镍-钛合金基体上介孔固相微萃取涂层的制备及其分析应用

Fiber coatings and their supports are the core and the key part of solid-phase microextraction(SPME), respectively. Great attention has been attracted to the strong combination of highly efficient fiber coatings with the strong mechanical supports. Active ZrO2 membrane will be deposited on Ni-Ti alloy wire with electrochemical technique in this work, followed by bonding of mesoporous hybrids with sol-gel procedures via co-condensation of tetramethyl orthosilicate (TMOS) and alkyltrimetroxysilane using room temperature ionic liquids imidazolium-tetrafluoroborates as templates and diluted hydrochloric acid as a catalyst. Thereafter the template will be removed by acetonitrile. Different mesoporous coatings on the surface of ZrO2 coated Ni-Ti alloy wire fibers will be obtained with large specific area and uniform mesopores under optimized conditions. Mesoporous fiber coatings will be characterized by fourier transform infrared spectrum (FT-IR), small angle X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), N2 adsorption-desorption isotherms and thermogravimetry. Benzene homologues(BTEX), polyaromatic hydrocarbons(PAHs), phthalate acid esters(PAEs), aromatic amines and nonylphenol will be used as model compounds to examine the extraction behavior of the custom-made Ni-Ti alloy wire fibers coated with mesoporous hybrids coupled to GC and HPLC. The mechanism will be discussed for different mesoporous fiber coatings. Finally these newly developed mesoporous coatings on Ni-Ti alloy wire fibers will employed to the pretreatment of various water samples in local area.

萃取涂层和基体材料是固相微萃取(SPME)技术的核心部位和关键部件，将高效萃取涂层材料和高强度基体结合一直是SPME的研究热点。本项目采用在Ni-Ti合金丝表面电沉积ZrO2镀膜，以咪唑型四氟硼酸盐室温离子液体为模板剂、正硅酸甲酯和硅烷化偶联剂为前驱体，采用溶胶-凝胶法在Ni-Ti合金丝上ZrO2镀膜表面一步合成介孔杂化涂层，用萃取法脱除模板，通过优化和控制溶胶-凝胶的组成及反应条件，在Ni-Ti合金丝表面制备比表面积大和孔道结构规整介孔微萃取涂层，得到高效长寿命微萃取头。用FT-IR、XRD、SEM、TEM、吸附-脱附法和TG表征其有机功能化修饰、形貌特征、介孔结构和热稳定性。将所制备的新型Ni-Ti合金丝用作SPME涂层与GC和LC联用，考察其对苯系物、多环芳烃、酞酸酯、苯胺类化合物和壬基酚的萃取性能，探讨其萃取机理；并将此类新型SPME杂化涂层应用于甘肃当地各类水样品的前处理中。

萃取涂层和基体材料是固相微萃取(SPME)技术的核心部位和关键部件，将高效萃取涂层材料和高强度基体牢固结合一直是SPME的研究热点。本项目以Ti丝、NiTi合金丝和不锈钢丝为基体，采用化学和电化学沉积法成功制备或组装了多种新型高效和/或选择性的多孔SPME纤维涂层，包括ZrO2纳米粒、介孔SiO2、TiO2纳米粒、纳米管、纳米片和纳米棒、表面修饰TiO2纳米结构、TiO2/NiO复合纳米管和纳米片、表面修饰TiO2/NiO复合纳米结构、多孔ZnO纳米材料、金纳米材料、银纳米材料、多孔聚苯胺及其氮掺杂碳化纳米材料，用FT-IR、XRD、SEM、吸附-脱附法和EDS能谱对其结构特征和表面元素组成进行了表征。纳米结构涂层极大地增加了比表面积，萃取富集效率高，涂层传质速度快，萃取平衡时间短，将所制备或组装的多种高效选择性金属基SPME纤维涂层与HPLC联用，考察了其对多环芳烃（PAHs）、多氯联苯（PCBs）、酞酸酯（PAEs）、紫外线吸收剂、酚类和苯胺类化合物的萃取性能，探讨了萃取机理，优化了相应的SPME条件；所开发的新型多孔SPME纤维涂层应用于当地各类环境水样中痕量分析物的富集分离和测定，建立的分析方法具有操作简便、吸附和解吸快速、灵敏度高的特点，分析结果具有良好的精密度和准确度。而且，采用项目研究所提出的SPME纤维制备或组装新方法或新策略，纤维微萃取涂层厚度精密可控，结合牢固，使用寿命长，一支纤维可完成整个分析过程，且不同批次纤维的制备重现性好