碳纳米管基离子印迹聚合物:形成、表征和电化学性能

K. Markiewicz, A. Wilczewska
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引用次数: 0

摘要

重金属污染环境在世界许多地区造成了严重的健康和生态问题[1]。因此,对其进行准确的分析测定具有重要意义。对电极进行化学修饰是提高金属离子测定电化学传感器灵敏度和选择性的有效途径。碳纳米管(Carbon nanotubes, CNTs)由于其高导电性,可以为电化学器件引入较强的电催化活性,因此已成功地应用于各种用途的电化学传感器的制造中[2]。离子印迹聚合物(IIPs)是一种对目标离子具有高选择性的高分子材料,其制备过程中产生了记忆效应。它们的其他优点是化学稳定性好、成本低、制备容易[3]。离子印迹聚合物功能化碳纳米管是一种很有前途的电极修饰材料。这项研究的目的是在碳纳米管和离子印迹聚合物的基础上形成新的选择性材料,用于修饰电极。该项目的第一阶段涉及碳纳米管与二硫代碳酸盐的共价功能化,二硫代碳酸盐是RAFT(可逆加成-破碎链转移)聚合中的链转移剂。碳纳米管与二硫代碳酸盐的功能化使得直接从纳米管表面进行聚合成为可能。通过二硫代碳素修饰的碳纳米管、模板离子(Pd)、功能单体和交联剂的混合物聚合,合成了碳纳米管- iip杂化体。聚合使用商业上可用的单体(如丙烯腈、丙烯酸)以及合成的单体,即对金属离子具有高亲和力的氨基腙硫代酸盐或硫脲基分子。用这种方法获得了几种碳纳米管- iip纳米杂化体。模板离子从聚合物网络中移除后,形成了与模板离子大小和形状互补的特定空腔。所得材料通过溶剂蒸发沉积在金电极上。利用拉曼光谱、傅里叶变换红外光谱、热重分析、扫描电镜和透射电镜等对所得材料进行了修饰和化学成分的研究。用循环伏安法和电化学阻抗法分析了材料的电化学性能。
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Carbon Nanotube-Based Ion Imprinted Polymers: Formation, Characterization and Electrochemical Properties
Extended Abstract Environment contamination by heavy metals cause serious health and ecological problems in many parts of the world [1]. Therefore, their accurate analytical determination is of great importance. Chemical modification of electrodes is an effective way to improve sensitivity and selectivity of electrochemical sensors used for metal ions determination. Carbon nanotubes (CNTs) due to their high electrical conductivity can introduce strong electrocatalytic activity to electrochemical devices, and thus, have been successfully applied in the fabrication of electrochemical sensors for various applications [2]. Ion-imprinted polymers (IIPs) are macromolecules showing high selectivity toward target ion related to a memory effect resulting from the process of their preparation. Their other advantages are chemical stability, low cost, and easiness of preparation [3]. Carbon nanotubes functionalized with ion-imprinted polymers are promising materials for electrodes modification. The aim of the study is formation of new selective materials based on carbon nanotubes and ion-imprinted polymers for modification of electrodes. The first stage of the project involved covalent functionalization of carbon nanotubes with dithiocarbonates, which are chain transfer agents in RAFT (reversible addition-fragmentation chain transfer) polymerization. Functionalization of CNTs with dithiocarbonates enables polymerization conducted directly from nanotube’s surface. CNT-IIP hybrids were synthesized by polymerizing a mixture of dithiocarbonate-modified CNTs, template ions (Pd), functional monomers and a crosslinker. Polymerizations were performed using commercially available monomers (e.g. acrylonitrile, acrylic acid) as well as synthesized ones i.e. carbamohydrazonothioate or thiourea-based molecules having high affinity to metal ions. In this way several CNT-IIP nanohybrids were obtained. The specific cavities complementary to the size and shape of the template ions were formed after their removal from the polymer network. The obtained materials were deposited on gold electrodes by solvent evaporation. Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning and transmission electron microscopy were employed to confirm modifications and study chemical composition of the obtained materials. Electrochemical properties were analysed by cyclic voltammetry and electrochemical impedance spectroscopy.
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