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Issue 26, 2018
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Modulating the oxygen reduction activity of heteroatom-doped carbon catalysts via the triple effect: charge, spin density and ligand effect

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Abstract

To enhance the intrinsic activity of and increase the number of active sites in heteroatom-doped graphene (doped-G), it is necessary to recognize the origin of its catalytic activity, and to search for a universal definition and description of the different active sites. Herein, we report an evaluation of a series of heteroatom-doped graphene materials as oxygen reduction reaction (ORR) catalysts with the aid of density functional theory (DFT) calculations. The results of the DFT calculations indicate that the intrinsic catalytic activity and the ORR mechanism depend on the triple effect, that is, the charge, the spin density and the coordinate state (ligand effect) of the carbon sites. The contribution of the above effects towards increasing the binding energies of *OOH or *OH has the following order: negative charge effect < positive charge effect < low spin effect < ligand effect < high spin effect. For nonmetallic single-heteroatom-doped-G, the triple effect separately activates the carbon sites around the doped atom. On each single carbon active site, only the end-on adsorption of *OOH is preferred, leading to the ORR following the associative mechanism, which has an intrinsic limitation in its overpotential of 0.44 V. However, for metal-doped-G and dual-heteroatom-doped-G, the triple effect can activate double carbon sites, and lead to the ORR following the dissociative mechanism, which breaks through the activity limitation of the associative mechanism, and further enhances the catalytic activity for the ORR. With comprehensive theoretical calculation, we conclude that it is possible for the heteroatom-doped-G, if well-modulated via the triple effect, to exceed Pt-based materials in catalysis of the ORR.

Graphical abstract: Modulating the oxygen reduction activity of heteroatom-doped carbon catalysts via the triple effect: charge, spin density and ligand effect

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Publication details

The article was received on 20 Apr 2018, accepted on 24 May 2018 and first published on 31 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01801D
Citation: Chem. Sci., 2018,9, 5795-5804
  • Open access: Creative Commons BY-NC license
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    Modulating the oxygen reduction activity of heteroatom-doped carbon catalysts via the triple effect: charge, spin density and ligand effect

    N. Yang, L. Li, J. Li, W. Ding and Z. Wei, Chem. Sci., 2018, 9, 5795
    DOI: 10.1039/C8SC01801D

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

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