引入亲水性侧链，使所得材料能够在水中进行均匀分散，另一方面发展一种能够控制所得材料相尺寸的合成方法，保证材料具有良好重复性的同时，也便于进一步研究材料的构性关系。

多维有机共轭化合物因其结构多样性以及独特的电化学、光物理特在近年的研究工作中备受关注，并且在多领域已经实现广泛拓展应用。相比于无机体系，有机材料体系具有分子结构高度可调，吸收光谱、能级易于进行精准剪裁修饰以及制备成本低廉等一系列优势，被认为是发展面向新时代、新需求的光电功能化应用材料体系的理想选择。在项目执行期内，申请人对以有机共轭单元为核心的多维化合物进行设计合成并在储能、光催化等领域进行初步探索。基于三聚茚、三聚茚酮、卟啉等有机共轭分子结构开发出一系列具有电化学、光物理性能的功能性化合物。共价有机骨架材料COF-TRO作为阴极活性材料制备全固态锂离子电池的比容量达到268 mAh/g；是采用该系类材料作为全固态锂离子电池阴极所达最高比容量之一；有机共轭分子笼TC1、TC3因其出色的超分子主-客体效应有望在未来的光催化研究中实现高性能催化。该系列研究工作对未来光电高分子、小分子材料的发展起到参考作用。