Trace Cu+-dominated band structure engineering in CuxIn0.25ZnSy for promoting photocatalytic H2 evolution

As an attractive semiconductor photocatalyst, (CuInS2)x-(ZnS)y has been intensively studied in photocatalysis, due to its unique layered structure and stability. Here, we synthesized a series of CuxIn0.25ZnSy photocatalysts with different trace Cu+-dominated ratios. The results show that doping with Cu+ ions leads to an increase in the valence state of In and the formation of a distorted S structure, simultaneously inducing a decrease in the semiconductor bandgap. When the doping amount of Cu+ ions is 0.04 atomic ratio to Zn, the optimized Cu0.04In0.25ZnSy photocatalyst with a bandgap of 2.16 eV shows the highest catalytic hydrogen evolution activity (191.4 μmol.h-1). Subsequently, among the common cocatalysts, Rh loaded Cu0.04In0.25ZnSy gives the highest activity of 1189.8 μmol·h-1, corresponding to an apparent quantum efficiency of 49.11 % at 420 nm. Moreover, the internal mechanism of photogenerated carrier transfer between semiconductors and different cocatalysts is analyzed by the band bending phenomenon.