The interaction of molecular oxygen with active sites of graphite: a theoretical study

The adsorption of molecular oxygen at defective edge sites of zigzag and armchair graphite surfaces has been investigated by adopting cluster models in conjunction with density functional theory. Several different types of chemisorbed O2 species are identified. It was found that the defect edge sites exhibit the significant catalytic role toward the adsorption and activation of molecular oxygen. The O2 molecule is not only able to strongly bind to these edge sites, but the O–O bond strength is obviously weakened. Moreover, the calculated adsorption energy for O2 adsorbed on the clean graphite basal surface is fairly consistent with the weak interaction nature of O2 with the surface observed in the experiment, indicating one-layer cluster model is an effective way to study O2 adsorption on graphite surface in terms of accuracy and computational cost, which is in agreement with previous experience. Whereas, we note that the local detailed arrangement of edge carbon atoms can play an important effect on the adsorption of O2 on defect surfaces.