Theoretical Investigation on the Reaction Pathways of the Oxygen Reduction Reaction on Graphene Codoped with Manganese and Phosphorus as a Potential Nonprecious Metal Catalyst

Nonprecious‐metal‐doped graphene catalysts have been proposed recently as promising candidates to substitute Pt catalysts for the oxygen reduction reaction (ORR) in fuel cells. We codoped Mn and P in divacancy graphene (MnP x , x =1–4) and we studied the stability and the catalytic activity for the ORR. The calculated formation energy indicates that MnP 2 ‐doped divacancy graphene is energetically the most stable. The MnP 2 moiety and its adjacent six C atoms are catalytically active sites for the ORR. The kinetically most favorable pathway is the hydrogenation of OOH to form O+H 2 O, which is a four‐electron process. The rate‐determining step is the second H 2 O formation, which has an energy barrier of 0.91 eV. The free energy diagrams show that for OOH hydrogenation into O+H 2 O all of the elementary steps are downhill at potentials of 0.0–0.67 V except for the second H 2 O formation.