Fabrication of a ternary CdS/ZnIn2S4/TiO2 heterojunction for enhancing photoelectrochemical performance: effect of cascading electron-hole transfer

A novel, three-dimensional, ternary CdS/ZnIn2S4/TiO2 heterojunction has been fabricated via a three-step facile hydrothermal method. In this structure, one-dimensional TiO2 nanorods were directly grown on conductive fluorine-doped tin oxide (FTO) substrates. Next, to form a ternary heterojunction of CdS/ZnIn2S4/TiO2, ZnIn2S4 nanosheets were designed on the TiO2 nanorods and sensitized by CdS nanograins. A systematic photoelectrochemical study shows that the photocurrent density of the ternary heterojunction architecture is as high as 1.4 mA cm(-2) at a potential of 0.1 V versus Ag/AgCl (under optimized conditions). A more detailed study shows that the photocurrent density is more than two times higher than that of a single CdS/TiO2 heterojunction (0.615 mA cm(-2)) and three times higher than that of ZnIn2S4/TiO2 (at 0.1 V vs. Ag/AgCl). This excellent photoelectrochemical performance is ascribed to the way that the band structure of TiO2 nanorods synergistically cascades with ZnIn2S4 and CdS, which allows for the absorption of a wider portion of the solar spectrum and improves the effective separation of the generated electron-hole pairs. Electrochemical impedance spectroscopy (EIS) studies also reveal the significant changes in both the interface resistance and the charge transfer resistance of the CdS/ZnIn2S4/TiO2 heterostructure. This can be attributed to the efficient hierarchical cascading that occurs during the electron-hole transfer from the excited CdS to TiO2 through the enlarged interface of ZnIn2S4 upon visible light illumination.