Mixtures and composites of Ag/Ag₂O and TiO₂ (P25) with varying mass ratios of Ag/Ag₂O were prepared, employing two methods. Mechanical mixtures (TM) were obtained by the sonication of a suspension containing TiO₂ and Ag/Ag₂O. Composites (TC) were prepared by a precipitation method employing TiO₂ and AgNO₃. Powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ag(0) and Ag₂O. The activity of the materials was determined employing methylene blue (MB) as the probe compound. Bleaching of MB was observed in the presence of all materials. The bleaching rate was found to increase with increasing amounts of TiO₂ under UV/vis light. In contrast, the MB bleaching rate decreased with increasing TiO₂ content upon visible light illumination. XRD and XPS data indicate that Ag₂O acts as an electron acceptor in the light-induced reaction of MB and is transformed by reduction of Ag⁺, yielding Ag(0). As a second light-induced reaction, the evolution of molecular hydrogen from aqueous methanol was investigated. Significant H₂ evolution rates were only determined in the presence of materials containing more than 50 mass% of TiO₂. The experimental results suggest that Ag/Ag₂O is not stable under the experimental conditions. Therefore, to address Ag/Ag₂O as a (photo)catalytically active material does not seem appropriate.

Photocatalyzed degradation of phenol in aqueous solution over surface impregnated TiO₂ (M = Cu, Cr, V) under UV-Vis (366 nm) and UV (254 nm) irradiation is described. Nanosized photocatalyts were prepared from TiO₂-P25 by wet impregnation, and characterized by X-ray diffraction, X-ray fluorescence, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, Raman spectroscopy, and adsorption studies. No oxide phases of the metal dopants were found, although their presence in the TiO₂-P25 lattice induces tensile strain in Cu-impregnated TiO₂-P25, whereas compressive strain in Cr- and V-impregnated TiO₂-P25. Experimental evidences support chemical and mechanical stability of the photocatalysts. Type IV N₂ adsorption–desorption isotherms, with a small H3 loop near the maximum relative pressure were observed. Metal surface impregnated photocatalysts are mesoporous with a similar surface roughness, and a narrow pore distribution around ca. 25 Å. They were chemically stable, showing no metal lixiviation. Their photocatalytic activity was followed by UV-Vis spectroscopy and HPLC–UV. A first order kinetic model appropriately fitted the experimental data. The fastest phenol degradation was obtained with M (0.1%)/TiO₂-P25, the reactivity order being Cu > V >> Cr > TiO₂-P25 under 366 nm irradiation, while TiO₂-P25 > Cu > V > Cr, when using 254 nm radiation. TOC removal under 366 nm irradiation for 300 min showed almost quantitative mineralization for all tested materials, while 254 nm irradiation for 60 min led to maximal TOC removal (ca. 30%). Photoproducts and intermediate photoproducts were identified by HPLC–MS, and appropriate reaction pathways are proposed. The energy efficiency of the process was analysed, showing UV lamps are superior to UVA lamps, and that the efficiency of the surface impregnated catalyst varies in the order Cu > V > Cr.

One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO₂-P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N₂ physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3–2.5 eV. The photocatalytic degradation of aqueous phenol over TiO₂-P25 and Co(X%)/TiO₂ was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO₂ being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation.

The determination of reaction pathways and identification of products of pollutants degradation is central to photocatalytic environmental remediation. This work focuses on the photocatalytic degradation of the herbicide Imazapyr (2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl) pyridine-3-carboxylic acid) under UV-Vis and visible-only irradiation of aqueous suspensions of Ca_xMnO_y-TiO₂, and on the identification of the corresponding degradation pathways and reaction intermediates. Ca_xMnO_y-TiO₂ was formed by mixing Ca_xMnO_y and TiO₂ by mechanical grinding followed by annealing at 500 °C. A complete structural characterization of Ca_xMnO_y-TiO₂ was carried out. The photocatalytic activity of the hetero-nanostructures was determined using phenol and Imazapyr herbicide as model pollutants in a stirred tank reactor under UV-Vis and visible-only irradiation. Using equivalent loadings, Ca_xMnO_y-TiO₂ showed a higher rate (10.6 μM·h⁻¹) as compared to unmodified TiO₂ (7.4 μM·h⁻¹) for Imazapyr degradation under UV-Vis irradiation. The mineralization rate was 4.07 µM·h⁻¹ for Ca_xMnO_y-TiO₂ and 1.21 μM·h⁻¹ for TiO₂. In the Ca_xMnO_y-TiO₂ system, the concentration of intermediate products reached a maximum at 180 min of irradiation that then decreased to a half in 120 min. For unmodified TiO₂, the intermediates continuously increased with irradiation time with no decrease observed in their concentration. The enhanced efficiency of the Ca_xMnO_y-TiO₂ for the complete degradation of the Imazapyr and intermediates is attributed to an increased adsorption of polar species on the surface of Ca_xMnO_y. Based on LC-MS, photocatalytic degradation pathways for Imazapyr under UV-Vis irradiation have been proposed. Some photocatalytic degradation was obtained under visible-only irradiation for Ca_xMnO_y-TiO₂. Hydroxyl radicals were found to be main reactive oxygen species responsible for the photocatalytic degradation through radical scavenger investigations.