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.

Fe-doped titania photocatalysts (with 1, 2.5, and 3.5 wt. % Fe nominal content), showing photocatalytic activity under visible light, were prepared by a soft-template assisted sol–gel approach in the presence of the triblock copolymer Pluronic P123. An undoped TiO₂ photocatalyst was also prepared for comparison. The photocatalysts were characterized by means of X-ray powder Diffraction (XRPD), Quantitative Phase Analysis as obtained by Rietveld refinement, Diffuse Reflectance (DR) UV−Vis spectroscopy, N₂ adsorption/desorption at −196 °C, electrophoretic mobility in water (ζ-potential), and X-ray photoelectron spectroscopy (XPS). The physico-chemical characterization showed that all the samples were 100% anatase phase and that iron was present both in the bulk and at the surface of the Fe-doped TiO₂. Indeed, the band gap energy (Eg) decreases with the Fe content, with Tauc’s plot determined values ranging from 3.35 (undoped TiO₂) to 2.70 eV (3.5 wt. % Fe). Notwithstanding the obtained Eg values, the photocatalytic activity results under visible light highlighted that the optimal Fe content was equal to 2.5 wt. % (Tauc’s plot determined Eg = 2.74 eV). With the optimized photocatalyst and in selected operating conditions, under visible light it was possible to achieve 90% AO7 discoloration together with a TOC removal of 40% after 180 min. The kinetic behavior of the photocatalyst was also analyzed. Moreover, the tests in the presence of three different scavengers revealed that the main reactive species are (positive) holes and superoxide species. Finally, the optimized photocatalyst was also able to degrade phenol under visible light.

The photocatalytic degradation of the emerging contaminant paracetamol in aqueous solution has been studied under 1 SUN (~1000 W m⁻²) in the presence of four commercial TiO₂ powders, namely sub-micrometric anatase and rutile, and nanometric brookite and P25 (the popular anatase/rutile mixture used as a benchmark in most papers). The rutile powder showed low activity, whereas, interestingly, the anatase and the brookite powders outperformed P25 in terms of total paracetamol conversion to carboxylic acids, which, according to the literature, are the final products of its degradation. To explain such results, the physicochemical properties of the powders were studied by applying a multi-technique approach. Among the physicochemical properties usually affecting the photocatalytic performance of TiO₂, the presence of some surface impurities likely deriving from K₃PO₄ (used as crystallization agent) was found to significantly affect the percentage of paracetamol degradation obtained with the sub-micrometric anatase powder. To confirm the role of phosphate, a sample of anatase, obtained by a lab synthesis procedure and having a “clean” surface, was used as a control, though characterized by nanometric particles and higher surface area. The sample was less active than the commercial anatase, but it was more active after impregnation with K₃PO₄. Conversely, the presence of Cl at the surface of the rutile did not sizably affect the (overall poor) photocatalytic activity of the powder. The remarkable photocatalytic activity of the brookite nanometric powder was ascribed to a combination of several physicochemical properties, including its band structure and nanoparticles size.

For the first time, Fe-doping (0.05, 1.0, and 2.5 wt.% Fe) was performed on a high-surface-area anatase/brookite TiO₂ by adopting a simple template-free sol-gel synthesis followed by calcination at a mild temperature. The powders’ textural and surface properties were characterized by following a multi-technique approach. XRD analysis showed that the anatase/brookite ratio slightly varied in the Fe-doped TiO₂ (from 76.9/23.1 to 79.3/22.7); Fe doping noticeably affected the cell volume of the brookite phase, which decreased, likely due to Fe³⁺ ions occupying interstitial positions, and retarded the crystallite growth. N₂ sorption at −196 °C showed the occurrence of samples with disordered interparticle mesopores, with an increase in the specific surface area from 236 m² g⁻¹ (undoped TiO₂) to 263 m² g⁻¹ (2.5 wt.% Fe). Diffuse Reflectance UV-Vis spectroscopy showed a progressive decrease in the bandgap energy from 3.10 eV (undoped TiO₂) to 2.85 eV (2.5 wt.% Fe). XPS analysis showed the presence of some surface Fe species only at 2.5 wt.% Fe, and accordingly, the ζ-potential measurements showed small changes in the pH at the isoelectric point. The photocatalytic degradation of simazine (a persistent water contaminant) both under UV and simulated solar light was performed as a probe reaction. Under UV light, Fe-doping improved simazine degradation in the sample at 0.05 wt.% Fe, capable of degrading ca. 77% simazine. Interestingly, the undoped TiO₂ was also active both under UV and 1 SUN. This is likely due to the occurrence of anatase/brookite heterojunctions, which help stabilize the photogenerated electrons/holes.

The reduction of nitrogen oxides (NO_x), critical pollutants from stationary to mobile sources, mainly relies on the selective catalytic reduction (NH₃-SCR) method, employing ammonia to reduce NO_x into nitrogen and water. However, conventional catalysts, while effective, pose both environmental and operational challenges. This study investigates ceria-zirconia-supported molybdenum-based catalysts, exploring the effects of zirconium doping and different catalyst synthesis techniques, i.e., co-precipitation and impregnation. The catalytic performance of the differently prepared samples was significantly influenced by the molybdenum incorporation method and the zirconium content within the ceria-zirconia support. Co-precipitation at higher temperatures resulted in catalysts with better structural attributes but slightly lower catalytic activity compared to those prepared via impregnation. Optimal NO_x reduction (close to 100%) was observed at a 15 mol% zirconium doping level when using the impregnation method.