共轭聚电解质的设计合成及其可见光催化产氢性能研究

In this project, cyclopentathiophene, fluorene and Pt-containing complex were chosen as building blocks, benzothiadiazole, oxadiazole and fluorene derivatives were introduced as linkers to synthesize different types of anionic and cationic conjugated polyelectrolytes. The visible-light-absorbing ability and charge carrier mobility of the polymers could be improved by electron-inducing effect between the incorporated conjugated unit in the main chain and photocatalytic active unit, which is expected to enhance their hydrogen production activities. The self-assembled morphologies, photophysical properties and hydrogen production performances of conjugated polyelectrolytes were also studied by modifying their side chains with different counterions or introducing different sulfonate side chains into the conjugated backbone. Besides, to develop highly efficient photocatalytic hydrogen production system, organic comonomers with different electronic and spatial features are introduced into platinum-containing conjugated backbone to optimize energy levels and photophysical properties of the polymers by metal to ligand charge transfer interaction.

以环戊联噻吩、芴及含铂配合物为构筑基元，苯并噻二唑、噁二唑及芴衍生物为连接体，合成不同结构特征的阴、阳离子型共轭聚电解质。通过在主链上引入不同的共轭单元，与光催化活性单元之间产生电子诱导效应，提高高分子对可见光区太阳光的吸收能力及载流子迁移效率以增强其产氢活性。通过在高分子侧链上修饰不同的抗衡离子或引入不同的磺酸根阴离子侧链，研究其在光催化体系中的自组装形态、光物理性质与产氢性能的内在关系。将不同电子效应及空间效应的有机配体引入铂炔基共轭高分子主链上，通过金属到配体中心电荷转移作用，调控高分子的能级带隙及光物理性质以发展高性能的光解水产氢体系。

利用太阳光驱动水分解生产氢气是转化并存储太阳能的理想手段之一，发展高效、廉价、稳定的半导体光催化剂是制约该技术大规模发展的关键。本项目以共轭聚电解质为研究主线，通过侧链工程优化共轭聚电解质的光生载流子分离与传输，实现了其光催化天然海水分解产氢性能的大幅度提升。发展了二元共轭聚电解质光催化产氢体系，通过阴离子型共轭聚电解质掺杂实现了阳离子型共轭聚电解质光催化产氢效率的显著提高。本项目的实施，揭示了共轭聚电解质在光催化体系中的自组装形态、光物理性质与光解水产氢性能的内在关系，提出了共轭聚电解质光催化水分解产氢性能增强的新途径，为发展高效有机半导体光催化产氢体系提供了新的思路和理论依据。