In photocatalytic studies, tetragonal bismuth vanadate (t-BiVO4) is not promising due to its wide band gap. However, according to previous studies, the tetragonal phase is inevitable when the monoclinic bismuth vanadate (m-BiVO4) is modified. Therefore, it is necessary to find ways to improve the photoresponse and photocatalytic ability of t-BiVO4 under visible light. In this study, Yb3+ and Tm3+ co-doped BiVO4 was synthesized by a simple hydrothermal method, and its microstructure, morphology and optical properties were characterized and analyzed by scanning electron microscope, transmission electron microscopy, Brunauer-Emmett-Teller, X-ray diffraction, Raman, X-ray photoelectron spectroscopy, diffuse reflectance spectra, photoluminescence, upconversion luminescence and other means. The results show that BiVO4:Yb3+/Tm3+ (BVYT) has a high content of tetragonal phase (about 80%), showing the characteristics of t-BiVO4. BVYT shows a higher separation efficiency of photogenerated carriers, its transient photocurrent response intensity increased by about 3 times, and the photocatalytic efficiency is significantly improved compare with the undoped m-BiVO4. Under simulated sunlight, BVYT completely degraded methylene blue (MB) solution and rhodamine B solution in 45 and 90 min, respectively, and the reaction rate was significantly improved. BVYT also shows excellent photocatalytic ability under visible light, about 35% of MB solution was degraded within 45 min under visible light irradiation (> 420 nm), this is because Yb3+ effectively promotes the upconversion luminescence of Tm3+ in response to visible light, and the energy cycle mechanism of Yb-Tm-Tm is proposed. Consequently, BiVO4 with high content of tetragonal phase has excellent photoactivity, even exceeding m-BiVO4. This is a novel discovery in the field of photocatalysis, which provides a broader application prospect for BiVO4 in photocatalysis.
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