【作者】 潘玉莹；

【导师】 马永钧；

【作者基本信息】 西北师范大学 ， 分析化学， 2010， 硕士

【摘要】 化学修饰电极是电化学及电分析化学研究的一个热点领域。在制备修饰电极的材料中,以普鲁士蓝为代表的多核金属铁氰化物具有其良好的化学性质和电化学性质。该薄膜修饰电极在物质检测、生物传感器、电池电极材料、固态电池等方面已得到了广泛的应用。基于上述原因,本文旨在研究新型的稀土掺杂类普鲁士蓝化学修饰电极,以提高其电催化活性和分析测定性能,同时也拓宽了它在电分析化学领域的应用范围。本文采用电化学沉积法制备了新型的稀土掺杂类普鲁士蓝化学修饰电极,首次发现了甲醇在该修饰电极上有良好的电催化活性及抗毒化作用,对甲醛有很好的电催化氧化作用,并将该修饰电极成功用于环境水样中甲醛含量的检测。本论文共分为四章:第一章:综述该部分主要综述了以下几个方面:(1)普鲁士蓝及类普鲁士蓝化学修饰电极的特点、制备方法以及表征方法,总结归纳了类普鲁士蓝化学修饰电极的分析应用情况,并对稀土铁氰化物化学修饰电极的发展趋势进行了展望。(2)简述了直接甲醇燃料电池的发展及存在的问题,列举了甲醇在各种铂基阳极材料及复合阳极催化剂上的电催化氧化行为。(3)甲醛的危害及常用的检测方法,甲醛在化学修饰电极上的电催化氧化行为及检测。这部分共引用文献119篇。第二章:通过电沉积法将铕-铁氰桥双核配合物修饰在铂电极表面(Eu-Fe film),首次发现甲醇在该修饰电极上有良好的电催化氧化活性及良好的抗毒化中间体的作用。通过对比甲醇在修饰电极与裸铂电极上的循环伏安数据,发现在修饰电极上甲醇的催化氧化电流增大了约20倍,且峰电位略有负移,并初步推测了甲醇在该修饰电极上氧化过程定速步骤的反应机理。第三章:通过电沉积法将掺杂钕离子(III)的类普鲁士蓝修饰在铂电极表面上(Nd-PB/Pt),发现甲醛在该修饰电极上有良好的电催化氧化活性及良好的抗中间体毒化作用。通过对比甲醛在修饰电极与裸铂电极上的循环伏安数据,发现在修饰电极上甲醛的催化氧化电流增大了约3倍,且峰电位略有负移;该电极对甲醛的伏安响应具有良好的重现性与稳定性。第四章:先将掺杂钕离子(III)的类普鲁士蓝修饰在铂电极表面上(Nd-PB/Pt),再通过电沉积法将铂微粒共沉积在修饰电极的表面,制备了铂微粒/类普鲁士蓝复合膜化学修饰电极(Pt /Nd-PB/Pt)。在优化的实验条件下,将该修饰电极用于甲醛的检测,甲醛的氧化峰电流与其浓度在1×10-4～1×10-2 mol/L范围内呈现出良好的线性关系,检测限为5×10-5 mol/L,测定了模拟黄河水样、模拟废水样的甲醛含量,回收率为95.6%～103.4%,结果令人满意。更多还原

【Abstract】 Chemically modified electrodes (CMEs) was one of the active research areas in modern electrochemistry and electroanalytical chemistry. Due to its good chemical properties and electrochemical properties, polynuclear metal hexacynoferrates, especially Prussian blue widely used in determination, bio-sensor, battery electrode materials, solid state batteries and so on. For these reasons, this paper aimed to develop a novel type of Prussian blue analogue chemically modified electrode, improving their electrocatalytic activity and analytical performance, expanding its applications in the electroanalytical chemistry field.A novel type of Prussian blue analogue chemically modified electrode was prepared by means of electrodeposition in this paper. It was discovered the electrocatalytic oxidation of methanol on the modified electrode for the first time, and the capacity of tolerated intermediates poison; It was unearthed for the electrocatalytic oxidation and determination of formaldehyde.There were four chapters in this paper:Chapter one: This part introduced briefly the following aspects: firstly,it was summed up the characteristics, preparation,characteristics and electroanalytical applications of Prussian blue and Prussian blue chemically modified electrode, and outlined the future prospects of the rare earth hexacyanoferrates chemically modified electrode. Secondly it was descripted the development and problems of the direct methanol fuel cell (DMFC), and list the literatures about the electrocatalytic oxidation behavior of methanol on the platinum anode catalyst and composite anode catalyst. In addition, it was introduced the hazards and the conventional detection methods of formaldehyde, and detection of formaldehyde on the chemically modified electrode.Chapter two: The Eu-Fe film modified electrode was prepared by means of electrodeposition and the electrocatalytic oxidation of methanol on the modified electrode was discovered for the first time. It was proved that the oxidation current of methanol in the modified electrode increased more than about 20 times, a slight negative shifted of peak potential of methanol oxidation and the electrode tolerated intermediates poison strongly by comparing cyclic voltammetry data of the electrocatalytic oxidation of the methanol at the modified electrode and the bare platinum electrode.Chapter three: The Nd-PB/Pt modified electrode was prepared by means of electrodeposition and discovered that there exist the electrocatalytic oxidation activity for formaldehyde and enhenced tolerated poison effect on the modified electrode. By comparing cyclic voltammetry data of the electrocatalytic oxidation of formaldehyde at the modified electrode and the bare platinum electrode, it was found that the oxidation current of formaldehyde on the modified electrode increased more than about 3 times, peak potential of formaldehyde oxidation shifted slight negatively. The modified electrode possessed good stability and reproducibility.Chapter four: After the Nd-PB/Pt modified electrode was prepared by means of electrodeposition, the electrodeposied platinum particles was attached on the modified electrode surface by means of constant potential electrolysis, in order to manufacture the platinum particles/Prussian blue composite film modified electrode(Pt/Nd-PB/Pt). This composite film modified electrode was successfully applied to determination of formaldehyde, and obtained good linearity in the formaldehyde concentration range of 1×10-4～1×10-2 mol/L with detection limit 5×10-5 mol/L under the optimum conditions. The proposed method was applied to the determination of formaldehyde in imitative Yellow water samples and imitative water samples with the recovery of 95.6%～103.4% and good results.更多还原