Solar Light-Induced Methylene Blue Removal over TiO/AC Composites and Photocatalytic Regeneration.

TiO-containing photocatalysts, which combine TiO with carbon-based materials, are promising materials for wastewater treatment due to synergistic photodegradation and adsorption phenomena. In this work, TiO/AC composites were produced by the in situ immobilization of TiO nanoparticles over activated carbon (AC) derived from spent coffee grains, using different TiO/AC proportions. The TiO/AC composites were tested as adsorbents (dark) and as photocatalysts in a combined adsorption+photocatalytic process (solar irradiation) for methylene blue (MB) removal from ultrapure water, and from a secondary effluent (SecEf) of an urban wastewater treatment plant. All the materials were characterized by XRD (X-ray powder diffraction), N adsorption-desorption isotherms at -196 °C, SEM (scanning electron microscopy), UV-Vis diffuse reflectance, FTIR (Fourier-transform infrared spectroscopy), TPD (temperature programmed desorption), XPS (X-ray photoelectron spectroscopy) and TGA (thermogravimetric analysis). The TiAC60 (60% C) composite presented the lowest band gap (1.84 eV), while, for TiAC29 (29% C), the value was close to that of bare TiO (3.18 vs. 3.17 eV). Regardless of the material, the solar irradiation improved the percentage of MB discolouration when compared to adsorption in dark conditions. In the case of simultaneous adsorption+photocatalytic assays performed in ultrapure water, TiAC29 presented the fastest MB removal. Nevertheless, both TiAC29 and TiAC60 led to excellent MB removal percentages (96.1-98.1%). UV-induced photoregeneration was a promising strategy to recover the adsorption capacity of the materials, especially for TiAC60 and AC (>95%). When the assays were performed in SecEf, all the materials promoted discolouration percentages close to those obtained in ultrapure water. The bulk water parameters revealed that TiAC60 allowed the removal of a higher amount of MB, associated with the overall improvement of the SecEf quality.