A reverse-micelle sol-gel method was chosen for the preparation of Fe-doped TiO2 samples that were employed in the photodegradation of the crystal violet dye under visible light irradiation in a batch reactor. The dopant amount was varied to assess the optimal photocatalyst composition towards the target dye degradation. The photocatalysts were characterized through a multi-technique approach, envisaging XRPD and QPA as obtained by Rietveld refinement, FE-SEM analysis, DR UV-vis spectroscopy, N2 adsorption/desorption isotherms measurement at -196 °C, ζ-potential measurement, and XPS analysis. The physical-chemical characterization showed that the adopted synthesis method allows obtaining NPs with uniform shape and size and promotes the introduction of Fe into the titania matrix, finally affecting the relative amounts of the three occurring polymorphs of TiO2 (anatase, rutile and brookite). By increasing the Fe content, the band gap energy decreases from 3.13 eV (with undoped TiO2) to 2.65 eV (with both 2.5 and 3.5 wt.% nominal Fe contents). At higher Fe content, surface Fe oxo-hydroxide species occur, as shown by DR UV-vis and XP spectroscopies. All the Fe-doped TiO2 photocatalysts were active in the degradation and mineralization of the target dye, showing a TOC removal higher than the undoped sample. The photoactivity under visible light was ascribed both to the band-gap reduction (as confirmed by phenol photodegradation) and to dye sensitization of the photocatalyst surface (as confirmed by photocatalytic tests carried out using different visible-emission spectra LEDs). The main reactive species involved in the dye degradation were determined to be positive holes.
Keywords: Fe-doped TiO2; TiO2 polymorphs; brookite; crystal violet; non-ionic surfactant; photocatalysis; visible light.