A Novel Aqueous Process for Preparation of Crystal Form-Controlled and Highly Crystalline BiVO₄ Powder from Layered Vanadates at Room Temperature and Its Photocatalytic and Photophysical Properties

BiVO4 photocatalysts for O2 evolution, which work under visible light irradiation, were prepared by an aqueous process. The BiVO4 photocatalysts were obtained by the reaction of layered potassium vanadate powder (KV3O8 and K3V5O14) with Bi(NO3)3 for 3 days in aqueous media at room temperature. Highly crystalline monoclinic and tetragonal BiVO4 were selectively synthesized by changing the ratio of vanadium to bismuth in the starting materials. X-ray diffraction and scanning electron microscopy measurements showed that the monoclinic BiVO4 was formed via a tetragonal BiVO4 intermediate. Tetragonal BiVO4 with a 2.9 eV band gap mainly possessed an ultraviolet absorption band while monoclinic BiVO4 with a 2.4 eV band gap had a characteristic visible light absorption band in addition to the UV band. The UV bands observed in the tetragonal and monoclinic BiVO4 were assigned to the band transition from O2p to V3d whereas the visible light absorption was due to the transition from a valence band formed by Bi6s or a hybrid orbital of Bi6s and O2p to a conduction band of V3d. The photocatalytic activity for O2 evolution from an aqueous silver nitrate solution under UV irradiation (300 < λ < 380 nm) on the tetragonal BiVO4 was comparable to that on the monoclinic BiVO4. The monoclinic BiVO4 also showed the high photocatalytic activity for the O2 evolution under visible light irradiation (λ > 420 nm). When the monoclinic BiVO4 was calcined at 700−800 K the activity was increased. The activity of this monoclinic BiVO4 was much higher than that of BiVO4 prepared by a conventional solid-state reaction. The quantum yield at 450 nm for the O2 evolution on the monoclinic BiVO4 was 9%.