纳米材料掺杂分子印迹聚合物修饰乙炔黑糊电极的制备及其对双酚A的检测分析

发布时间：2018-07-01 12:10

本文选题：双酚A + 分子印迹聚合物　；参考：《江苏大学》2017年硕士论文

【摘要】：双酚A是一种低毒性化学物质,对人体皮肤、消化道、呼吸道、角膜等有中等强度刺激性,并且双酚A具有模拟雌激素的效果,能破坏荷尔蒙。因此,研究一种既简便有效的方法去检测环境样品中痕量双酚A,非常有意义。实验采用表面分子印迹技术,以双酚A为目标分子,制备了双酚A分子印迹聚合物,以分子印迹材料、石墨烯、四氧化三铁、纳米金为电极修饰材料,制备了三种修饰电极,考察了修饰电极的电化学性能,研究了pH值、印迹材料用量、扫描速率、吸附时间对电化学性能的影响,优化了电化学工作站的分析检测条件,在最优条件下考察了方法的检出限,线性范围。并且将三种电极都用于环境样品中双酚A的分析检测。主要研究内容包括以下三个方面:(I)以双酚A为模板分子,4-乙烯基吡啶为功能单体,沉淀聚合法制备了双酚A分子印迹聚合物,采用Hummers法制备氧化石墨烯,并将其还原得到石墨烯。利用自制的石墨烯和分子印迹材料对碳糊电极进行修饰,对石墨烯和分子印迹材料的进行了表征,研究了自制电极的电化学性能,考察了MIPs浓度、时间、扫描速率对电化学传感器分析检测的影响,优化了最佳分析检测条件,在最优条件下,方法的检出限为9.63×10-11 g/L。并将其用于环四种实际环境样品中双酚A的分析检测,相对标准偏差为1.7-3.5%(N=5),加标回收率在95%-103%之间,实验还将此法与传统高效液相色谱法对比,研究结果表明,液相色谱和实验所用方法具有显著相关性。(II)用石墨烯、四氧化三铁、分子印迹聚合物修饰乙炔黑糊电极得到新型碳糊电极,研究了自制电极的电化学性能,考察了分子印迹材料浓度、吸附时间、扫描速率、pH等对电极分析检测性能的影响,在最优条件下,考察了自制电极对双酚A的分析检测性能,方法的检出限为6.34×10-10 g/L(3σ),最后将此电极用于环境样品中双酚A的分析检测,相对标准偏差为2.8%—3.6%(N=5),加标回收率在90%-102%之间。(III)为了减轻石墨烯的氧化团聚,实验选择加入纳米金,制备得到纳米金-还原石墨烯复合材料,将双酚A分子印迹材料和纳米金-还原石墨烯复合材料修饰到碳糊电极表面得到纳米金-石墨烯-分子印迹聚合物修饰碳糊电极,研究了自制电极的电化学性能,考察了pH值、分子印迹材料浓度、吸附时间、扫描速率等条件对电化学工作站分析检测性能的影响,优化了分析检测条件,考察了方法的检出限,此法的检出限为1.27×10-11 g/L,并将此方法用于环境样品中四种实际样品的分析检测,相对标准偏差为2.1%-3.6%(N=5),加标回收率在95%-100%之间。
[Abstract]:Bisphenol A (BPA) is a low toxic chemical substance which has moderate irritation to human skin, digestive tract, respiratory tract, cornea and so on. Bisphenol A has the effect of mimicking estrogen and can destroy hormones. Therefore, it is of great significance to study a simple and effective method for the determination of trace bisphenol A in environmental samples. Using surface molecular imprinting technique and bisphenol A as target molecule, three kinds of modified electrodes were prepared by using molecularly imprinted materials, graphene, ferric oxide and gold nanoparticles as electrode modification materials. The effects of pH value, amount of imprinted materials, scanning rate and adsorption time on the electrochemical performance of the modified electrode were investigated. The analytical conditions of the electrochemical workstation were optimized. The detection limit and linear range of the method are investigated under the optimal conditions. The three kinds of electrodes were used for the analysis and detection of bisphenol A in environmental samples. The main research contents include the following three aspects: (I) bisphenol A molecularly imprinted polymer was prepared by precipitation polymerization and graphene oxide was prepared by Hummers method using bisphenol A as template molecule and vinyl pyridine as functional monomer. It was reduced to graphene. The carbon paste electrode was modified with graphene and molecularly imprinted materials. The electrochemical properties of the electrode were studied. The concentration and time of MIPs were investigated. The effect of scanning rate on the analysis and detection of electrochemical sensors was studied. The optimum analytical and detection conditions were optimized. The detection limit of the method was 9.63 脳 10 ~ (-11) g / L under the optimal conditions. The method was applied to the determination of bisphenol A in four real environmental samples. The relative standard deviation was 1.7-3.5% (N5), and the recovery rate was between 95% and 103%. The method was also compared with the traditional high performance liquid chromatography (HPLC). There is a significant correlation between liquid chromatography and experimental methods. (II) A new type of carbon paste electrode was prepared by modifying acetylene black paste electrode with graphene, iron trioxide and molecularly imprinted polymer. The electrochemical properties of the self-made electrode were studied. The effects of the concentration of molecularly imprinted materials, adsorption time, scanning rate and pH on the performance of the electrode were investigated. Under the optimum conditions, the analytical performance of the self-made electrode for bisphenol A was investigated. The detection limit of the method was 6.34 脳 10 ~ (-10) g / L (3 蟽). Finally, the electrode was used for the determination of bisphenol A in environmental samples. The relative standard deviation was 2.8% -3.6% (N5), and the recovery rate was between 90% and 102%. (III) in order to reduce the oxidation agglomeration of graphene, nano-gold was added. The nano-gold-reduced graphene composite was prepared. The nano-gold graphene-molecularly imprinted polymer modified carbon paste electrode was prepared by modifying bisphenol A molecularly imprinted material and nano-gold-reduced graphene composite onto the surface of the carbon paste electrode. The electrochemical performance of self-made electrode was studied. The effects of pH value, concentration of molecularly imprinted materials, adsorption time and scanning rate on the performance of electrochemical workstation were investigated. The detection limit of this method was 1.27 脳 10 ~ (-11) g / L, and the method was applied to the analysis of four kinds of environmental samples. The relative standard deviation was 2.1 ~ 3.6% (N5) and the recovery rate was between 95% and 100%.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.1;TB383.1

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