Exciton quenching due to copper diffusion limits the photocatalytic activity of CdS/Cu₂S nanorod heterostructures

The formation of donor/acceptor junctions in hybrid nanomaterials is predicted to enhance photocatalytic activity as compared to single-component semiconductor systems. Specifically, nanomaterials containing a junction of n-type cadmium sulfide (CdS) and p-type copper sulfide (Cu₂S) formed via cation exchange have been proposed as potential photocatalysts for reactions such as water splitting. Herein, we study the elemental distribution of Cu within these nanostructures using analytical transmission electron microscopy techniques. The resulting effects of this elemental distribution on photocatalytic activity and charge dynamics were further studied using a model photoreduction reaction and transient absorption spectroscopy. We find that copper diffusion in the hybrid nanostructure quenches the exciton lifetime and results in low photocatalytic activity; however, this effect can be partially mitigated via selective extraction. These results provide a deeper understanding of the physical processes within these hybrid nanostructures and will lead to more rational design of photocatalyst materials.