【作者】 杨海青；

【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20世纪70年代以来发展起来的一种电极,目前已广泛应用于涉及环境、生命、材料科学、能源、电子工业等分析领域。随着对化学修饰电极研究的深入,将各种具有良好化学性能的修饰材料与常规的金属电极相结合,可制备出性能优于常规金属电极的复合电极。在诸多的化学修饰材料中,普鲁士蓝具有独特的结构,其良好的化学和电化学稳定性,制备成本低等优点,在功能材料、电化学传感器、离子识别和分子磁性物质等方面得到了广泛的应用。在普鲁士蓝中掺杂铕,可制备出性能比普鲁士蓝更佳的膜,我们称之为稀土掺杂类普鲁士蓝膜。结合此类普鲁士蓝膜和常规铋膜电极的优点,本文利用电化学沉积法在玻碳电极上先镀一层稀土掺杂类普鲁士蓝膜,再镀铋膜,制备出了铕离子掺杂类普鲁士蓝复合铋膜电极,并进行了一些分析应用研究。实验表明,本实验室率先制备出的铕离子掺杂类普鲁士蓝复合铋膜电极可成功用于环境水样中痕量铟、奶制品与药品中痕量锌和药片中异烟肼的测定。该电极具有灵敏度高、稳定性好、电位窗宽、抗干扰能力强和使用寿命长等特点,具有潜在的应用价值。本论文包括以下四部分:第一章:综述该部分阐述了电位溶出分析方法的特点,介绍了汞膜在电位溶出分析法中的作用。接着介绍了铋及铋化合物的性质,铋膜的制备方法与分析应用,简要探讨了化学修饰型复合铋膜电极产生的必然性、制备方法及其在电化学溶出分析方面的应用。最后,对复合型类普鲁士蓝化学修饰电极在电位溶出分析中的发展趋势和应用做了展望。这部分共引用文献104篇。第二章:复合铋膜电极阳极溶出法测定水样中痕量铟的研究在玻碳电极上采用电化学沉积法制备了新型铕离子掺杂普鲁士蓝复合铋膜电极,建立了用示差脉冲阳极溶出法测定环境水样中痕量铟的分析方法。讨论了铟在常规铋膜电极和复合铋膜电极上的溶出性能,对铋膜的厚度、支持电解质、测定底液的pH、富集时间和富集电位等参数进行了优化。在最佳实验条件下,铟的阳极溶出峰电流与其浓度在2²0μg/L和20¹00μg/L范围内分别呈良好的线性关系,检测下限为0.15μg/L（S/N=3）,相对标准偏差RSD小于2.0%。该法用于实际水样中痕量铟的测定,样品回收率为97.5%～103%。实验结果表明:该电极的适用性好,灵敏度高,稳定性强。第三章:复合铋膜电极阳极溶出法测定痕量锌采用预镀铋电化学沉积法制备了铕离子掺杂类普鲁士蓝复合铋膜电极,建立了阳极溶出伏安法测定痕量锌的新方法。实验结果表明:锌在0.03 mol/L的酒石酸钠（pH=4.5）溶液中可得到灵敏的阳极溶出峰;最佳实验条件下,于-1.4 V富集120 s后,锌的溶出峰电流与其浓度在10⁵40μg/L（r=0.99987）范围内呈良好的线性关系,检出限为1.38μg/L（S/N=3）,相对标准偏差为0.94%（n=8）。该法可用于奶制品和药品中锌含量的测定,回收率为99.3%¹01%。第四章:复合铋膜电极阳极溶出伏安法测定药物中的异烟肼提出了一种用复合铋膜电极阳极溶出伏安法测定药物中异烟肼的分析方法。以复合铋膜作工作电极,饱和甘汞电极作参比电极,铂电极作辅助电极,在0.01 mol/L的醋酸-醋酸钠缓冲溶液中,用阳极溶出伏安法测定异烟肼的含量。异烟肼的峰电流与异烟肼浓度在8.0×10^-8～2.0×10^-6 mol/L范围内呈良好的线性关系。富集60 s后,测定的检测下限为1.8×10^-8 mol/L。该法简单、快速。电极的优点在于线性范围宽,重现性好,使用寿命长,用于异烟肼片剂的测定,结果满意。更多还原

【Abstract】 Chemically modified electrode was developed since 1970s, and had been widely applied in the fields related to environmental science, life science, materials science, energy power, electronics, etc. With the advancement in the study of chemically modified electrodes, the composite electrodes whose performance were higher than that of conventional metal electrodes can been manufactured through combination of some kinds of modifiers of good chemical properties with metal electrodes. Though there were many types of chemically modified materials, Prussian blue was one of the most widely used, such as in the fields of functional materials, electrochemical sensors, ion identification and molecular magnetic materials, etc, due to its advantages of unique structure, good chemical and electrochemical stability, low cost. By means of doping Eu3+ ions in the Prussian blue, a film called europium-doped Prussian blue analogue （Eu-PB） film whose performance was superior to that of the Prussian blue was prepared. With combination of the advantages of both the europium-doped Prussian blue （Eu-PB） film modified electrode and the coventional bismuth film electrod, an europium-doped Prussian blue （Eu-PB） composite bismuth film was prepared using the electrochemical deposition method, and the samples analysis was made on this electrode. The results of the experiments showed that the europium-doped Prussian blue （Eu-PB） composite bismuth film can been successfully used in the determination of trace Indium in environmental water samples, the determination of trace Zinc in dairy products and the determination of isoniazid in pharmaceuticals. This electrode had the advantages of high sensitivity, good stability, wide potential window, high anti-interference performance, long service life. Therefore, this electrode had high potential value for application.This thesis includes the following four chapters:Chapter I: OverviewThis chapter described the characteristics of potential stripping analysis, the role of mercury membrane in electrochemical stripping analysis, and the characteristic of mercury film. Then it introduced the features of bismuth and its compounds, the preparation methods and applications of the bismuth film electrode. It also briefly discussed the necessity, preparation and application of the chemically modified bismuth film composite electrode. The last part of this chapter prespectd the development trends of the europium-doped Prussian blue （Eu-PB） composite bismuth film electrode in potential stripping analysis, and included the purpose and significance of the research in this thesis. The references of this part included a total of 104 items.ChapterⅡDetermination of Trace Indium in Water Samples by Anodic Stripping Voltammetry on Composite Bismuth Film ElectrodeA novel composite bismuth film electrode （GC/Eu-PB/BFE） was prepared by electrodepositing bismuth film on the glassy carbon matrix which was modified with europium-doped Prussian blue analogue （Eu-PB）. In addition, trace levels of Indium was determined by anodic stripping voltammetry using the GC/Eu-PB/BFE as a working electrode. The comparison of stripping properties of In3+ between the common bismuth and the composite bismuth had been studied. Some of effect factors such as the thickness of bismuth film, supporting electrolyte, pH of determining solution, deposition time and deposition potential were optimized. Under the optimum conditions, good linearity was obtained in the concentration range of 2²0μg/L and 20¹00μg/L, respectively. The limit of detection was 0.15μg/L and relative standards error was under 2.0%. The method had been applied to the determination of Indium ion in environment water samples with the recovery of 97.5%¹03%。The results showed that the composite bismuth film （GC/Eu-PB/BFE） had been applicable to analysis with high sensibility and good stability.ChapterⅢDetermination of Trace Zinc by Anodic Stripping Voltammetry Composite Bismuth Film ElectrodeA composite bismuth film electrode （GC/Eu-PB/BFE） was prepared by electrodepositing bismuth film on the glassy carbon which was modified with europium-doped Prussian blue （Eu-PB）. A new method for the determination of zinc was developed using the GC/Eu-PB/BFE. The results revealed that the sensitive stripping peak of zinc ions was obtained in 0.03 mol/L tartrate solutions （pH=4.5）. Under the optimum conditions, the good linearity of zinc ions were obtained in the concentration range of 10⁵40μg/L （r=0.99987） after 120 s’deposition at -1.4 V. The limit of detection was 1.38μg/L （S/N=3） and relative standards error was 0.94% （n=8）. The method had been applied to the determination of zinc in dairy and medicine samples with the recovery of 99.3%¹01.2%.ChapterⅣDetermination of isoniazid in medicine by Anodic Stripping Voltammetry on Composite Bismuth Film ElectrodeThis paper presented an analytical method which was used in determination isoniazid in drug by composite bismuth film electrode anodic stripping voltammetry. The method was used to determine isoniazid in 0.01 M acetic acid-sodium acetate buffer solution. The composite bismuth film electrode was used as the working electrode, the saturated calomel electrode was used as a reference electrode and platinum electrode was used as an auxiliary electrode. The good linearity between peak current and concentration was obtained in the concentration range of 8.0×10^-82.0×10^-6 mol/L. The limit of detection was 1.8×10^-8 mol/L after 60 s deposition procedure. It can be seen from obtained results that the composite bismuth film working electrode had advantages of high linear range, good reproducibility and performance. Moreover, satisfied results of measuring isoniazid were got.更多还原