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The photocatalytic mineralization of 2-chlorophenol (2-CP) and 2-nitrophenol (2-NP) was investigated using α-Bi₂O₃. The experiments were performed both in complete spectrum and in the visible region (420–800 nm) of the sunlight. The materials were fully characterized by means of UV–vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis and field emission scanning electron microscopy (FESEM). α-Bi₂O₃ showed considerably higher activity for the mineralization of 2-nitrophenol and 2-chlorophenol under natural sunlight exposure, however still appreciable activity was observed in the visible region. Formation of surface nanocomposites Bi₂O_4−x–Bi₂O₃ was observed under sunlight irradiation due to the presence of UV light. The sunlight exposed Bi₂O₃, i.e. Bi₂O_4−x–Bi₂O₃ composite, showed …