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石墨烯氧化物的单硫化及还原:一锅法合成的氧还原材料的混合催化

Monothiolation and Reduction of Graphene OxideviaOne-Pot Synthesis: Hybrid Catalyst for Oxygen Reduction

作者:Chun Kiang Chua;Martin Pumera;

关键词:graphene,hybrid materials,catalysis,chemical functionalization,electrochemistry

DOI:https://doi.org/10.1021/acsnano.5b00438

发表时间:2015年

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摘要

石墨烯的功能化提供了多种可能性,可以改善对石墨烯的处理,并在石墨烯上进一步实现化学转化。主要以杂原子为基础的功能团对石墨烯的功能化以增强其化学和物理性质的研究受到了密切关注,但通常会导致杂原子以不同的功能团形式嫁接在石墨烯上。在这里,我们展示了氧化石墨烯可以被功能化为主要是一种硫基官能团,并同时被还原为单硫醇功能化的石墨烯。硫醇功能化的石墨烯表现出高电导率和异质电子转移率。石墨烯中还嵌入了一小量的锰杂质,这些杂质来自之前的石墨氧化过程,有助于硫醇功能化的石墨烯在碱性介质中作为混合电催化剂进行氧还原反应,其起始电位低于铂/碳。对石墨烯的进一步表征是通过X射线光电子能谱、扫描电子显微镜和能谱、傅里叶变换红外光谱、热重分析、拉曼光谱和电化学阻抗光谱进行的。这种材料属于高活性电催化剂的混合类别。


Abstract

The functionalization of graphene provides diverse possibilities to improve the handling of graphene and enable further chemical transformation on graphene. Graphene functionalized with mainly heteroatom-based functional groups to enhance its chemical and physical properties is intensively pursued but often resulted in grafting of the heteroatoms as various functional groups. Here, we show that graphene oxide can be functionalized with predominantly a single type of sulfur moiety and reduced simultaneously to form monothiol-functionalized graphene. The thiol-functionalized graphene shows a high electrical conductivity and heterogeneous electron transfer rate. Graphene is also embedded with a trace amount of manganese impurities originating from a prior graphite oxidation process, which facilitates the thiol-functionalized graphene to function as a hybrid electrocatalyst for oxygen reduction reactions in alkaline medium with an onset potential lower than for Pt/C. Further characterizations of the graphene are performed with X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, and electrochemical impedance spectroscopy. This material contributes to the class of hybrids that are highly active electrocatalysts.