界面聚合构建一维纳米结构PEDOTs及其与TiO2复合材料的光解水性能

TiO2-mediated semiconductor photocatalytic water-splitting for hydrogen evolution is an important solar photochemical conversion way to achieving clean energy. Modification of TiO2 with conducting polymer PEDOTs possesses special advantages on breaking through the barriers of TiO2 from its large bandgap and low quantum efficiency. However, its giant application potential in the field of photocatalytic water-splitting hasn't been explored. This project will take the design and synthesis of EDOTs monomers as the basis and then fabricate one-dimensional (1D) nanostructured PEDOTs via interfacial chemical oxidative polymerization in solution phases. After loading TiO2 via in situ hydrolysis of titanium sources and the deposition of Pt nanoparticles as co-catalysts via Ultraviolet reduced chloroplatinic acid, a series of ternary Pt/TiO2/PEDOTs nanofibril composites will be achieved. Their applications for Visible-light-irritated water splitting hydrogen production and related reaction dynamical mechanism will be investigated. The surface/interface effect of semiconductor heterojunction and the migration mechanisms of the photoexcited carriers will be studied. Special attention will be put to establish the construction methodologies of 1D nanostructured PEDOTs, and clarify its synergistic effect on extending the Visible-light absorption, enhancing the separation and migration efficiency of photoinduced electrons and holes, and improving the dispersion and recyclability of TiO2. Through clarifying the relation between structures and performances, this work will promote the development of the conducting polymer nanocomposites in the field of photocatalysis, and provide certain theoretical guidance and technical support.

TiO2半导体光解水制氢是太阳能光化学转化获取清洁能源的重要途径。导电聚合物PEDOTs改性对突破TiO2宽禁带和量子效率低的瓶颈具有独特优势，但在该领域的应用潜能尚未被发掘。本项目拟以EDOTs单体结构设计与合成为基础，采用溶剂相界面化学氧化聚合策略，构建一维纳米结构的PEDOTs，并通过钛源水解法原位负载TiO2和氯铂酸紫外光还原法沉积助催化剂Pt，构建三元Pt/TiO2/PEDOTs纳米纤维复合材料。研究其可见光分解水制氢性能及反应动力学，探明复合材料表/界面异质结效应和光生载流子迁移机制，重点建立一维纳米结构PEDOTs的构建方法学，明晰其在拓展TiO2可见光吸收、提高光生载流子分离和迁移效率、改善分散性回收性等方面的协同作用，揭示结构—性能关联，藉此推动导电聚合物纳米复合材料在半导体光催化领域的发展，并提供理论指导和技术支撑。

TiO2光催化剂的可见光响应是限制其在光解水获取清洁氢能源应用的核心问题之一。PEDOTs改性有望突破TiO2宽禁带和量子效率低的瓶颈。本项目以EDOTs的结构设计与合成为基础，采用溶剂相界面有序聚合方法，构建聚合物一维纳米结构，并与并噻吩或苝二酰亚胺（PTCDI）结构单元结合，构建一维纳米分子聚集体。通过负载TiO2和沉积助催化剂Pt，构建纳米纤维复合材料，探究其可见光分解水制氢效果，揭示结构—性能关联。主要研究内容和结果如下：.（1）从溶解性、稳定性、分子平面性、光学吸收、能级结构、载流子迁移率、分子共轭程度等几方面开展了EDOTs分子的设计，合成了EDOT的氧族杂原子替代类似物、丙撑衍生物、二聚体（bisEDOT）、三聚体（triEDOT）、D-A构型的齐聚物等二十余种衍生物；并引入立体结构规整且具有刚性平面结构的并噻吩（TT、DTT）和PTCDIs，合成了二十余种与EDOT共聚和基于PTCDI单元的齐聚物；建立了合成策略和方法。.（2）通过电化学聚合、界面化学氧化聚合、分子界面自组装等溶剂相技术手段，获取了噻吩衍生物、EDOTs的聚合物及PTCDIs的聚集体一维纳米纤维结构，探究了前驱体结构-溶剂体系-方法路线-聚合物或聚集体形貌结构等之间的内在关联。.（3）研究了PEDOTs和PTCDIs等一维纳米纤维与TiO2和助催化剂Pt复合材料的构建，及其可见光催化分解水应用效果，揭示了材料的优势和缺陷，提出了光电催化新思路，实现了多孔一维纳米纤维薄膜电极的构建。.这些工作为将推动导电聚合物纳米复合材料在光催化和光电催化能源转化领域的发展，并提供材料、技术和经验支撑。