Removal of tetracycline by BiOBr microspheres with oxygen vacancies: Combination of adsorption and photocatalysis

Oxygen vacancy-containing BiOBr microspheres with dual functions of adsorption-photocatalysis were synthesized by a simple solvothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR) and UV-vis diffuse reflectance spectroscopy (DRS). BiOBr microspheres with oxygen vacancies exhibited a higher adsorptive and photocatalytic activity for the removal of tetracycline (TC) than that of defect-deficient BiOBr microspheres. After adsorption for 30 min and visible light irradiation for 90 min, about 94% of TC was removed by oxygen vacancy-containing BiOBr microspheres, and TC removal efficiency performed effectively in a wide pH range from 3.1 to 11.00. Almost all inorganic anions, such as Cl-, SO2 - 4, PO3 - 4, CO2 - 3and NO - 3, inhibited the removal of TC by BiOBr microspheres and their inhibition effects followed the order of PO3 - 4 > SO2- 4 > CO2- 3 > Cl- > NO - 3. The surface hydroxyl groups had no effect on TC adsorption, and the adsorption of TC on BiOBr was mainly through the anion exchange process. The existence of oxygen vacancies facilitated the generation of superoxide radicals (O-2(-center dot)) which were the dominant reactive oxygen species for TC degradation in BiOBr suspension. The adsorptive and photocatalytic performance of oxygen vacancy-containing BiOBr decreased to different degrees after three cycles mainly due to the formation of surface complex.