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A DFT study of the ORR on M–N3 (M = Mn, Fe, Co, Ni, or Cu) co-doped graphene with moiety-patched defects

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Abstract

Graphene-based nanomaterials have potential as electrocatalysts for the oxygen reduction reaction (ORR) due to their unique physical and chemical properties. In this study, the mechanism of the ORR on M–N3 (M = Mn, Fe, Co, Ni, Cu) co-doped graphene with defects is investigated using dispersion-corrected density functional theory (DFT) computations. The results show that Mn-N3-Gra, Co-N3-Gra, and Ni-N3-Gra are more thermodynamically stable than Fe-N3-Gra and Cu-N3-Gra. Only Mn-N3-Gra exhibits some catalytic activity at pH < 11.327 while M-N3-Gra (M = Fe, Co, Ni, and Cu) are not suitable ORR catalysts. Under acidic conditions at pH = 0, the overpotentials of the optimal 4e− catalytic path are 0.56 V, 0.849 V, and 0.381 V for Mn-N3-Gra, Co-N3-Gra, and Ni-N3-Gra, respectively. These values are consistent with experimental results. These results indicate that Ni-N3-Gra, the optimal catalyst in this study, is comparable with Pt. The M-N3-Gra (M = Fe, Cu) catalysts cannot promote ORR under acid conditions.

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Funding

The authors acknowledge the financial support of the KEY LABORATORY OF METAL CELL OF SICHUAN PROVINCE. The calculations are performed on resources provided by the High Performance Computing Center of Tianjin University and those provided by the School of Chemical Engineering and Technology in Tianjin University.

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  1. School of the Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Qiangqiang Gao

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Gao, Q. A DFT study of the ORR on M–N3 (M = Mn, Fe, Co, Ni, or Cu) co-doped graphene with moiety-patched defects. Ionics 26, 2453–2465 (2020). https://doi.org/10.1007/s11581-019-03376-9

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  • DOI: https://doi.org/10.1007/s11581-019-03376-9

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