Cobalt or Nickel Doped SiC Nanocages as Efficient Electrocatalyst for Oxygen Reduction Reaction: A Computational Prediction

In this paper, the oxygen reduction reaction (ORR) activities and mechanisms on pristine and doped Si60C60 nanocages were predicted by DFT methods. The calculation results indicate that pristine Si60C60 has a relatively low ORR activity due to its excessive adsorption energies of ORR species when compared with Pt(111) catalyst. However, doping Si60C60 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 Co1Si59C60 and Ni1Si59C60 nanocages can catalyze ORR through two main reaction pathways: one is initiated by the end-on adsorption of O2 on the top of doped metal site, and will be completed via a H2OO dissociation pathway; the other is initiated by the bridge adsorption of O2 molecule, and will be completed via an OOH dissociation pathway. Based on the calculated data, we conclude that Ni1Si59C60 possesses higher ORR activity than Co1Si59C60 catalyst.