Electronic structure of aqueous two-dimensional photocatalyst

The electronic structure, in particular the band edge position, of photocatalyst in presence of water is critical for photocatalytic water splitting. We propose a direct and systematic density functional theory (DFT) scheme to quantitatively predict band edge shifts and their microscopic origins for aqueous 2D photocatalyst, where thousands of atoms or more are able to be involved. This scheme is indispensable to correctly calculate the electronic structure of 2D photocatalyst in the presence of water, which is demonstrated in aqueous MoS2, GaS, InSe, GaSe and InS. It is found that the band edge of 2D photocatalysts are not rigidly shifted due to water as reported in previous studies of aqueous systems. Specifically, the CBM shift is quantitatively explained by geometric deformation, water dipole and charge redistribution effect while the fourth effect, i.e., interfacial chemical contact, is revealed in the VBM shift. Moreover, the revealed upshift of CBM in aqueous MoS2 should thermodynamically help carriers to participate in hydrogen evolution reaction (HER), which underpin the reported experimental findings that MoS2 is an efficient HER photocatalyst. Our work paves the way to design 2D materials in general as low-cost and high-efficiency photocatalysts.

Automated summary

The study introduces a DFT scheme to quantitatively predict band edge shifts and origins in aqueous 2D photocatalysts, revealing that the band edges are not rigidly shifted and explaining the phenomena through geometric deformation, water dipole, and charge redistribution effects. The upshift of CBM in aqueous MoS2 is found to thermodynamically assist carriers in the hydrogen evolution reaction, supporting its efficiency as a photocatalyst in experiments.