Origin of Oxygen in Graphene Oxide Revealed by O and O Isotopic Labeling.

Wet-chemical oxidation of graphite in a mixture of sulfuric acid with a strong oxidizer, such as potassium permanganate, leads to the formation of graphene oxide with hydroxyl and epoxide groups as the major functional groups. Nevertheless, the reaction mechanism remains unclear and the source of oxygen is a subject of debate. It could theoretically originate from the oxidizer, water, or sulfuric acid. In this study, we employed 18O and 17O labeled reagents to experimentally elucidate the reaction mechanism and, thus, determine the origin of oxo-functional groups. Our findings reveal the multifaceted roles of sulfuric acid, acting as a dispersion medium, a dehydrating agent for potassium permanganate, and an intercalant. Additionally, it significantly acts as a source of oxygen next to manganese oxides. Through O solid-state magic-angle spinning (MAS) NMR experiments, we exclude water as a direct reaction partner during oxygenation. With labeling experiments, we conclude on mechanistic insights, which may be exploited for the synthesis of novel graphene derivatives.