Mechanistic Insights on Functionalization of Graphene with Ozone

[Image: see text] The exposure of graphene to O(3) results in functionalization of its lattice with epoxy, even at room temperature. This reaction is of fundamental interest for precise lattice patterning, however, is not well understood. Herein, using van der Waals density functional theory (vdW-DFT) incorporating spin-polarized calculations, we find that O(3) strongly physisorbs on graphene with a binding energy of −0.46 eV. It configures in a tilted position with the two terminal O atoms centered above the neighboring graphene honeycombs. A dissociative chemisorption follows by surpassing an energy barrier of 0.75 eV and grafting an epoxy group on graphene reducing the energy of the system by 0.14 eV from the physisorbed state. Subsequent O(3) chemisorption is preferred on the same honeycomb, yielding two epoxy groups separated by a single C–C bridge. We show that capturing the onset of spin in oxygen during chemisorption is crucial. We verify this finding with experiments where an exponential increase in the density of epoxy groups as a function of reaction temperature yields an energy barrier of 0.66 eV, in agreement with the DFT prediction. These insights will help efforts to obtain precise patterning of the graphene lattice.