Revisiting the Oxidation of Graphite: Reaction Mechanism, Chemical Stability, and Structure Self-Regulation

To fully understand the chemical structure of graphene oxide and the oxidation chemistry of sp2 carbon sites, we conducted a practical experiment and density functional theory combined study on the oxidation process of graphite. The nuclear magnetic resonance, thermogravimetric analysis, and X-ray photoelectron spectroscopy results of unhydrolyzed oxidized graphite indicate that the oxidation process involves the intercalating oxidation, where electrically neutral species is the oxidizing agent, and the diffusive-oxidation, where MnO3+ is the oxidizing agent. An intrinsic formation and conversion path of oxygen-containing functional groups is proposed based on the experimental results and further interpreted with the aid of frontier molecular orbital theory and density functional theory. Meanwhile, the two unique features of the oxidation process of graphite, the chemistry stability of oxygen-containing functional groups in the strong oxidizing medium, and the self-regulation of the oxidation process are theoretically reasoned.