基于纳米复合材料修饰电极的过氧化氢传感器的研究

发布时间：2018-02-03 02:29

本文关键词： 纳米复合材料氧化石墨烯电化学传感器过氧化氢　出处：《青岛科技大学》2015年硕士论文　论文类型：学位论文

【摘要】：过氧化氢(H202)作为一种简单、常见的小分子化合物,在生物系统和实际应用中均有重要意义,开发简便、有效的H202电化学传感器吸引了越来越多研究人员的关注。本文采用新型纳米复合材料构建无酶型过氧化氢电化学传感器,可实现对H202含量的有效测定。主要工作如下：1.采用Fe304磁性纳米粒子(MNPs),氧化石墨烯(GO)和第四代聚酰胺-胺型树枝状高分子(PAMAM-G4)构建电化学传感器检测过氧化氢。先合成Fe3O4-GONPs,再与PAMAM结合,将此复合材料修饰在金电极表面作为工作电极。由于Fe3O4MNPs具有模拟酶性质,并且有很好的生物相容性,而GO拥有多个含氧官能团,能与Fe3O4MNPs耦合成石墨烯薄片,显示出优异的综合性能。PAMAM表面活性基团密度高,结构均匀,可以与其他材料通过静电作用自行组装成膜。结合了三者优异的性能,通过电流-时间曲线法实现对H202的检测。在最优实验条件下,所制备的传感器对H202浓度的响应线性范围为2.0×105～1.0×10-3mol·L-1(相关系数为0.9950,n=10),检出限为2.0 x 10-6mol.L-1(3σ),同时对实际样品进行了加标回收实验,回收率为96.9%～108.1%。该修饰电极具有优异的电化学性能,重现性好,稳定期长,制备简便,可以很好的应用于过氧化氢的检测。2.采用循环伏安法,将聚噻吩-氧化石墨烯复合物膜和普鲁士蓝(PB)膜层层聚合在玻碳电极表面,制备H202的电化学传感器。由于PB膜良好的电催化性能及类似于人工过氧化物酶的性质,已经被广泛应用于生物传感器领域。而聚噻吩-氧化石墨烯膜有良好的电化学稳定性,两者协同作用,为H2O2的检测提供了可能。利用电流-时间曲线法检测H202,在最优实验条件下,线性范围为1.0×10-6～1.0×10-4mol·L-1,相关系数为0.9965,检出限是3.2×1()-7mol·L-1(36)。实验表明,通过电化学聚合制备的导电聚合物膜稳定性好,所制备的传感器易于保存,稳定性好,对于H202的检测具有潜在的应用价值。3.以氧化石墨烯和尿素为原料,按照一定比例通过水热反应合成氮掺杂的氧化石墨烯材料。将氮掺杂氧化石墨烯与金纳米粒子层层自组装于玻碳电极表面,实现对H202的检测。由于尿素的加入,使得GO中大量含氧基团脱去,使其具有丰富的网络多孔结构,大大增强了材料的电容性能。同时金纳米粒子具有良好的电催化和电化学特征,结合二者的优良电学性能,在最佳条件下,通过差分脉冲伏安法(DPV)对H202进行了检测。在浓度为1.0 x 10-7mo1.L-1到1.0×10-5 mol·L-1的范围内,H202的浓度与电流响应成良好的线性关系,其检出限是4.9 × 10-8mol·L-1。此传感器操作简便,重现性好,表明氮掺杂氧化石墨烯在电化学传感器领域有良好的应用前景。
[Abstract]:As a simple and common small molecule compound, H _ 2O _ 2 (H _ 2O _ 2) has important significance in biological system and practical application, and its development is simple and convenient. The effective electrochemical sensor of H202 has attracted more and more attention of researchers. In this paper, a new type of hydrogen peroxide electrochemical sensor without enzyme was constructed by using new nanocomposites. The content of H202 can be effectively determined. The main work is as follows: 1. Adopt Fe304 magnetic nanoparticles (MNPs). The electrochemical sensor was constructed to detect hydrogen peroxide with 4th generation polyamide-amine dendritic polymer (PAMAM-G4). First, Fe3O4-GONPs was synthesized. Combined with PAMAM, the composite was modified on the surface of gold electrode as a working electrode. Because Fe3O4MNPs has mimic enzyme properties and has good biocompatibility. Go has many oxygen-containing functional groups, which can be coupled with Fe3O4MNPs to form graphene sheet, showing excellent comprehensive properties. The surface active group density of PamAm is high and the structure is uniform. The film can be self-assembled by electrostatic interaction with other materials. Combined with the excellent properties of the three materials, the detection of H202 can be realized by current-time curve method. Under the optimal experimental conditions. The linear range of the sensor to the concentration of H202 is 2.0 脳 10 ~ (-5) 渭 mol 路L ~ (-1) (correlation coefficient is 0.9950). The detection limit is 2.0 x 10-6 mol 路L ~ (-1) 3 蟽 ~ (-1). The recovery of the modified electrode is 96. 9 and 108.1. The modified electrode has excellent electrochemical performance, good reproducibility, long stable period and simple preparation. It can be well used in the detection of hydrogen peroxide .2.The polythiophene oxide graphene oxide composite membrane and Prussian blue PB) film were polymerized on the surface of glassy carbon electrode by cyclic voltammetry. The electrochemical sensor of H202 was prepared. Due to the excellent electrocatalytic performance of PB membrane and the properties similar to artificial peroxidase. It has been widely used in biosensors, and the polythiophene oxide graphene film has good electrochemical stability. The method of current-time curve was used to detect H202.The linear range of H _ 2O _ 2 was 1.0 脳 10 ~ (-6) 渭 mol 路L ~ (-1) under the optimum experimental conditions, and the linear range was 1.0 脳 10 ~ (-4) mol 路L ~ (-1). The correlation coefficient was 0.9965, and the detection limit was 3.2 脳 1mol 路L-1. The results showed that the conductive polymer film prepared by electrochemical polymerization had good stability. The sensor is easy to preserve and has good stability. It has potential application value for the detection of H202. It uses graphene oxide and urea as raw materials. The nitrogen-doped graphene oxide materials were synthesized by hydrothermal reaction in a certain proportion. The nitrogen-doped graphene oxide and gold nanoparticles were self-assembled on the surface of glassy carbon electrode. Because of the addition of urea, a large number of oxygen-containing groups were removed from go, which made it have abundant network porous structure. At the same time, gold nanoparticles have good electrocatalytic and electrochemical characteristics, combined with their excellent electrical properties, under the best conditions. H202 was determined by differential pulse voltammetry in the range of 1.0 x 10-7 mol 路L -1 to 1.0 脳 10 ~ (-5) mol 路L ~ (-1). The detection limit of H202 is 4.9 脳 10 ~ (-8) mol 路L ~ (-1). The sensor is easy to operate and has good reproducibility. It shows that nitrogen doped graphene oxide has a good application prospect in the field of electrochemical sensors.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33;TP212

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