Size Optimization of a N-Doped Graphene Nanocluster for the Oxygen Reduction Reaction

[Image: see text] N-Doped graphene nanoclusters (N-GNCs) are promising electrocatalysts for the oxygen reduction reaction (ORR) at the cathode of fuel cells. In this study, the dependence of the ORR activity on the size of N-GNCs was investigated using first-principles calculations based on density functional theory. The maximum electrode potential (U(Max)) was estimated from the free energy of the reaction intermediates of the ORR. U(Max) was predicted to show a volcanic trend with respect to the cluster size. The results suggest that C(215)H(36)N with a radius of 13.6 Å is the best candidate for ORRs and is better than platinum in terms of U(Max). The volcano-shaped plot of U(Max) is attributed to the switch of the reaction step that determines U(Max), which is caused by the destabilization of reaction intermediates. Such changes in the stability of the intermediates can be explained by the decrease in the local density of states at the reaction site, which is due to the development of the so-called edge state at the zigzag edge. The establishment of experimental techniques to control the cluster size and doping position will be the key to superior catalyst preparation in the future.