Excited-State Properties of CuInP2S6 Monolayer as Photocatalyst for Water Splitting

In recent years, two-dimensional (2D) materials of ferroelectricity have been illustrated to have great potential in solar energy conversion processes such as photocatalytic water splitting, although the optical properties of such materials are rarely discussed. In combination with the first-principles calculations, many-body Green's function method was used to obtain the excited-state properties of the representative CuInP2S6 to unravel the ingredients affecting the photocatalytic behavior. In particular, quasiparticle (QP) band gap correction and bound exciton binding energy are 1.25/1.38 and 0.93/0.87 eV for paraelectric/ferroelectric CuInP2S6, respectively. In addition to facilitating the charge carrier recombination, here we emphasize that the large exciton binding energy reduces the reduction potential of the photoexcited electrons. In bilayer structures, the improved photocatalytic performance should be ascribed to the type-II band alignment and large band edge offsets (0.44 and 0.33 eV for CuInP2S6), rather than the increased light absorption due to the reduced band gap.