Electronic structures of the MoS 2 /TiO 2 (anatase) heterojunction: influence of physical and chemical modifications at the 2D- or 1D-interfaces.

To tackle the challenge of CO 2 photoreduction, semiconducting layered transition metal dichalcogenides like MoS 2 have attracted much attention due to their tunable 2D nano-structures. By using advanced periodic density functional theory calculations (HSE06 functional), we provide a systematic quantification of the optoelectronic properties of various interfacial heterostructures composed of 2H-MoS 2 and anatase TiO 2 . We systematically determine the band gaps, and conduction band (CB) and valence band (VB) positions to figure out the nature of the heterojunction. Two main surface orientations of anatase TiO 2 particles, (101) and (001), are considered with 2D-MoS 2 nanosheets or nanoribbons forming either a 2D physical (van der Waals) or through a 1D chemical interface. The possibility to chemically modify the MoS 2 /TiO 2 interface, either by sulfidation or hydration, and its effect on the electronic structure are deeply investigated. These modifications in the heterostructure lead to important changes in the electronic properties and charge transfer between the two materials which impact both photon absorption properties and charge carrier dynamics suspected to influence in turn the photocatalytic activity. While a type I hetrojunction is found for the 1D chemical interface, a type II heterojunction with appropriate CB/VB positions for CO 2 reduction and H 2 O oxidation is identified for the 2D physical interface which could lead to the targeted Z-scheme mechanism with strong potential interest in photocatalysis applications.