离子液体增效的新型固相微萃取头的电化学制备、表征及应用

Solid-phase microextraction (SPME) is a promising sampling and sample pretreatment technique. It has great application potential and attracts increasing interesting of researchers. In this project we intend to fabricate ionic liquid (IL, including liquid polymeric ionic liquids) functionalized netlike nano-structure coatings through one-step electrodeposition of polymer and polymer?nano-material on metal wires (such as stainless steel wire). Thus we can greatly improve the property of SPME fibers and make them not only have high extraction capacity, sensitivity, flexility and stability, but also present rapid extraction /desorption rate and good fabrication controllability. In addition, by using organic medium to promote the electrodeposition of some monomers with difficult to dissolve and/or electrodeposit in aqueous medium; and by introducing/or doping carbon nano-material, IL and monomer of conductive polymers to improve the electric conductivity of nonconducting polymer films, thus we can realize the controllable fabrication of these polymer coatings. Through these ways we can make full use of different electrodeposition monomers/or polymers and greatly expand the application scope of SPME fibers prepared by electrodeposition. Meanwhile,by varying the electrodeposition parameters, solution composition and IL we will control the thickness, micro-structure and selectivity of SPME coatings; through adopting various techniques and instrumental methods we will explore their appearance, micro-structure and property, and study the related electrodeposition mechanism and the action mechanism of ILs. On this basis, through optimizing the coating / or electrolyte-solution composition and preparation procedure we intend to fabricate several fibers with high-performance for the high sensitive determination of different noxious substances in environmental and food samples. In this project the substrate, the composition and microstructure of the coating and the fabrication method are full considered and they will be optimized and well combined，and the introduced IL can improve the microstructure and enhance the extraction efficiency of electrodeposited coatings, hence the obtained SPME fibers will present good performance. Through this project the different weakness of IL-based, nano-material based and polymer-based fibers can be overcome to great extent, and the development and application of SPME technique will be greatly promoted.

固相微萃取是一种具有广泛应用前景的试样前处理技术，本项目拟通过电沉积法在金属丝表面一步制备离子液体（IL)功能化的纳米网络结构聚合物和聚合物-纳米材料涂层，使所得萃取头既有很强的萃取功能、好的柔韧性和稳定性，又有高的萃取/解析速度和制备可控性，从而全面提高其性能。通过采用有机介质，使在水溶液中难溶、难电沉积的物质得以电沉积；通过掺杂碳纳米材料、IL及与导电聚合物单体共沉积使非导电性沉积膜的导电性改善，以实现其可控制备，从而大大增加电沉积涂层种类。通过改变电沉积参数、溶液组成和IL种类，调控涂层厚度、结构和选择性；运用多种技术对涂层形貌、结构性能进行表征；同时，探讨相关电沉积机理和IL的增效机制。在此基础上，优化组合，研制多种类型用于环境、食品试样前处理及色谱分析的高性能固相微萃取头。这将克服目前基于IL、纳米材料、聚合物等的固相微萃取头各自存在的不足，推动该技术的进一步发展和应用。

固相微萃取（SPME）是一种具有广泛应用前景的试样前处理技术，其核心是萃取头和涂层，但目前它们仍存在一些不足。本项目对金属丝表面离子液体（IL，包括聚合离子液体，下同）掺杂的复合SPME涂层的电化学制备方法、涂层结构、性能和应用等开展了系统研究。.在水和非水介质中，对吡咯、噻酚、苯胺、咔唑、吲哚乙酸及其衍生物和混合物在金属丝表面的电聚合及所得聚合膜的结构与萃取性能进行了考察。通过在IL、IL功能化的碳纳米管(CNT)溶液中浸泡，将IL负载在多孔电聚膜上制备简便、耐用、高效的复合涂层，对其形貌、结构和性能进行了表征，并将其用于脂肪醇、卤代芳烃、苯类等的SPME-色谱分析。.开展了水和非水介质中多种IL（包括亲水、疏水、酸性IL）掺杂的上述系列单体电聚合和共聚合涂层的制备，及它们的组成、结构、比表面、亲疏水性、稳定性、耐用性等的表征。分别考察了它们对脂肪醇、芳香酯、胺、卤代芳烃、苯类、多环芳烃、氨基甲酸盐杀虫剂等的顶空或直接浸入萃取性能。通过富集因子、检测限等评价萃取选择性和萃取能力。探讨了溶液组成、电聚合参数及IL种类、浓度对涂层组成、结构、形貌和萃取性能的调控作用与IL的增效机制。在此基础上研制了系列性能好的萃取头。.在分散有IL功能化的CNT、IL功能化石墨烯(GN)、CNT-GN-IL复合材料或IL与CNT、GN等的溶液中，通过电化学方法制备了IL和纳米材料掺杂的聚苯胺、聚3,4-乙烯二氧噻吩、聚咔唑及苯胺-环氧丙烷、苯胺-间氨基苯甲酸共聚物等复合SPME涂层；考察了纳米材料、IL及聚合物的作用方式及它们对复合涂层的结构与萃取性能等的影响，系统研究了它们的结构性能的调控方法，针对目标分析物优化了组合和制备条件。.将研制的各种萃取头与商用和文献报道的萃取头进行了比较，多种萃取头表现出优异的性能，在热稳定性（高达350℃）、萃取能力（检测限低至ng L-1级）、耐用性（可反复使用200次以上）及选择性等方面均有明显提高。同时将它们与气相色谱结合用于系列实际样品（包括废水、土壤、果疏、饮品等）中的多种成分的检测，表现出了良好的实用性。