Charge Carriers Cascade in a Ternary TiO2/TiO2/ZnS Heterojunction: A DFT Study

Composite materials whose band alignment induces a favorable separation of photogenerated electrons and holes often reveal a stronger photocatalytic activity compared to their separate components. As shown by experiments, titania composites display a heterojunction between the anatase (101)‐(001) surfaces, where the former stabilizes electrons and the latter the holes. In principle, an even more efficient carriers separation is achieved if a third component with high hole‐stabilizing capability, ZnS(110), is growth on anatase (001). However, even though this ternary TiO2/TiO2/ZnS composite material displays good photoactivity, it does not overperform the TiO2/TiO2 one. In this paper an explanation of this evidence is provided by means of periodic hybrid DFT calculations, showing how Coulomb forces play a role against the separation of charge carriers predicted based on the relative energy of the band edges. This highlights the necessity to explicitly account for structural and electronic junction's effects, as well as charge carriers’ localization. Getting the band back together: In the bottom is reported the band alignment of three independent units, TiO2 (101), TiO2 (001), ZnS (110). In the top is reported the favorable charge‐carriers location, while the further migration of the e− increases the energy of the system.