Probing π-π stacking modulation of g-C3N4/graphene heterojunctions and corresponding role of graphene on photocatalytic activity

[Display omitted] The photoelectrochemical properties of g-C3N4 sheet are modified by the π-π stacking interaction with graphene, and the corresponding role of graphene on the surface chemical reactions is investigated by density functional theory. The calculated cohesive energies and the lattice mismatch energies indicate that g-C3N4 and graphene are in parallel contact and can form a stable heterojunction. According to our calculated energy band structures and work functions of g-C3N4/graphene heterojunctions, the band edge modulations by graphene are discussed and corresponding photoinduced charge transfer processes are analyzed in detail. It is found that the incorporating of graphene into g-C3N4 facilitates the separation of photoinduced e–/h+ pairs and the oxidation capacity enhancement of the photoinduced holes with the downshifting of the valence band edge of g-C3N4 layer. It is identified that the inhomogeneous onsite energies between interlayer and the band edge modulations are induced by the inhomogeneous charge redistribution between interlayer caused by graphene. Further, the initial dynamic reaction processes of oxygen atoms in g-C3N4/graphene heterojunctions also confirm the significant role of graphene on the surface chemical reactions.