Composition effect on the carrier dynamics and catalytic performance of CuInS/ZnS quantum dots for light driven hydrogen generation.

Water soluble CuInS/ZnS quantum dots (QDs) represent one of the most promising single component photocatalysts for the hydrogen evolution reaction (HER). In this work, we report the effect of cation composition in CuInS/ZnS QDs on the carrier relaxation and charge separation dynamics as well as their photocatalytic performance for the HER. With decreasing Cu to In ratio (increasing Cu deficiency), we observed slightly faster electron trapping and carrier recombination but significantly improved photocatalytic activity for the HER. This can be attributed to the enhanced electron transfer (ET) from the sacrificial donor to CuInS/ZnS QDs resulting from the lower valence band (larger driving force for ET) of QDs with higher Cu deficiency. This work not only provides important insight into the mechanistic origins of the HER but also demonstrated that altering the composition in CuInS/ZnS QDs is a viable approach to further improve their performance for solar to fuel conversion.