硫族钼化物纳米复合材料修饰玻碳电极的制备及其在分析化学中的应用研究

发布时间：2018-01-15 21:24

本文关键词：硫族钼化物纳米复合材料修饰玻碳电极的制备及其在分析化学中的应用研究　出处：《兰州大学》2015年硕士论文　论文类型：学位论文

【摘要】：本硕士学位论文以具有光电催化特征的纳米半导体硫族钼化物为基质,配以其他不同的功能材料制备了几种不同的复合材料,然后将所制复合材料用于修饰玻碳电极(GCE),构建了相应的电化学传感器。最终将所制备的传感器用于药物、双氧水等物质的分析方法学构建。主要内容包括：1.制备了聚二烯丙基二甲基氯化铵(PDDA)功能化的石墨烯(G, graphene)、二硫化钼(MoS2)纳米花状材料PDDA-G-MoS2。然后利用库仑力和金硫键作用原理将纳米金自组装在PDDA-G-MoS2上制得Au/PDDA-G-MoS2复合材料。最终将Au/PDDA-G-MoS2修饰在GCE表面得到Au/PDDA-G-MoS2/GCE传感器,将其用于丁香酚的灵敏检测。用循环伏安法(CV)研究了修饰电极自身的电化学行为以及丁香酚的电极反应特征；在0.1 M pH=5.5的醋酸-醋酸钠缓冲溶液中+0.582 V电位下,连续添加不同浓度的丁香酚,通过其安培响应绘制了丁香酚的工作曲线。在0.1μM到440 μM范围,氧化峰电流与丁香酚的浓度有良好的线性关系,检测限为0.036 μM(S/N=3)。所建立的分析方法已用于实际样品中丁香酚的检测,效果令人满意。2.以MoS2为模板通过简单的水热法合成Pt纳米粒子,得到Pt-MoS2复合纳米材料。用透射电镜(TEM)、高分辨透射电镜(]HR-TEM)、电化学交流阻抗法(EIS)和X射线光电子能谱分析(XPS)等手段系统表征了所制得的复合纳米材料。以GCE为基底电极,构建了Pt-MoS2/GCE生物传感器,并用于对H2O2类酶催化分析。用CV法和时间-电流曲线表征了该传感器的电化学行为。在N2饱和的磷酸缓冲溶液(PBS)中,所构建生物传感器对H2O2还原反应呈现明显的电催化活性。H2O2还原电流与浓度在4×10-6～4.85×10-2 mol L-1范围内有良好的线性关系；检测限为1×10-6 mol L-1(S/N=3)。此工作表明在Pt-MoS2复合纳米材料中由于Pt-S键的原因促成Pt纳米粒子在二硫化钼表面合成,使得Pt-MoS2复合纳米材料相对于单独纳米Pt而言有更好的催化活性。3.用水热合成法合成了不同形貌的纳米MoSe2材料。所制得的材料分别用场发射扫描电镜(FE-SEM)、HR-TEM、XRD和XPS进行了系统的形貌和组成分析。然后将不同形貌MoSe2修饰于GCE表面,用线性扫描伏安法(LSV)和Tafel曲线法研究了4oSe2/GCE的电化学行为以及用于析氢反应(HER)的催化活性。本工作结果表明通过改变反应物比例可以调控MoSe2材料的形貌进而影响其催化活性。
[Abstract]:In this master's degree thesis, several kinds of composite materials were prepared based on nano-semiconductor molybdate with photocatalytic characteristics and other functional materials. Then the composite material was used to modify the glassy carbon electrode and the corresponding electrochemical sensor was constructed. Finally, the prepared sensor was used for medicine. Construction of analytical methodology for hydrogen peroxide and other substances. The main contents include: 1. Preparation of poly (diallyl) dimethyl ammonium chloride PDDA-functionalized graphene (G, graphene). Molybdenum disulfide (MoS _ 2). Nanocrystalline PDDA-G-MoS2.Then Au/PDDA-G-MoS2 complex was prepared by self-assembly of nano-gold onto PDDA-G-MoS2 by using the interaction principle of Kulun force and gold-sulfur bond. Finally, Au/PDDA-G-MoS2 was modified on the surface of GCE to obtain Au/PDDA-G-MoS2/GCE sensor. The electrochemical behavior of the modified electrode and the electrode reaction characteristics of eugenol were studied by cyclic voltammetry (CV). Different concentrations of eugenol were added at 0.582V potential in the buffer solution of acetic acid-sodium acetate at 0. 1 M pH=5.5. The operating curve of eugenol was plotted by its amperometric response. In the range of 0.1 渭 M to 440 渭 M, the oxidation peak current had a good linear relationship with the concentration of eugenol. The detection limit is 0.036 渭 m ~ (-1) S / N ~ (3 +). The established analytical method has been applied to the determination of eugenol in practical samples. Using MoS2 as template, Pt nanoparticles were synthesized by a simple hydrothermal method, and Pt-MoS2 composite nanomaterials were obtained by transmission electron microscopy (TEM). High resolution transmission electron microscopy (HR-TEM). The composite nanomaterials were characterized by electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). GCE was used as substrate electrode. Pt-MoS2/GCE biosensor was constructed. The electrochemical behavior of the sensor was characterized by CV method and time-current curve in N2 saturated phosphoric acid buffer solution (PBSs). The biosensor showed obvious electrocatalytic activity for H _ 2O _ 2 reduction. The reduction current and concentration of H _ 2O _ 2 were 4 脳 10 ~ (-6) ~ 4.85 脳 10 ~ (-2) mol. There is a good linear relationship in the range of L-1; The detection limit is 1 脳 10 ~ (-6) mol / L ~ (-1) S / N ~ (3). The results show that Pt nanoparticles are synthesized on the surface of molybdenum disulfide due to the Pt-S bond in Pt-MoS2 composite nanomaterials. The Pt-MoS2 composite nano-materials have better catalytic activity than the single nano-Pt. 3. Hydrothermal synthesis of nano-sized MoSe2 materials with different morphologies. The prepared materials are used respectively. Field Emission scanning Electron Microscopy (. FE-SEM). The morphology and composition of GCE were analyzed by HR-TEMX XRD and XPS, and the different morphologies of MoSe2 were modified on the surface of GCE. The electrochemical behavior of 4oSe2 / GCE and its application to hydrogen evolution were studied by linear sweep voltammetry (LSVV) and Tafel curve method. The results show that the morphology of MoSe2 materials can be controlled by changing the reactants ratio, and the catalytic activity can be affected by changing the ratio of reactants.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33;O657.1

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