本文選題：石墨烯 + 功能團(tuán)化改性�。� 參考：《天津大學(xué)》2015年博士論文

【摘要】：石墨烯是一種新型二維碳納米材料,獨(dú)特的物理結(jié)構(gòu)賦予了它諸多優(yōu)異性能,尤其是大比表面積、高電子傳輸能力和高電化學(xué)催化活性使其在電化學(xué)檢測領(lǐng)域得到了廣泛關(guān)注。然而,石墨烯功能團(tuán)化改性以及作為電極材料與被檢測底物的相互作用機(jī)理等方面還存在很多問題,限制了其在電化學(xué)檢測領(lǐng)域的深入研究和應(yīng)用進(jìn)程。本論文重點(diǎn)研究石墨烯材料的含氧、含氮和含硫基團(tuán)化改性,及改性對(duì)石墨烯材料物化性質(zhì)和電化學(xué)檢測性能的影響。取得了以下創(chuàng)新性成果:(1)通過控制水合肼和氧化石墨烯(GO)的反應(yīng)時(shí)間,有效控制了石墨烯表面含氧基團(tuán)的種類和數(shù)量,進(jìn)一步用電化學(xué)方法研究了含氧基團(tuán)在檢測重金屬離子銅的過程中所起的作用,發(fā)現(xiàn)含氧基團(tuán)尤其是羧基在水溶液中解離所帶的表面負(fù)電荷對(duì)銅離子的檢測具有非常重要的促進(jìn)作用,甚至比石墨烯材料的導(dǎo)電性更為重要,拓寬了人們對(duì)石墨烯材料的認(rèn)識(shí)。開發(fā)了一種臭氧/雙氧水/超聲耦合氧化法制備富羧基石墨烯量子點(diǎn)(GQDs)的方法,此法操作簡便、便于控制且成本較低,并且得到的GQDs材料具有較高的純度。(2)利用批量平衡法、Zeta電位法和循環(huán)伏安法研究了氨基和碳骨架氮元素對(duì)石墨烯材料表面電位的影響,發(fā)現(xiàn)氨基的質(zhì)子化可以提高石墨烯材料的表面電位,從而提高石墨烯材料對(duì)帶負(fù)電荷底物的吸附和檢測性能。(3)開發(fā)了一種利用硫酸鎂和GO高溫固相反應(yīng)制備單一噻吩型硫摻雜的石墨烯的方法,反應(yīng)條件可以有效控制硫元素的含量和存在狀態(tài),還研究了硫改性對(duì)石墨烯形貌和性能的影響,系統(tǒng)研究了多巴胺在硫摻雜石墨烯材料電極表面的電化學(xué)行為。(4)開發(fā)了一種通過在電解液中添加含有硫、氮物質(zhì),在電解還原GO的同時(shí)將氮硫元素?fù)诫s進(jìn)石墨烯的方法。并以添加劑乙二胺為主要研究對(duì)象,表明乙二胺通過與GO表面含氧基團(tuán)的親和取代反應(yīng)與酰胺化反應(yīng)接入,電解將酰胺基團(tuán)還原為亞胺基。所得產(chǎn)物具有良好的電化學(xué)性質(zhì)及其電化學(xué)檢測性能。
[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.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ127.11;O657.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 王斌;常雁紅;智林杰;;高產(chǎn)量制備石墨烯及其優(yōu)異的重金屬離子檢測性能(英文)[J];新型炭材料;2011年01期

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本文編號(hào)：1858739