Enhanced Visible‐Light Hydrogen‐Production Activity of Copper‐Modified ZnxCd1−xS

Copper modification is an efficient way to enhance the photocatalytic activity of ZnS-based materials; however, the mechanisms of Cu(2+) surface and bulk modifications for improving the activity are quite different. In this work, two different synthetic pathways were devised to prepare surface and bulk Cu(2+)-modified Znx Cd1-x S photocatalysts through cation-exchange and coprecipitation methods, respectively. Different Cu(2+) modifications brought different effects on the phase structure, morphology, surface area, optical property, as well as the photocatalytic H2-production activity of the final products. The optimized Cu(2+)-surface-modified Znx Cd1-x S photocatalyst has a high H2-production rate of 4638.5 μmolh(-1) g(-1) and an apparent quantum efficiency of 20.9% at 420 nm, exceeding that of Cu(2+)-bulk-modified catalyst at the same copper content. Cu(2+) surface modification not only brings a new electron-transferring pathway (interfacial charge transfer), but also produces new surface active sites for H2 evolution, reducing the recombination rate of photogenerated charge carriers.