Toward Improving the Graphene–Semiconductor Composite Photoactivity via the Addition of Metal Ions as Generic Interfacial Mediator

We report a simple and general approach to improve the transfer efficiency of photogenerated charge carriers across the interface between graphene (GR) and semiconductor CdS by introducing a small amount of metal ions (Ca(2+), Cr(3+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) as "mediator" into their interfacial layer matrix, while the intimate interfacial contact between GR and CdS is maintained. This simple strategy can not only significantly improve the visible-light-driven photoactivity of GR-CdS semiconductor composites for targeting selective photoredox reaction, including aerobic oxidation of alcohol and anaerobic reduction of nitro compound, but also drive a balance between the positive effect of GR on retarding the recombination of electron-hole pairs photogenerated from semiconductor and the negative "shielding effect" of GR resulting from the high weight addition of GR. Our current work highlights that the significant issue on improving the photoactivity of GR-semiconductor composites via strengthening interfacial contact is not just a simple issue of tighter connection between GR and the semiconductor, but it is also the optimization of the atomic charge carrier transfer pathway across the interface between GR and the semiconductor.