A simplified method for synthesis of band-structure-controlled (CuIn) xZn 2(1- x) S 2 solid solution photocatalysts with high activity of photocatalytic H 2 evolution under visible-light irradiation

Abstract

(CuIn) x Zn 2(1- x) S 2 ( x = 0.01–0.5) microspheres were prepared by a simple hydrothermal method. They were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–Visible diffuse reflectance spectra (UV–Vis), Raman scattering spectra and Brunauer-Emmett-Teller (BET) surface area measurement. It was found that the (CuIn) x Zn 2(1- x) S 2 samples formed solid solution only in the presence of surfactant cetyltrimethylammonium bromide (CTAB). CTAB enabled the increase of the surface area for the (CuIn) x Zn 2(1- x) S 2 solid solutions. Diffuse reflection spectra of the solid solutions shifted monotonically to long wavelength side as the value of x increased. The photocatalytic H 2 evolution activity under visible-light irradiation of the solid solutions was evaluated. The result showed that the activity depended on their corresponding compositions closely. Ru (1.5 wt%)-loaded (CuIn) 0.2Zn 1.6S 2 showed the highest photocatalytic activity of 198.09 μmol h −1 under visible-light irradiation, and the apparent quantum yield amounted to 15.45% at 420 nm. Furthermore, the density functional theory (DFT) calculations showed that the solid solution with the ration of ZnS and CuInS 2, 6:1, was a direct band gap semiconductor. The valence band consisted of the hybrid orbital of S 3p and Cu 3d and the conduction band consisted of In 5s5p orbital mixed with Zn 4s4p. The energy band structure resulted in the visible-light response of the solid solution, and affected its photocatalytic performance.