A quantum mechanical approach to the oxidation mechanism of graphene oxide (GO).

Elucidation of the reaction mechanism concerning the oxidation above the face and at the edge of a large, oxidized graphene (GO) cluster, namely CHO, by molecular oxygen in the first excited state (Δ) was achieved with quantum mechanical calculations using the ONIOM two-layer method. Oxidation on the face of the aforementioned cluster leads to the formation of an ozone molecule, whereas oxygen molecule attack at the edge of the oxidized graphene surface either launches an ozonide -a five-membered ring species- formation during its outward approach or an 1,3-dioxetane -a four-membered ring species- production along its inward invasion. A detailed examination of the proposed pathways suggests that the ozonide formation should overcome almost one and a half times an adiabatic energy barrier with respect to the ozone production and is strongly exergonic by up to -50.1 kcal mol, supporting the experimental findings that both compounds are critically involved in the explosive deoxygenation of GO. On the other hand, the 1,3-dioxetane alternative pathway is considered even more exergonic, although it requires an overwhelming adiabatic energy barrier of 29.8 kcal mol to accomplish its target.