基于CuAAC点击反应的二茂铁基聚噻吩的合成及其对氧化锌纳米线的共价表面修饰研究

The inorganic/organic nanocomposites become the hot spot in the area of functional material fabrication. Ferrocene-based polythiophene derivatives are a class of organic materials with excellent electrical, magnetic, catalytic, and redox properties. Zinc Oxide, one of the most concerned inorganic semiconductor materials also shows unique optical, electrical, magnetic properties. Thus it is of key importance for the preparation of composites combined the properties of these two materials. At present, a lot of research work reported the generation of P-type conductive polymer/N-type zinc oxide composites material utilizing spin coating or oxidized or electrochemical polymerization on the surface of zinc oxide, and their applications in devices such as organic solar cell, light-emitting diode etc. Due to the high surface energy, random active layer morphology, and weak physical adsorption and desorption on the formed interface, it still has great limitation for the application of the obtained composites materials. CuAAC ‘click’ reaction is a convenient and reliable tool for molecule design, organic synthesis and material surface modification, this proposal combines CuAAC reaction and many other synthetic tools for covalently grafting of ferrocene-based polythiophene onto surface of zinc oxide nanowires, by enhancing interfacial interaction to improve compatibility of materials, and deliver more stable, orderly, and high load organic/inorganic nanocomposites. Via the reduction of ferrocene and weak coordination of abundant triazole-pentacycles on the surface of nanocomposites, obtained via CuAAC reactions, the transition metal nanoparticles could be prepared and stabilized on surface of ferrocene-based polythiophene grafted ZnO nanowires, and the photoelectric properties and applications will be explored for the obtained multifunctional composite materials.

无机/有机复合材料是功能材料制备领域的热点。二茂铁基聚噻吩是一类具有优异电、磁、催化及氧化还原性能的有机材料，无机半导体ZnO也具有独特的光、电、磁性能，制备融合这两者特性的复合材料具有重要意义。目前很多报道采用旋涂或在ZnO表面氧化或电化学聚合制备p型导电聚合物/n型ZnO复合材料，用于太阳能电池、发光二级管等器件中，但因界面高表面能、无规的活性层形态和弱物理吸附与脱除，所得复合材料的应用仍有很大局限性。CuAAC点击反应是分子设计、有机合成及材料表面修饰便捷可靠的工具，本项目将联用CuAAC反应等多种合成手段将二茂铁基聚噻吩衍生物共价链接到ZnO上，通过界面强共价键的构筑提高材料的相容性，制备稳定、有序、高负载的复合材料；并通过复合材料表面的三唑五元环对过渡金属的弱配位和二茂铁的还原作用，制备茂基聚噻吩修饰的ZnO纳米线表面稳定的过渡金属纳米粒子，并探究所得多功能复合材料的性能和应用。

无机/有机复合材料是功能材料制备领域的热点。二茂铁基聚噻吩是一类具有优异电、磁、催化及氧化还原性能的有机材料，无机半导体ZnO也具有独特的光、电、磁性能，制备融合这两种材料特性的复合材料具有重要意义。目前很多报道采用旋涂或在ZnO表面氧化或电化学聚合制备p型导电聚合物/n型ZnO复合材料，用于太阳能电池、发光二级管等器件中，但因界面高的表面能、无规的活性层形态和弱物理吸附与脱除，所得复合材料的应用仍有很大局限性。 CuAAC点击反应是分子设计、有机合成及材料表面修饰中便捷可靠的工具，本项目联用点击反应等多种合成手段将二茂铁基聚噻吩共价链接到ZnO上，通过界面强共价键的构筑提高材料的相容性，制备稳定、有序、高负载的复合材料；通过将带荧光的微囊藻毒素（MC-LR）适配体DNA共价固定在氧化锌纳米线上，通过MC-LR与其适配体的特异性作用制备了基于氧化锌的MC-LR传感器，在水质监控中会有重要应用。