A density functional theory study on oxygen reduction reaction on nitrogen-doped graphene.

Nitrogen (N)-doped carbons reportedly exhibit good electrocatalytic activity for the oxygen reduction reaction (ORR) of fuel cells. This work provides theoretical insights into the ORR mechanism of N-doped graphene by using density functional theory calculations. All possible reaction pathways were investigated, and the transition state of each elementary step was identified. The results showed that OOH reduction was easier than O-OH breaking. OOH reduction followed a direct Eley-Rideal mechanism (the OOH species was in gas phase, but H was chemisorbed on the surface) with a significantly low reaction barrier of 0.09 eV. Pathways for both four-electron and two-electron reductions were possible. The rate-determining step of the two-electron pathway was the reduction of O₂ (formation of OOH), whereas that of the four-electron pathway was the reduction of OH into H₂O. After comparing the barriers of the rate-determining steps of the two pathways, we found that the two-electron pathway was more energetically favored than the four-electron pathway.