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.