  Electron paramagnetic resonance (EPR) study of air-physisorbed defective
carbon nano-onions evidences in favor of microwave assisted formation of
weakly-bound paramagnetic complexes comprising negatively-charged O2- ions and
edge carbon atoms carrying pi-electronic spins. These complexes being located
on the graphene edges are stable at low temperatures but irreversibly
dissociate at temperatures above 50-60 K. These EPR findings are justified by
density functional theory (DFT) calculations demonstrating transfer of an
electron from the zigzag edge of graphene-like material to oxygen molecule
physisorbed on the graphene sheet edge. This charge transfer causes changing
the spin state of the adsorbed oxygen molecule from S = 1 to S = 1/2 one. DFT
calculations show significant changes of adsorption energy of oxygen molecule
and robustness of the charge transfer to variations of the graphene-like
substrate morphology (flat and corrugated mono- and bi-layered graphene) as
well as edges passivation. The presence of H- and COOH- terminated edge carbon
sites with such corrugated substrate morphology allows formation of ZE-O2-
paramagnetic complexes characterized by small (<50 meV) binding energies and
also explains their irreversible dissociation as revealed by EPR.
