Atomic Mechanism of Electrocatalytically Active Co–N Complexes in Graphene Basal Plane for Oxygen Reduction Reaction

Superior catalytic activity and high chemical stability of inexpensive electrocatalysts for the oxygen reduction reaction (ORR) are crucial to the large-scale practical application of fuel cells. The nonprecious metal/N modified graphene electrocatalysts are regarded as one of potential candidates, and the further enhancement of their catalytic activity depends on improving active reaction sites at not only graphene edges but also its basal plane. Herein, the ORR mechanism and reaction pathways of Co–N co-doping onto the graphene basal plane have been studied by using first-principles calculations and ab initio molecular dynamics simulations. Compared to singly N-doped and Co-doped graphenes, the Co–N co-doped graphene surface exhibits superior ORR activity and the selectivity toward a four-electron reduction pathway. The result originates from catalytic sites of the graphene surface being modified by the hybridization between Co 3d states and N 2p states, resulting in the catalyst with a moderate binding ability to oxygenated intermediates. Hence, introducing the Co–N4 complex onto the graphene basal plane facilitates the activation of O2 dissociation and the desorption of H2O during the ORR, which is responsible for the electrocatalyst with a smaller ORR overpotential (∼1.0 eV) that is lower than that of Co-doped graphene by 0.93 eV. Our results suggest that the Co–N co-doped graphene is able to compete against platinum-based electrocatalysts, and the greater efficient electrocatalysts can be realized by carefully optimizing the coupling between transition metal and nonmetallic dopants in the graphene basal plane.