Fabrication of Large‐Scale Hierarchical ZnO Hollow Spheroids for Hydrophobicity and Photocatalysis

Abstract

We report here the preparation of a crystalline, pure hexagonal phase of ZnO as hollow 500-800 nm spheroids in the presence of organic bases, such as pyridine, using zinc acetate as the precursor salt. The spheroids exhibit unique 3D hierarchical architectures, like cocoons, and demonstrate improved superhydrophobic (water contact angle, 150 degrees) character due to the inherited air-trapped capillarity within the cocoon structure. The simple synthetic strategy used in this process is modified hydrothermolysis (MHT), which represents a general approach and may contribute to the formation mechanism of the hollow nanostructures with highly improved porosity. Depending on the concentration of the precursor salt, it has been possible to cover glass plates or the inner wall of a reaction vessel with ZnO nanocrystals. A low salt concentration (<0.01 M) allows the easy preparation of a superhydrophobic glass surface, whereas a high salt concentration (>0.01 M) results in the precipitation of cocoons at the bottom of the reaction vessel as a solid mass together with a deposited thin film of ZnO nanocrystals covering the inner wall of the glass vessel. The thickness of the film successively grows through repetitive hydrothermolysis processes for which a low salt concentration (<0.01 M) was employed. Because of the hollow cocoon-like morphology, the surface area of the film is greatly increased, which makes it accessible for functionalization by incoming substrates from both sides (internally and externally) and helps to drive a competent photocatalytic dye degradation pathway. The heterocyclic base pyridine exclusively develops cocoons. Thus, the mechanism of self-aggregation of ZnO nanocrystals under MHT reaction conditions has been studied and the characterization of the compounds has been supported with physical measurements.