三维石墨烯纳米复合材料的制备、催化性质研究及应用

发布时间：2018-06-18 04:19

本文选题：三维石墨烯纳米复合材料 + 原位自组装　；参考：《兰州大学》2015年硕士论文

【摘要】：三维石墨烯纳米复合材料具有优异的物理和化学性质,在不同的科学研究领域都起着非常重要的作用。其中,金属负载,尤其是贵金属掺杂的三维石墨烯纳米复合材料的制备及其应用研究越来越成为纳米材料科学、生命科学、分析化学等领域科研工作者的研究重点和热点之一。三维石墨烯纳米复合材料除具有传统二维石墨烯的性质外,还具有独特的机械性能、良好的电子传导能力、超大的比表面积和较好的生物兼容性等特性,在离子电池、电化学器件、能量储存、生物传感器、催化等方面都有着非常广泛的应用。关于三维石墨烯复合材料的制备方法已有许多报道,但是一般都需要分步进行、操作复杂、需要额外添加还原剂,而且制得的金属颗粒尺寸分布不均匀、三维结构不明显,尤其是对于双金属负载的三维石墨烯结构而言,其制备和性质研究越来越成为热点。本论文在前人工作的基础上,围绕双金属负载的三维石墨烯纳米复合材料的制备方法、催化性质及在分析化学中的应用研究,开展了下述的研究工作：(1)建立了一种简单的一步原位自组装合成双金属负载三维石墨烯纳米复合物的新方法,并初步考察了其对对硝基苯酚(4-NP)降解反应的催化性能和重复利用性；(2)深入研究了该纳米复合材料的类酶催化性质,并建立了操作简单、灵敏度高、选择性好的比色检测双氧水、谷胱甘肽和葡萄糖的新方法：(3)基于该纳米复合材料的催化特性,研究了其对电化学催化双氧水分解的响应行为,并将其用于环境样品和生活用品中残余双氧水的分析检测。第一章：介绍了三维石墨烯纳米复合材料的性质、研究现状、制备方法、特性等基础知识及其在电化学器件、传感器、催化材料等领域的应用。第二章：通过一步方法原位合成了双金属负载的三维石墨烯纳米复合材料：三氯化铁和氯化钯前驱体通过静电作用吸附到氧化石墨烯(GO)片层表面,并通过调节pH值使形成的氢氧化铁和氢氧化钯分散在GO片层上,再经分步热还原及自组装形成三维还原型氧化石墨烯四氧化三铁-钯(3DRGO_Fe3O4-Pd)纳米复合材料。通过多种表征分析,证明材料制备成功并确定了材料的具体结构及组成。进而,以对硝基苯酚的降解反应作为模型反应,考察了3DRGO_Fe3O4-Pd纳米复合材料的催化能力。实验结果表明,该纳米复合物具有很好的催化活性和较高的重复利用率,在环境污染物的催化降解中有着广阔的应用前景。第三章：研究表明,3DRGO_Fe3O4-Pd纳米复合材料同时具有类氧化物酶和类过氧化物酶的催化活性,且其类过氧化物酶的活性更高,能够催化H202分解并氧化反应底物3,3’,5,5’-四甲基联苯胺(TMB)显现蓝色。本章中,以TMB-H202显色体系为模型反应,重点考察了3DRGO_Fe3O4-Pd的类过氧化物酶催化活性。与过氧化氢酶(HRP)类似,其催化活性也受pH值、温度、催化剂用量以及H202浓度的影响。通过与单金属负载的纳米复合材料对比,发现3DRGO_Fe3O4-Pd具有更高的类过氧化物酶催化活性,主要是由于3DRG0上负载的Fe304和Pd纳米颗粒间的协同作用引起的。3DRGO_Fe3O4-Pd具有优异的批次稳定性、放置稳定性和重复利用性,经重复催化使用10次,其结构、形貌及纳米颗粒的粒径仍基本保持不变。经与其他类酶材料对比,发现3DRGO_Fe3O4-Pd对反应底物H202具有很好的亲和力和较快的反应速率。第四章：鉴于3DRGO_Fe3O4-Pd纳米复合材料对双氧水分解的较强催化能力,本章中,将其滴涂到玻碳电极上,在电化学条件下,考察了其对双氧水分解的催化行为。经与负载单金属的纳米复合材料对比,发现3DRGO_Fe3O4-Pd纳米复合物在催化双氧水分解方面有更好的电化学活性。分别在不同扫描速度下,研究了修饰电极的循环伏安曲线,发现电子在修饰电极表面的转移主要受表面控制。该修饰电极用于双氧水检测的线性范围为9.3×10-8-1.58×10-2 M,检出限为37nM,灵敏度为183.58μAcm-2mM-1。最后,该方法被成功地用于环境样品和生活用品中残留双氧水的检测,为实际样品中双氧水的检测提供了新的方法。
[Abstract]:Three dimensional graphene nanocomposites have excellent physical and chemical properties and play a very important role in different scientific research fields. Among them, the preparation and application of metal load, especially the three dimensional graphene nanocomposites doped by precious metals, are becoming more and more important in nanomaterial science, life science and analytical chemistry. In addition to the properties of traditional two-dimensional graphene, three-dimensional graphene nanocomposites have unique mechanical properties, good electronic conductivity, large specific surface area and better biological compatibility, in ion batteries, electrochemical devices, energy storage, and biology. There have been extensive applications in sensors, catalysis and other aspects. There have been many reports on the preparation methods of three-dimensional graphene composites, but generally, it is necessary to carry out step by step, complicated operation, and the need for additional reducing agent, and the size distribution of the metal particles is uneven, and the three-dimensional structure is not obvious, especially for the bimetal load. The preparation and properties of the three dimensional graphene are becoming more and more hot. On the basis of the previous work, the research work on the preparation methods, catalytic properties and application in analytical chemistry of the three-dimensional graphene nanocomposites supported by the bimetallic load has been carried out. (1) a simple one is established. A new method for the synthesis of bimetallic loaded 3-dimensional graphene nanocomposites by self assembly in situ, and its catalytic performance and repeatability for the degradation of p-nitrophenol (4-NP) were preliminarily investigated. (2) the catalytic properties of the nanocomposites were studied in depth, and a colorimetric assay with simple operation, high sensitivity and good selectivity was established. New methods for measuring hydrogen peroxide, glutathione and glucose: (3) based on the catalytic properties of the nanocomposites, the response behavior to the decomposition of hydrogen peroxide catalyzed by electrochemical catalysis is studied and used for the analysis and detection of residual hydrogen peroxide in environmental samples and living articles. Chapter 1: the properties of the three-dimensional graphene nanocomposites are introduced. Research status, preparation methods, properties and other basic knowledge and applications in electrochemical devices, sensors, catalytic materials and other fields. Second chapter: one step method in situ synthesis of bimetal loaded three-dimensional graphene nanocomposites: iron trichloride and palladium chloride precursors adsorbed to the GO layer by electrostatic action On the surface, the formation of iron hydroxide and palladium hydroxide is dispersed on the GO layer by adjusting the pH value, and then the three-dimensional reductive graphite oxide palladium (3DRGO_Fe3O4-Pd) nanocomposite is formed by stepwise thermal reduction and self-assembly. Through a variety of characterization analysis, it is proved that the preparation of the material is successful and the specific structure and group of the material are determined. Furthermore, the catalytic ability of 3DRGO_Fe3O4-Pd nanocomposites was investigated with the degradation reaction of p-nitrophenol as a model reaction. The experimental results showed that the nanocomposites had good catalytic activity and high reutilization rate. The third chapter: the study table. The 3DRGO_Fe3O4-Pd nanocomposite has the catalytic activity of the oxide like enzyme and the peroxidase, and the activity of its peroxidase is higher. It can catalyze H202 decomposition and oxidize the substrate 3,3 ', 5,5' - four methylbiphenyl amine (TMB) shows blue. In this chapter, the TMB-H202 color system is used as the model reaction, and the 3D is focused on the 3D. The activity of RGO_Fe3O4-Pd like peroxidase. Similar to catalase (HRP), its catalytic activity is also influenced by pH, temperature, catalyst dosage and H202 concentration. By comparing with the nanocomposites loaded with mono metal, it is found that 3DRGO_Fe3O4-Pd has a higher activity of peroxidase catalysis, mainly due to the load on 3DRG0. The synergistic action between Fe304 and Pd nanoparticles has excellent batch stability, placement stability and reutilization. The structure, morphology and particle size of nanoparticles remain basically unchanged after 10 times of repeated catalytic use. Compared with other enzyme like materials, it is found that 3DRGO_Fe3O4-Pd has a reaction to the reaction substrate H202. Good affinity and fast reaction rate. Fourth chapter: in view of the strong catalytic ability of 3DRGO_Fe3O4-Pd nanocomposites to decompose hydrogen peroxide, in this chapter, they are applied to the glassy carbon electrode. Under the electrochemical condition, the catalytic behavior of hydrogen peroxide decomposition is investigated. By comparing with the supported monometallic nanocomposites, 3D has been found. The RGO_Fe3O4-Pd nanocomposites have better electrochemical activity in the catalytic decomposition of hydrogen peroxide. The cyclic voltammetry curves of the modified electrodes are studied at different scanning speeds. It is found that the transfer of electrons on the surface of the modified electrode is mainly controlled by the surface. The linear range of the modified electrode is 9.3 x 10-8-1.58 x 10-2 M for the detection of dioxygen water. The detection limit is 37nM and the sensitivity is 183.58 micron Acm-2mM-1.. The method has been successfully used for the detection of residual hydrogen peroxide in environmental samples and daily necessities, which provides a new method for the detection of hydrogen peroxide in the actual samples.
【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】：O643.36;TB33

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