Synthesis of TiO2@WO3/Au Nanocomposite Hollow Spheres with Controllable Size and High Visible-Light-Driven Photocatalytic Activity

A new nanocomposite was reported as a good-performance photocatalyst, i.e., double-shelled, positively and negatively charged, nanostructured hollow spheres with supported Au nanoparticles (NPs). TiO2, WO3, and Au NPs were coated successively onto the functionalized polystyrene (PS) template spheres. The as-synthesized product PS@TiO2@WO3/Au nanocomposites were calcined at elevated temperature and then intact double-shelled TiO2@WO3/Au hollow spheres were obtained. The dispersity, morphology, size, and lattice of TiO2@WO3/Au hollow spheres were investigated by SEM and TEM. The presence of TiO2 hollow sphere and WO3/Au shell was proved by HAADF-STEM and XRD images. The photodegradation activity for rhodamine B and trimesic acid (i.e., color and colorless aromatic pollutants) in decreasing order were TiO2@WO3/Au, TiO2–WO3, P25. Under visible-light irradiation, the photodegradation rate of rhodamine B and trimesic acid for TiO2@WO3/Au was 94% and 95%, respectively, which exhibited a significant increase of 62% and 80% as compared with P25. The synergistic effect of coupling TiO2 hollow spheres with WO3 shell and Au NPs on photocatalytic performance was proved by this article. First, Au NPs deposited in WO3 shell and loaded on TiO2 shell separately act as electron trap site and surface plasmon resonance-sensitizer, respectively, and hence the photogenerated electron–hole separation rate was improved. Second, the visible-light absorption of TiO2 hollow spheres was increased by the coexistence of WO3 and Au and unique hierarchical mesoporous architectures of TiO2@WO3/Au. Finally, the surface charge of TiO2@WO3/Au and rhodamine B was negative and positive, respectively, the affinity between them could be improved by electrical attractions, and then the major bottleneck in heterogeneous photocatalysis (i.e., poor affinity between pollutants and photocatalyst) could be broken. The optimal hollow sphere size of TiO2@WO3/Au was 450 nm, which was proved by the photodegradation of aromatic pollutants and photoreduction of Cr(VI).