石墨烯官能团化改性及其在电化学检测中的应用研究

发布时间：2018-05-07 22:26

本文选题：石墨烯 + 功能团化改性　；参考：《天津大学》2015年博士论文

【摘要】：石墨烯是一种新型二维碳纳米材料,独特的物理结构赋予了它诸多优异性能,尤其是大比表面积、高电子传输能力和高电化学催化活性使其在电化学检测领域得到了广泛关注。然而,石墨烯功能团化改性以及作为电极材料与被检测底物的相互作用机理等方面还存在很多问题,限制了其在电化学检测领域的深入研究和应用进程。本论文重点研究石墨烯材料的含氧、含氮和含硫基团化改性,及改性对石墨烯材料物化性质和电化学检测性能的影响。取得了以下创新性成果:(1)通过控制水合肼和氧化石墨烯(GO)的反应时间,有效控制了石墨烯表面含氧基团的种类和数量,进一步用电化学方法研究了含氧基团在检测重金属离子铜的过程中所起的作用,发现含氧基团尤其是羧基在水溶液中解离所带的表面负电荷对铜离子的检测具有非常重要的促进作用,甚至比石墨烯材料的导电性更为重要,拓宽了人们对石墨烯材料的认识。开发了一种臭氧/双氧水/超声耦合氧化法制备富羧基石墨烯量子点(GQDs)的方法,此法操作简便、便于控制且成本较低,并且得到的GQDs材料具有较高的纯度。(2)利用批量平衡法、Zeta电位法和循环伏安法研究了氨基和碳骨架氮元素对石墨烯材料表面电位的影响,发现氨基的质子化可以提高石墨烯材料的表面电位,从而提高石墨烯材料对带负电荷底物的吸附和检测性能。(3)开发了一种利用硫酸镁和GO高温固相反应制备单一噻吩型硫掺杂的石墨烯的方法,反应条件可以有效控制硫元素的含量和存在状态,还研究了硫改性对石墨烯形貌和性能的影响,系统研究了多巴胺在硫掺杂石墨烯材料电极表面的电化学行为。(4)开发了一种通过在电解液中添加含有硫、氮物质,在电解还原GO的同时将氮硫元素掺杂进石墨烯的方法。并以添加剂乙二胺为主要研究对象,表明乙二胺通过与GO表面含氧基团的亲和取代反应与酰胺化反应接入,电解将酰胺基团还原为亚胺基。所得产物具有良好的电化学性质及其电化学检测性能。
[Abstract]:Graphene is a new two-dimensional carbon nanomaterials, and its unique physical structure has given it many excellent properties, especially for its large specific surface area, high electron transport ability and high electrochemical catalytic activity, which has attracted wide attention in the field of electrochemical detection. However, there are still many problems in the functional group modification of graphene and the interaction mechanism between graphene as electrode material and the detected substrate, which limits the further research and application of graphene in the field of electrochemical detection. In this paper, the effects of the modification of oxygen, nitrogen and sulfur groups on the physicochemical properties and electrochemical detection properties of graphene materials were studied. By controlling the reaction time of hydrazine hydrate and graphene oxide (GOO), the species and number of oxygenated groups on the surface of graphene were effectively controlled. Furthermore, the role of oxygen-containing groups in the detection of heavy metal ion copper was studied by electrochemical method. It is found that the surface negative charge of oxygen groups, especially carboxyl groups, has a very important role in the detection of copper ions, even more important than the conductivity of graphene materials, which broadens the understanding of graphene materials. An ozone / hydrogen peroxide / ultrasonic coupled oxidation method for the preparation of carboxyl-rich graphene quantum dots (GQDs) was developed. The method is easy to operate, easy to control and low in cost. And the GQDs material has high purity.) the effects of amino and carbon skeleton nitrogen elements on the surface potential of graphene materials were studied by batch equilibrium method and cyclic voltammetry. It is found that the protonation of amino groups can increase the surface potential of graphene materials. In order to improve the adsorption and detection properties of graphene materials with negative charge substrates, a method was developed to prepare single thiophene sulfur doped graphene by solid state reaction of magnesium sulfate and go at high temperature. The effect of sulfur modification on the morphology and properties of graphene was studied. The electrochemical behavior of dopamine on the surface of sulfur-doped graphene electrode was systematically studied. A method was developed for electroreduction of go and doping of nitrogen and sulfur into graphene by adding sulfur and nitrogen into the electrolyte. Taking the additive ethylenediamine as the main research object, it was shown that the amide group was electrolytically reduced to imino group by the affinity substitution reaction and amidation reaction between the ethylene diamine and the oxygen-containing group on go surface. The obtained products have good electrochemical properties and electrochemical detection performance.
【学位授予单位】：天津大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ127.11;O657.1

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