▎ 摘　　要

The goal of this study is to provide insight into the mechanism of the oxygen reduction reaction (ORR) on N-doped graphene surfaces. Using density functional theory and a computational hydrogen electrode model, we studied the energetics of the ORR intermediates, the effect of the position of the reaction site, and the effect of the position of the N modification relative to the active site on model graphene surfaces containing one or two N atoms. We found that scaling relations can be derived for N-doped graphenes as well, but the multiplicity of the surface should be taken into account. On the basis of the scaling relations between intermediates OOH* and OH*, the minimal overpotential is 0.33 V. Analysis of the data showed that N atoms in the meta position usually decrease the adsorption energy, but those in the ortho position aid the adsorption. The outer position on the zigzag edge of the graphene sheet also promotes the adsorption of oxygenated species, while the inner position hinders it. Looking at the most effective active sites, our analysis shows that the minimal overpotential can be approached with various doping arrangements, which also explains the contradicting results in the literature. The dissociative pathway was also investigated, but we found only one possible active site; therefore, this pathway is not really viable. However, routes not preferred thermodynamically pose the possibility of breaking the theoretical limit of the overpotential of the associative pathway.