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新型碳材料修饰电极在电分析中的应用研究

Studies on the New Carbon Materials Modified Electrodes in Electroanalytical Application

【作者】 吴燕慧

【导师】 朱连德;

【作者基本信息】 东北师范大学 , 分析化学, 2010, 硕士

【摘要】 本论文主要研究了新型碳材料电极的制备及其在电分析基础研究中的应用。主要包括两部分内容:新型碳纳米纤维糊修饰电极的制备及其在电分析中的应用和1,10-菲咯啉-5,6-二酮/有序介孔碳复合材料膜修饰电极对NADH的电催化研究。具体的研究工作主要集中在以下几部分:(1)优化了制备碳纳米纤维糊电极(CNFPE)的实验条件,将碳纳米纤维糊电极的电化学行为与传统碳糊电极(CPE)做了对比,并比较了一些具有生物活性的分子在两种电极上的电化学响应。结果表明在相同的几何面积时,CNFPE对这些生物分子有更大的电流响应,氧化还原电位也有了明显的改善,显示了碳纳米纤维糊电极在电分析应用中的优势。在相同的实验条件下分别利用CNFPE和CPE检测了H2O2和NADH,结果表明CNFPE相对于CPE在检出限、灵敏度、线性范围等方面都有了明显的提高,进一步证明了CNFPE比CPE具有更好的电化学活性,更适宜电分析的应用。(2)通过自发吸附的方式将1,10-菲咯啉-5,6-二酮稳定地组装到有序介孔碳修饰玻碳电极表面,制备了1,10-菲咯啉-5,6-二酮/有序介孔碳复合膜修饰电极。以电化学方法对修饰电极进行了详细表征,在理论上计算了1,10-菲咯啉-5,6-二酮/有序介孔碳/玻碳电极与NADH之间的催化反应速率常数(kh),并与1,10-菲咯啉-5,6-二酮/玻碳电极与NADH之间的催化反应速率常数(kh)进行了比较,发现前者比后者提高了482倍以上。很好的说明了1,10-菲咯啉-5,6-二酮/有序介孔碳复合膜修饰电极对NADH有较高的催化活性,在-0.1V电位下,检测NADH得到了良好的结果,灵敏度为5.763μA/mM,检出限为0.98μM(信噪比为3),线性范围可达350μM。

【Abstract】 In this dissertation, efforts have been devoted to the fabrication and basic research in electroanalytical applications of novel carbon materials modified electrodes. The dissertation consists of two main parts: one is electroanalytical applications of carbon nanofibers paste modified electrode and the other is the electrochemical electrocatalytic oxidation of NADH with 1, 10-phenanthroline-5,6-dione functionalized ordered mesoporous carbon (PD/OMC) composite film modified electrode . The main works of the dissertation are as follows:1) Surface renewable carbon nanofibers paste electrodes (CNFPE) were fabricated by mechanical mixing carbon nanofibers (CNF) with mineral oil. The electrochemical behavior of such electrodes has been compared with conventional carbon paste electrode (CPE) and thoroughly evaluated with respected to the electrochemistry of some biological molecules. In all cases, CNFPE provide better reversibility with substantial decreased overpotential, better defined peak shape, and higher sensitivity compared with CPE. In addition, CNFPE and CPE were employed as H2O2 and NADH probes. The obtained experimental results further demonstrated remarkable electrochemical advantages of CNFPE compared with CPE for electroanalytical applications.2) The PD molecules were assembled on the surface of ordered mesoporous carbon through spontaneous adsorption modified glassy carbon electrode (PD/OMC/GCE). Electrochemical behaviors of the resulting electrode were investigated thoroughly with cyclic voltammetry, we studied the kinetics of the catalytic reaction and the catalytic reaction rate constant (kh) for NADH of PD/OMC/GCE in comparison with PD/GCE. The catalytic reaction rate constant (kh) of PD/OMC/GCE was calculated to be about 482 times larger than that of PD/GCE. Based on the results, a new NADH sensor was successfully established using the PD/OMC/GCE. Under a lower operation potential of -0.1 V, NADH could be detected linearly up to a concentration of 350μM with a lower detection limit of 0.98μM (S/N=3) as well as a high sensitivity of 5.763μA/mM.

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