Covalent Modification of Graphene Quantum Dots by Fullerene C60 Derivative

J. Breczko, Marta Kirmuc, Diana M Bobrowska, V. Kirianchuk, K. Winkler
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Abstract

Extended Abstract Graphene quantum dots (GQDs) are a relatively new class of carbon nanomaterials with a promising potential use. The unique physico-chemical properties of GQDs are intermediate between the features exhibited by nanoparticles, which results from their small size (diameter <30 nm) and features typical for carbon nanostructures with high specific surface area, as the consequence of the fact that GQDs are fragments of a graphene plane [1]. The high reactivity of GQD edges allowing them to be functionalized with oxygen containing groups and to increase their dispersability while good electrochemical properties have been maintained. Presented results are focused on synthesis of a hybrid system between fullerene C60 and GQDs structures based on covalent modification. In the first step, a 1,3-dipolar cycloaddition reaction to obtain the pyrrolidine fullerene derivative was performed. It involved the introduction of fullerene C60 in the toluene solution containing sarcosine and 4hydroxybenzaldehyde and maintaining the mixture at boiling temperature for 12 h, according to the procedure described in the literature [2]. In parallel, the GQDs modified with carboxylic groups were obtained by ultrasonification of graphite flakes in a nitrating mixture under high temperature conditions [3]. The hydrophilic functional groups, formed mainly at the edges of the GQDs, have reacted with the added thionyl chloride and allow to obtain more reactive acid chloride groups. In the final step, fullerene C60 pyrrolidone was covalently bonded to the functionalized GQDs to form hybrid C60-GQDs. Synthesized C60/GQDs material was characterized by microscopic (TEM, SEM) as well as by spectroscopic methods (FTIR, Raman) to confirm each step modifications. According to the combination of GQDs exhibiting large specific capacitance and fullerenes allowing the faradaic processes to occur, obtained hybrid system was expected to act as an interesting charge exchange mediator. Therefore, electrochemical studies were undertaken and the potential of C60/GQDs system as an electrode material of the capacitors was examined.
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富勒烯C60衍生物对石墨烯量子点的共价修饰
石墨烯量子点(GQDs)是一类相对较新的碳纳米材料,具有广阔的应用前景。GQDs独特的物理化学性质介于纳米颗粒所表现出的特征之间,这是由于它们的小尺寸(直径<30 nm)和具有高比表面积的碳纳米结构的典型特征,这是由于GQDs是石墨烯平面[1]的片段。GQD边缘的高反应性使其能够与含氧基团进行官能团化,并在保持良好电化学性能的同时增加其分散性。研究结果主要集中在基于共价修饰的富勒烯C60和GQDs结构之间的杂化体系的合成。第一步采用1,3-偶极环加成反应制得吡咯烷类富勒烯衍生物。它包括在含有肌氨酸和4羟基苯甲醛的甲苯溶液中引入富勒烯C60,并根据文献[2]中描述的程序将混合物在沸点下保持12小时。同时,在高温条件下,对石墨薄片在硝化混合物中进行超声波处理,得到了羧基修饰的GQDs。主要在GQDs边缘形成的亲水官能团与添加的亚硫酰氯发生反应,从而得到活性更强的酸性氯基团。最后一步,富勒烯C60吡咯烷酮与功能化的GQDs共价结合,形成杂化的C60-GQDs。对合成的C60/GQDs材料进行了微观表征(TEM, SEM)和光谱表征(FTIR, Raman),以确认每一步的修饰。根据具有大比电容的GQDs和允许法拉第过程发生的富勒烯的组合,所获得的杂化体系有望作为一种有趣的电荷交换介质。因此,对C60/GQDs体系进行了电化学研究,并对其作为电容器电极材料的潜力进行了考察。
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