Solar photothermo-catalysis is a fascinating multi-catalytic approach for volatile organic compounds (VOCs) removal. In this work, we have explored the performance and the chemico-physical features of non-critical, noble, metal-free MnOx-ZrO2 mixed oxides. The structural, morphological, and optical characterizations of these materials pointed to as a low amount of ZrO2 favoured a good interaction and the ionic exchange between the Mn and the Zr ions. This favoured the redox properties of MnOx increasing the mobility of its oxygens that can participate in the VOCs oxidation through a Mars-van Krevelen mechanism. The further application of solar irradiation sped up the oxidation reactions promoting the VOCs total oxidation to CO2. The MnOx-5 wt.%ZrO2 sample showed, in the photothermo-catalytic tests, a toluene T90 (temperature of 90% of conversion) of 180 °C and an ethanol T90 conversion to CO2 of 156 °C, 36 °C, and 205 °C lower compared to the thermocatalytic tests, respectively. Finally, the same sample exhibited 84% toluene conversion and the best selectivity to CO2 in the ethanol removal after 5 h of solar irradiation at room temperature, a photoactivity similar to the most employed TiO2-based materials. The as-synthetized mixed oxide is promising for an improved sustainability in both catalyst design and environmental applications.

A non-conventional approach to prepare titanium dioxide-reduced graphene oxide (TiO2-rGO) nanocomposites based on solar photoreduction is here presented. The standard hydro-solvothermal synthesis of the TiO2-rGO composites requires high temperatures and several steps, whereas the proposed one-pot preparation allows one to obtain the photocatalysts with a simple and green procedure, by exploiting the photocatalytic properties of titania activated by the solar irradiation. The TiO2-rGO catalysts were tested in the solar photodegradation of a widely adopted toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining the 97% of degradation after 3 h of irradiation. The as-prepared TiO2-rGO composites were more active compared to the same photocatalysts prepared through the conventional thermal route. The structural, optical, and textural properties of the composites, determined by Raman, Photoluminescence, Fourier Transform InfraRed (FTIR), UV-vis diffuse reflectance (DRS) spectroscopies, and N2 absorption-desorption measurements, showed as the solar irradiation favors the reduction of graphene oxide with higher efficiency compared to the thermal-driven synthesis. Furthermore, the possible toxicity of the as-synthesized composites was measured exposing nauplii of microcrustacean Artemia sp. to solutions containing TiO2-rGO. The good results in the 2,4-D degradation process and the easiness of the TiO2-rGO synthesis allow to consider the proposed approach a promising strategy to obtain performing photocatalysts.

A nanometric hybrid system consisting of a Fe3O4 magnetic nanoparticles modified through the growth of Fe-based Metal-organic frameworks of the MIL (Materials Institute Lavoiser) was developed. The obtained system retains both the nanometer dimensions and the magnetic properties of the Fe3O4 nanoparticles and possesses increased the loading capability due to the highly porous Fe-MIL. It was tested to load, carry and release temozolomide (TMZ) for the treatment of glioblastoma multiforme one of the most aggressive and deadly human cancers. The chemical characterization of the hybrid system was performed through various complementary techniques: X-ray-diffraction, thermogravimetric analysis, FT-IR and X-ray photoelectron spectroscopies. The nanomaterial showed low toxicity and an increased adsorption capacity compared to bare Fe3O4 magnetic nanoparticles (MNPs). It can load about 12 mg/g of TMZ and carry the drug into A172 cells without degradation. Our experimental data confirm that, after 48 h of treatment, the TMZ-loaded hybrid nanoparticles (15 and 20 μg/mL) suppressed human glioblastoma cell viability much more effectively than the free drug. Finally, we found that the internalization of the MIL-modified system is more evident than bare MNPs at all the used concentrations both in the cytoplasm and in the nucleus suggesting that it can be capable of overcoming the blood-brain barrier and targeting brain tumors. In conclusion, these results indicate that this combined nanoparticle represents a highly promising drug delivery system for TMZ targeting into cancer cells.

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Atmospheric pressure (AP) vapor phase processes such as spatial atomic layer deposition (S-ALD) and AP-metalorganic chemical vapor deposition (AP-MOCVD) are becoming increasingly important for their use in a variety of...