Abstract
Nanostructured hybrid heterojunctions have been studied widely for photocatalytic applications due to their superior optical and structural properties. In this work, the impact of angstrom thick atomic layer deposited (ALD) ZnO shell layer on photocatalytic activity (PCA) of hydrothermal grown single crystalline TiO2 nanowires (NWs) is systematically explored. We showed that a single cycle of ALD ZnO layer wrapped around TiO2 NWs, considerably boosts the PCA of the heterostructure. Subsequent cycles, however, gradually hinder the photocatalytic activity (PCA) of the TiO2 NWs. Various structural, optical, and transient characterizations are employed to scrutinize this unprecedented change. We show that a single atomic layer of ZnO shell not only increases light harvesting capability of the heterostructure via extension of the absorption toward visible wavelengths, but also mitigates recombination probability of carriers through reduction of surface defects density and introduction of proper charge separation along the core-shell interface. Furthermore, the ultrathin ZnO shell layer allows a strong contribution of the core (TiO2) valence band holes through tunneling across the ultrathin interface. All mechanisms responsible for this enhanced PCA of heterostructure are elucidated and corresponding models are proposed.