Engineering Charge Transfer Characteristics in Hierarchical Cu₂S QDs @ ZnO Nanoneedles with p⁻n Heterojunctions: Towards Highly Efficient and Recyclable Photocatalysts.

Equipped with staggered gap p-n heterojunctions, a new paradigm of photocatalysts based on hierarchically structured nano-match-shaped heterojunctions (NMSHs) Cu₂S quantum dots (QDs)@ZnO nanoneedles (NNs) are successfully developed via engineering the successive ionic layer adsorption and reaction (SILAR). Under UV and visible light illumination, the photocatalytic characteristics of Cu₂S@ZnO heterojunctions with different loading amounts of Cu₂S QDs are evaluated by the corresponding photocatalytic degradation of rhodamine B (RhB) aqueous solution. The results elaborate that the optimized samples (S3 serial specimens with six cycles of SILAR reaction) by means of tailored the band diagram exhibit appreciable improvement of photocatalytic activities among all synthesized samples, attributing to the sensitization of a proper amount of Cu₂S QDs. Such developed architecture not only could form p⁻n junctions with ZnO nanoneedles to facilitate the separation of photo-generated carries but also interact with the surface defects of ZnO NNs to reduce the electron and hole recombination probability. Moreover, the existence of Cu₂S QDs could also extend the light absorption to improve the utilization rate of sunlight. Importantly, under UV light S3 samples demonstrate the remarkably enhanced RhB degradation efficiency, which is clearly testified upon the charge transfer mechanism discussions and evaluations in the present work. Further supplementary investigations illustrate that the developed nanoscale Cu₂S@ZnO heterostructures also possess an excellent photo-stability during our extensive recycling photocatalytic experiments, promising for a wide range of highly efficient and sustainably recyclable photocatalysts applications.