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Graphite Oxides: Effects of Permanganate and Chlorate Oxidants on the Oxygen Composition
Authors:Chun Kiang Chua  Prof Zdeněk Sofer  Prof Martin Pumera
Institution:1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Science, Nanyang Technological University, 21 Nanyang Link, 637371 (Singapore);2. Institute of Chemical Technology, Department of Inorganic Chemistry, Technická 5, 166 28 Prague 6 (Czech Republic)
Abstract:Research on graphene materials has refocused on graphite oxides (GOs) in recent years. The fabrication of GO is commonly accomplished by using concentrated sulfuric acid in conjunction with: a) fuming nitric acid and KClO3 oxidant (Staudenmaier); b) concentrated nitric acid and KClO3 oxidant (Hofmann); c) sodium nitrate for in situ production of nitric acid in the presence of KMnO4 (Hummers); or d) concentrated phosphoric acid with KMnO4 (Tour). These methods have been used interchangeably in the graphene community, since the properties of GOs produced by these different methods were assumed as almost similar. In light of the wide applicability of GOs in nanotechnology applications, in which presence of certain oxygen functional groups are specifically important, the qualities and functionalities of the GOs produced by using these four different methods, side‐by‐side, was investigated. The structural characterizations of the GOs would be probed by using high resolution X‐ray photoelectron spectroscopy, nuclear magnetic resonance, Fourier transform infrared spectroscopy, and Raman spectroscopy. Further electrochemical applicability would be evaluated by using electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses highlighted that the oxidation methods based on permanganate oxidant (Hummers and Tour methods) gave GOs with lower heterogeneous electron‐transfer rates and a higher amount of carbonyl and carboxyl functionalities compared with when using chlorate oxidant (Staudenmaier and Hofmann methods). These observations indicated large disparities between the GOs obtained from different oxidation methods. Such insights would provide fundamental knowledge for fine tuning GO for future applications.
Keywords:electrochemistry  graphite oxides  materials science  oxidation  oxygen‐containing groups
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