In this study, a novel type oxygen reduction reaction (ORR) electrocatalyst is explored using density functional theory (DFT); the catalyst consists of transition metal M and heteroatom N4 co-doped in vacancy fullerene (M-N4-C64, M = Fe, Co, and Ni). Mulliken charge analysis shows that the metal center is the reaction site of ORR. PDOS analysis indicates that in M-N4-C64, the interaction between Fe-N4-C64 and the adsorbate is the strongest, followed by Co-N4-C64 and Ni-N4-C64. This is consistent with the calculated adsorption energies. By analyzing and comparing the adsorption energies of ORR intermediates and activation energies and reaction energies of all elemental reactions in M-N4-C64 (M = Fe, Co, and Ni), two favorable ORR electrocatalysts, Fe-N4-C64 and Co-N4-C64, are selected. Both exhibited conduction through the more efficient 4e- reduction pathway. Moreover, PES diagrams indicate that the whole reaction energy variation in the favorable ORR pathways of Fe-N4-C64 and Co-N4-C64 is degressive, which is conducive to positive-going reactions. This study offers worthwhile information for the improvement of cathode materials for fuel cells.
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