Selective Preparation of Monoclinic and Tetragonal BiVO₄with Scheelite Structure and Their Photocatalytic Properties

BiVO4 powder with scheelite structure was obtained by hydrolyzing a nitric acid solution of Bi(NO3)3 and Na3VO4 with bases (Na2CO3 and NaHCO3) at room temperature. Tetragonal BiVO4 of a high-temperature form was obtained after 4.5 h of preparation time while monoclinic BiVO4 was done after 46 h. Although the structure and the band gap of tetragonal BiVO4 with scheelite structure were similar to those of monoclinic BiVO4, the photocatalytic activity of the tetragonal BiVO4 for O2 evolution from an aqueous AgNO3 solution under visible light irradiation was negligible. In contrast, the monoclinic BiVO4 showed high photocatalytic activity. Distortion of a Bi−O polyhedron by a 6s2 lone pair of Bi3+ plays an important role for high photocatalytic activity of the monoclinic BiVO4 under visible light irradiation.