Novel Bi₂W₂O₉ and Bi₂Mo₂O₉ with irregular polyhedron structure were successfully synthesized by a hydrothermal method. Compared to ordinary Bi₂WO₆ and Bi₂MoO₆, the modified structure of Bi₂W₂O₉ and Bi₂Mo₂O₉ were observed, which led to an enhancement of photocatalytic performance. To investigate the possible mechanism of enhancing photocatalytic efficiency, the crystal structure, morphology, elemental composition, and optical properties of Bi₂WO₆, Bi₂MO₆, Bi₂W₂O₉, and Bi₂Mo₂O₉ were examined. UV-Vis diffuse reflectance spectroscopy revealed the visible-light absorption ability of Bi₂WO₆, Bi₂MO₆, Bi₂W₂O₉, and Bi₂Mo₂O₉. Photoluminescence (PL) and photocurrent indicated that Bi₂W₂O₉ and Bi₂Mo₂O₉ pose an enhanced ability of photogenerated electron–hole pairs separation. Radical trapping experiments revealed that photogenerated holes and superoxide radicals were the main active species. It can be conjectured that the promoted photocatalytic performance related to the modified structure, and a possible mechanism was discussed in detail.

The construction of semiconductor heterojunction photocatalysts that improve the separation and transfer of photoinduced charge carriers is an effective and widely employed strategy to boost photocatalytic performance. Herein, we have successfully constructed a CdS/Ag/Bi₂WO₆ Z-scheme heterojunction with an Ag-bridge as an effective charge transfer channel by a facile process. The heterostructure consists of both CdS and Ag nanoparticles anchored on the surface of Bi₂WO₆ nanosheets. The photocatalytic efficiency of the CdS/Ag/Bi₂WO₆ system was studied by the decontamination of tetracycline (TC) and Rhodamine B (RhB) under visible light irradiation (λ ≥ 420). The results exhibited that CdS/Ag/Bi₂WO₆ shows markedly higher photocatalytic performance than that of CdS, Bi₂WO₆, Ag/Bi₂WO₆, and CdS/Bi₂WO₆. The trapping experiment results verified that the ^•O₂⁻ and h⁺ radicals are the key active species. The results of photoluminescence spectral analysis and photocurrent responses indicated that the CdS/Ag/Bi₂WO₆ heterojunctions exhibit exceptional efficiency in separating and transferring photoinduced electron−hole pairs. Based on a series of characterization results, the boosted photocatalytic activity of the CdS/Ag/Bi₂WO₆ system is mostly due to the successful formation of the Ag-bridged Z-scheme heterojunction; these can not only inhibit the recombination rate of photoinduced charge carriers but also possess a splendid redox capacity. The work provides a way for designing a Z-scheme photocatalytic system based on Ag-bridged for boosting photocatalytic performance.