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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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) represents one of the most fundamental techniques capable of satisfying the strict technological requirements imposed by the rapidly evolving electronic components industry. The actual scaling trend is rapidly leading to the fabrication of nanoscaled devices able to overcome limits of the present microelectronic technology, of which the memristor is one of the principal candidates. Since their development in 2008, TiO2 thin film memristors have been identified as the future technology for resistive random access memories because of their numerous advantages in producing dense, low power-consuming, three-dimensional memory stacks. The typical features of ALD, such as self-limiting and conformal deposition without lineof- sight requirements, are strong assets for fabricating these nanosized devices. This work focuses on the realization of memristors based on low-temperature ALD TiO2 thin films. In this process, the oxide layer was directly grown on a polymeric photoresist, thus simplifying the fabrication procedure with a direct liftoff patterning instead of a complex dry etching process. The TiO2 thin films deposited in a temperature range of 120-230°C were characterized via Raman spectroscopy and x-ray photoelectron spectroscopy, and electrical current-voltage measurements taken in voltage sweep mode were employed to confirm the existence of resistive switching behaviors typical of memristors. These measurements showed that these low-temperature devices exhibit an ON/OFF ratio comparable to that of a high-temperature memristor, thus exhibiting similar performances with respect to memory applications. [ABSTRACT FROM AUTHOR]