高导电二维聚苯胺及衍生物晶体膜的可控合成、结构与性能

To compete with their inorganic analogues in all possible application areas, the charge carrier mobility and ordering of polyaniline need to be greatly improved. To address this challenge, we will explore molecules which can be self-assembled into highly ordered structures at interfaces, to guide the alignments of aniline and its derivatives into dynamic periodic structures with tunable molecular interactions at interfaces, then initiate the polymerization of anilines at both para- and ortho-positions, establish a methodology for controlled synthesis of two-dimensional polyaniline and their derivative membranes, aiming to achieve crystalline two-dimensional polyaniline and derivative membranes with highly ordered areal repeating units and structure control on the molecular level, increasing the conductivity significantly, hoping to solve the low motility of charge carriers due to hoping among different chains in conditional polyaniline. We will delineate the microstructures of polyaniline and their derivative membranes, such as crystallization degree, domain sizes and molecular structures. We will increase the conductivity of the crystalline membranes by introducing defects in a controlled manner, systematically investigate the conductivity of the membranes before and after introducing defects, and establish a structure-property relationship between the conductivity and microstructures of the membranes. We will explore the synthesized crystalline membranes as electrode materials for supercapacitors, create supercapacitors with superior performance, and establish a structure-property relationship between the microstructure of the membranes and performance of the supercapacitors, paving the way for the design of supercapacitors with controlled performance. Accordingly, the proposed project is expected to have significant implications in both theory and application in the near future.

在可能的应用领域中传统聚苯胺与对应的无机材料相比，存在载流子迁移率低、难于形成有序结构等亟待解决的关键科学问题。针对这一科学问题，本项目拟在界面上形成结构高度有序的诱导剂膜，通过相互作用控制，动态地将苯胺及衍生物排列成高度有序结构，在界面上引发苯胺同时发生邻位和对位聚合，建立可控制备二维聚苯胺及衍生物晶体膜的方法，获得具有高度规整网状结构的二维聚苯胺及衍生物晶体膜，实现导电性能的极大提升，避免传统聚苯胺（线性结构）导电时载流子须在不同的分子链间跃迁造成的迁移速率显著下降。在阐明二维聚苯胺及衍生物晶体膜的微观结构如结晶度、晶畴尺寸和分子结构的基础上，对晶体膜可控植入缺陷点，提高晶体膜的导电性能，揭示晶体膜的结构与性能的内在关联。以获得的晶体膜为超级电容器电极材料，制备高性能的超级电容器，探讨膜的微观结构与器件性能的关系，为设计性能可控的超级电容器提供理论依据，具有重要的理论和实际应用价值。

针对有机二维聚合物因规整度（结晶度）差导致性能不佳如电子迁移率低等问题，在气/液界面和结构诱导剂/水界面，通过界面作用力调控，以结构诱导剂等外界刺激调控单体和前驱体的动态自组装，减少高度规整二维聚合物形成的熵变，控制聚合过程，促进产物高度规整排列，建立了可控制备高度规整二维聚合物的方法，获得了得具有高度规整网状结构的二维聚苯胺膜，所得二维聚苯胺膜的电子迁移率可达250 S cm-1. 在近原子分辨尺度下对二维聚合物膜化学结构、聚集态结构和缺陷结构的基础上，揭示了二维聚合物膜的化学结构、聚集态结构和缺陷结构与电导、传感和电催化性能之间的内在关联，为设计结构和性能可控的二维聚合物及其器件提供了理论指导，具有重要的理论和实际应用价值。