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The oxygen reduction reaction (ORR) catalytic mechanism and activity on B12N12 and B60N60 nanocages were investigated in detail by density functional theory methods. The calculated results indicate that all the adsorption energies of ORR intermediates on B12N12 are close to those known for the Pt(111) catalyst, implying that it can be an effective catalyst for the ORR, with catalytic properties similar to Pt. A relative energy profile suggests that the ORR process could spontaneously take place on the studied two BN nanocages, with a four-electron reduction mechanism. More importantly, during the entire reduction process, the BN nanocages can provide dual-catalytic sites, especially in the second and third H transfer step, further accelerating the ORR pathways. Thus, the synergistic catalytic effect between B and N atoms is demonstrated to be considerable in BN nanocages.

In this paper, the oxygen reduction reaction (ORR) activities and mechanisms on pristine and doped Si 60 C 60 nanocages were predicted by DFT methods. The calculation results indicate that pristine Si 60 C 60 has a relatively low ORR activity due to its excessive adsorption energies of ORR species when compared with Pt(111) catalyst. However, doping Si 60 C 60 with Co or Ni elements can largely reduce the adsorption energies of ORR species, indicating the enhancement of the catalytic activity. At the same time, all of the changes on reaction energy of ORR steps become downhill in the relative energy landscapes, indicating the spontaneous nature of the ORR. Furthermore, both Co 1 Si 59 C 60 and Ni 1 Si 59 C 60 nanocages can catalyze ORR through two main reaction pathways: one is initiated by the end-on adsorption of O 2 on the top of doped metal site, and will be completed via a H 2 OO dissociation pathway; the other is initiated by the bridge adsorption of O 2 molecule, and will be completed via an OOH dissociation pathway. Based on the calculated data, we conclude that Ni 1 Si 59 C 60 possesses higher ORR activity than Co 1 Si 59 C 60 catalyst.

Summary In the present work, the catalytic activity of metal‐fullerene C58M (M = Mn, Fe, Co, Ni, and Cu) toward oxygen reduction reaction (ORR) and CO oxidation has been explored by detailed density functional theory calculations. Firstly, the binding energy of various ORR species (OOH, O, and OH) on C58M and the corresponding adsorption structures are calculated. The results show that the adsorption strength of any ORR species on C58M follows the order of C58Mn > C58Fe > C58Co > C58Ni > C58Cu and C58Co shows the closest binding energy compared with the Pt(111) surface. Further analysis of the free energy change of ORR indicates that C58Co, C58Ni, and C58Fe have different degrees of catalytic activities, with the calculated free energy change of rate‐determining step of −0.70, −0.32, and −0.04 eV, respectively. On the basis of the above results, the C58Co obviously has the highest ORR activity, with a relatively small overpotential of 0.53 V. In addition, the adsorption free energy of OH can be used as a good descriptor for ORR activity due to the nearly linear relationships between ∆G*OOH, ∆G*O, and ∆G*OH. At last, the catalytic property of C58Co toward CO oxidation reaction is also explored. The calculated results show that CO oxidation on C58Co follows LH mechanism and the rate‐determining step is recognized as *CO + *O2 → *OOCO, with the energy change of −0.13 eV.

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