聚(3,4-烷撑二氧噻吩)类导电聚合物纳米空心球-Au纳米复合材料的制备与电催化活性研究

The project intends to choose the 3,4-ethylenedioxythiophene, 3,4-propylene dioxythiophene , mercaptomethylene substituted 3,4-ethylenedioxy thiophene, mercaptomethylenesubstituted 3,4-propylenedioxythiophene and hollow sulfur nanosphere(template) for preparing poly(3,4-alkyldioxythiophene) conducting polymer hollow nanospheres-Au nanocomposites by in situ polymerization, polymer reduction, and physical blending methods, respectively. These nanocomposites will be applied for electrochemical detection of dopamine and ascorbic acid, and the electro-catalytic activity of these nanocomposites toward the electrochemical detection of dopamine and ascorbic acid will be evaluated. The effect of thiol group on the uniform dispersion of Au nanoparticles in the composite as well as the effects on the electro-lcatalytic activity of composite will be discussed. The project will explore the advantages and deficiencies of different methods, and take a deep studies on the controllable and reproducible reaction for composing to evaluate the application of hollow sulfur nano spheres as hard for the preparation of the this type of composites. And, with the systematic characterization and testing on composite materials, the project will take deep studies on the effect and contribution of structure and molar ratio of PEDOT type conducting polymers on the properties and functions of composite materials, and the relations between the structures and properties of these composites,as well as the effects of the reaction conditions on the reaction rate, structure of composites, crystallinity, electro-catalytic activity will be discussed. At last, the theoretical and practical bases for future application of poly (3,4-alkyldioxy thiophene) conducting polymer hollow nanospheres-Au nanocomposites as electrochemical sensor will be supplied.

本项目拟以3,4-乙撑二氧噻吩、3,4-丙撑二氧噻吩、巯基亚甲基取代-3,4-乙撑二氧噻吩、巯基亚甲基取代-3,4-丙撑二氧噻吩为单体，纳米硫空心球为硬模板，以Au纳米颗粒为无机相，采用原位聚合法、聚合物还原法和物理共混法等手段制备中空纳米聚(3,4-烷撑二氧噻吩)类导电聚合物纳米空心球-Au纳米复合材料，并通过该类复合材料对多巴胺和抗坏血酸的电化学检测，评价该类材料对目标物的电催化活性。研究巯基对Au纳米颗粒在复合材料中的均匀分散以及对电催化活性的影响。探索不同方法中，复合过程的可控性即反应的均匀性和重现性等问题，实现可控均匀复合，从而全面评价纳米硫空心球为硬模板法制备该系列复合材料的应用前景。通过对复合材料的物理化学性能的研究，探讨复合物中各组分结构、尺度、分散性及其在复合材料中的所占比例对材料整体功能的贡献和影响。最终为该结构类复合材料在电化学传感器领域内的应用提供理论和实践基础。

本项目以EDOT类单体为有机相，分别以Au纳米材料、氮掺杂石墨烯、多孔硅、g-C3N4、碳纳米材料(SRFC、YRFC、MWCNT)为无机相，采用不同模板制备了PEDOT类空心球/Au的二元复合材料和与氮掺杂石墨烯的三元复合材料；采用原位聚合法制备了PEDOT类聚合物与多孔硅和碳材料的系列复合物；采用溴催化法、固相加热法、原位氧化聚合法制备PEDOT/ g-C3N4复合材料。探讨了反应条件和方法对复合材料结构与性能的影响，研究了在结构中引入巯基官能团对Au纳米颗粒均匀稳定负载及复合材料电催化性能的贡献，分析了聚合物和无机相组分在复合材料中所占比例对材料整体结构与电催化性能的影响，系统的研究了该类复合材料在电化学传感器方面的应用。研究结果表明：以SiO2为模板制备的PEDOT类空心球/Au的二元复合材料对抗坏血酸、多巴胺、尿酸生物小分子具有较好的电催化性能。在PEDOT结构单元中引入甲基硫醇使得Au纳米材料被更加均匀、稳定的负载在聚合物空心纳米球表面，PEDOT类空心球/Au复合物中加入氮掺杂石墨烯，皆可提高了该类复合材料对金纳米材料的高分散性和其电催化活性。PEDOT 纳米空心球/Au/N-Gr 对AA,DA和UA具有较好的的线性关系，线性范围分别为1.5-100 μM，0.08-80 μM，0.2-70 μM。Poly(EDOT-MeSH)纳米空心球/Au/N-Gr复合物对AA, DA, UA和NO2-，其线性范围分别为0.5-65 μM,0.02-60 μM,0.06-55 μM以及0.1-70 μM。PEDOT-(MeSH)/Si PProDOT(Me SH)2 /Si对重金属离子(Cd2+、Pb2+、Hg2+)具有更低的检出浓度和更高的灵敏度。其中PProDOT-(MeSH)2/Si复合材料对Cd2+、Pb2+、Hg2+的检测限分别为8.3 nM、4.7 nM、8.0 nM。溴催化法制备得到的PEDOT/10 wt% g-C3N4和PEDOT/10 wt% N-GNP具有较高的线性检测范围、较低的检出限和较高的电催化能力。多壁碳纳米管、黄壳结构的碳纳米球、葡萄糖球等碳纳米材料分别于PProDOT进行复合后，其复合材料的电催化能力和电储存能力均有明显提高。