Removal of hexavalent chromium from water by Z-scheme photocatalysis using TiO2 (rutile) nanorods loaded with Au core–Cu2O shell particles

All-solid-state Z-scheme photocatalysts, containing Cu₂O, TiO₂ (rutile), and Au as the electron mediator, were prepared and applied to the reduction of Cr(VI) in aqueous solutions. The Cu₂O–Au–TiO₂ composites were prepared by loading Au core–Cu₂O shell hemisphere particles on TiO₂ (rutile) nanorods using a two-step photocatalytic deposition process. Under ultraviolet–visible (UV–vis) light illumination, the Cu₂O–Au–TiO₂ composites exhibited higher photocatalytic Cr(VI) reduction activities than those exhibited by single TiO₂ (rutile) and Cu₂O. In this reaction, a precipitate containing Cr, which was considered to be Cr(OH)₃, was deposited site-selectively on the Au core–Cu₂O shell particles of the composites, indicating that the reduction site of the composite was Cu₂O, and the reaction proceeded according to the Z-scheme. The Cu₂O–Au–TiO₂ composites also exhibited photocatalytic activity under visible light illumination. The oxidation state of Cu in the Cu₂O–Au–TiO₂ composite gradually changed from Cu(I) to Cu(II) during the photocatalytic Cr(VI) reduction. However the composite maintained its high photocatalytic performance even after oxidation. The role of Au in the Cu₂O–Au–TiO₂ composite was examined by comparing the properties of the Cu₂O–Au–TiO₂ composite with those of the Cu₂O–TiO₂ composite prepared via direct Cu₂O deposition on TiO₂.