杯芳烃及衍生物修饰碳糊电极的制备与应用研究

发布时间：2018-11-24 15:31

【摘要】：杯芳烃具有较丰富的活性位点、高度选择性空腔、以及优秀的电子传导能力,故而基于杯芳烃及衍生物制备的化学修饰电极在电化学分析检测中扮演重要角色。本文制备了三种杯芳烃及衍生物修饰碳糊电极,研究了铜离子、汞离子、铅离子及对苯二酚的电化学行为。主要内容概括如下:(1)以对叔丁基杯[4]芳烃(H4L)为修饰剂通过直接混合法制备了H4L-CPE,并采用电化学法对电极性能进行了表征。在该修饰碳糊电极上研究了Cu~(2+)的电化学行为,得出了一些重要的电化学参数,并与Cu~(2+)在裸碳电极的电化学行为作了对比,结果发现Cu~(2+)在该修饰电极上出现明显的特征吸收峰,说明该修饰电极对Cu~(2+)有明显的电催化作用。在最优条件下,通过循环伏安法探究了氧化峰电流值与Cu~(2+)浓度之间的线性关系,结果发现Cu~(2+)浓度在2.5×10-7~1.0×10-5 mol/L范围内呈良好线性关系,最低检出限1.33×10-8 mol/L(按3倍信噪比计算)。利用对叔丁基杯芳[4]烃修饰的碳糊电极对Cu~(2+)的检测有较好的稳定性和重现性,为高灵敏度、高选择性测定痕量Cu~(2+)提供了一种新的方法。(2)以硫杂杯[4]芳烃为修饰剂制备了硫杂杯[4]芳烃修饰碳糊电极,懫用循环伏安法研究该修饰电极对Pb~(2+)和对苯二酚的电化学行为。在该修饰电极上研究了Pb~(2+)和对苯二酚的电化学行为,并绘制了Pb~(2+)和对苯二酚的标准曲线。由曲线可知Pb~(2+)浓度在1.0×10-7~1.0×10-5 mol/L的区间拥有良好线性关系,最低检出限是1.56×10-8 mol/L;对苯二酚浓度在5.0×10-8~1.0×10-5 mol/L的区间内线性关系良好,最低检出限为6.5×10-8 mol/L。研究了干扰物质的影响和模拟水样的检测。该修饰电极制备简单,选择吸附能力强,成本低,灵敏度高、抗干扰能力强,可用于制备检测Pb~(2+)和对苯二酚的电化学传感器。(3)以硫杂杯-4-冠-6为修饰剂制备了硫杂杯-4-冠-6修饰碳糊电极。该修饰电极具有丰富的活性位点和较小的电子转移阻力。懫用循环伏安法考察Hg~(2+)在该修饰电极上的电化学行为,研究了影响电极性能的可能因素并得到了相关电化学参数,线性响应范围为1.0×10-8~1.0×10-5 mol/L,最低检出限为7.62×10-9 mol/L,对模拟水样的加标回收,结果令人满意。
[Abstract]:Calixarene has abundant active sites, highly selective cavity and excellent electronic conductivity. Therefore, chemically modified electrodes based on calixarene and its derivatives play an important role in electrochemical analysis. Three kinds of calixarene and their derivatives modified carbon paste electrodes were prepared. The electrochemical behaviors of copper, mercury, lead and hydroquinone were studied. The main contents are summarized as follows: (1) H4L-CPE was prepared by direct mixing method with p-tert-Ding Ji calix [4] arene (H4L) as modifier, and the electrode performance was characterized by electrochemical method. The electrochemical behavior of Cu~ (2) was studied at the modified carbon paste electrode. Some important electrochemical parameters were obtained and compared with the electrochemical behavior of Cu~ (2) at the bare carbon electrode. The results show that Cu~ (2) has obvious characteristic absorption peak on the modified electrode, which indicates that the modified electrode has obvious electrocatalytic effect on Cu~ (2). Under the optimal conditions, the linear relationship between the oxidation peak current value and the concentration of Cu~ (2) was investigated by cyclic voltammetry. The results showed that the concentration of Cu~ (2) was linear in the range of 2.5 脳 10 -7 渭 m 1.0 脳 10 -5 mol/L. The lowest detection limit is 1.33 脳 10 ~ (-8) mol/L (3 times signal-to-noise ratio). The carbon paste electrode modified with p-tert-Ding Ji calix [4] hydrocarbon has good stability and reproducibility for the detection of Cu~ (2). A new method for the determination of trace Cu~ (2) with high selectivity is provided. (2) Thiocuca [4] arene modified carbon paste electrode has been prepared by using thiachax [4] arene as modifier. The electrochemical behavior of the modified electrode for Pb~ (2) and hydroquinone was studied by cyclic voltammetry. The electrochemical behaviors of Pb~ (2) and hydroquinone were studied at the modified electrode, and the standard curves of Pb~ (2) and hydroquinone were drawn. The curve shows that the concentration of Pb~ (2) is linear in the range of 1.0 脳 10 ~ (-7) mol/L and the lowest detection limit is 1.56 脳 10 ~ (-8) mol/L;. The linear range of hydroquinone concentration is 5.0 脳 10 ~ (-8) mol/L for 1.0 脳 10 ~ (-5) mol/L, and the lowest detection limit is 6.5 脳 10 ~ (-8) mol/L.. The influence of interfering substances and the detection of simulated water samples were studied. The modified electrode has the advantages of simple preparation, strong selective adsorption ability, low cost, high sensitivity and strong anti-interference ability. It can be used to prepare electrochemical sensors for the detection of Pb~ (2) and hydroquinone. (3) Thiaza-4-crown-6 modified carbon paste electrode was prepared with thiaza-4-crown-6 as modifier. The modified electrode has abundant active sites and small electron transfer resistance. The electrochemical behavior of Hg~ (2) on the modified electrode was investigated by cyclic voltammetry. The possible factors affecting the performance of the modified electrode were studied and the related electrochemical parameters were obtained. The linear response range was 1.0 脳 10-8 mol/L,. The minimum detection limit is 7.62 脳 10 ~ (-9) mol/L, for the recovery of simulated water samples, and the results are satisfactory.
【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.1

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