Widely Tuneable Composition and Crystallinity of Graded Na1+xTaO3±Î´ Thin Films Fabricated by Chemical Beam Vapor Deposition.

Combinatorial approach has been widely recognized as a powerful strategy to develop new-higher performance materials and shed the light on the stoichiometry-dependent properties of known systems. Herein, we take advantage of the unique features of chemical beam vapor deposition to fabricate compositionally graded Na1+xTaO3±Î´ thin films with −0.6 < x < 0.5. Such a varied composition was enabled by the ability of the employed technique to deliver and combine an extensive range of precursors flows over the same deposition area. The film growth occurred in a complex process, where precursor absolute flows, flow ratios, and substrate temperature played a role. The deviation of the measured Na/Ta ratios from those predicted by flow simulations suggests that a chemical-reaction limited regime underlies the growth mechanism and highlights the importance of the Ta precursor in assisting the decomposition of the Na one. The crystallinity was observed to be strongly dependent on its stoichiometry. High under-stoichiometries (e.g., Na0.5TaO3−δ) compared to NaTaO3 were detrimental for the formation of a perovskite framework, owing to the excessive amount of sodium vacancies and oxygen vacancies. Conversely, a well-crystallized orthorhombic perovskite structure peculiar of NaTaO3 was observed from mildly under-stoichiometric (e.g., Na0.9TaO3−δ) to highly over-stoichiometric (e.g., Na1.5TaO3+δ) compositions.

A review of recent and emerging antimicrobial nanomaterials in wastewater treatment applications.

In this paper, we present a critical review on antimicrobial nanomaterials with demonstrated potential for application as a disinfection technology in wastewater treatment. Studies involving fabrication and testing of antimicrobial nanomaterials for wastewater treatment were gathered, critically reviewed, and analyzed. Our review shows that there are only a few eligible candidate nanoparticles (NPs) (metal and metal oxide) that can adequately serve as an antimicrobial agent. Nanosilver (nAg) was the most studied and moderately understood metal NPs with proven antimicrobial activity followed by ZnO (among antimicrobial metal oxide NPs) which outperformed titania (in the absence of light) in efficacy due to its better solubility in aqueous condition. The direction of future work was found to be in the development of antimicrobial nanocomposites, since they provide more stability for antimicrobial metal and metal oxides NPs in water, thereby increasing their activity. This review will serve as an updated survey, yet touching also the fundamentals of the antimicrobial activity, with vital information for researchers planning to embark on the development of superior antimicrobial nanomaterials for wastewater treatment applications.

The influence of nitrogen doping on the electronic structure of the valence and conduction band in TiO2.

X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS) provide a unique opportunity to probe both the highest occupied and the lowest unoccupied states in matter with bulk sensitivity. In this work, a combination of valence-to-core XES and pre-edge XAS techniques are used to determine changes induced in the electronic structure of titanium dioxide doped with nitrogen atoms. Based on the experimental data it is shown that N-doping leads to incorporation of the p-states on the occupied electronic site. For the conduction band, a decrease in population of the lowest unoccupied d-localized orbitals with respect to the d-delocalized orbitals is observed. As confirmed by theoretical calculations, the N p-states in TiO2 structure are characterized by higher binding energy than the O p-states which gives a smaller value of the band-gap energy for the doped material.

Integrated Nano- and Macroscale Investigation of Photoinduced Hydrophilicity in TiO2 Thin Films.

The hydrophilicity of titanium dioxide has been investigated for films, deposited on glass by e-beam evaporation, being exposed to UV radiation and subjected to thermal annealing. The wettability alteration has been showed to depend upon both treatments, and insights into how to introduce more stable hydrophilicity into these films have been presented for the sake of boosting their commercial value. Observations from multiple length scales to assess the wetting behavior of as-deposited and high-temperature annealed samples were assessed through macroscopic measurements, i.e., water contact angle measurements, showing that the annealed crystalline samples, treated at 500 °C, are much more hydrophilic (SCA ≈ 20°) than as-deposited TiO2 films (SCA ≈ 90°), and the nanoscopic experiments performed by amplitude modulation (AM) atomic force microscopy (AFM) indicated that this increased hydrophilicity is related to an enhanced adhesion force and surface energy, resulting in the partial crystallization of TiO2 and the consequent formation of crystals on its surface rather than being related to morphologic differences. XRD and Raman measurements have highlighted that the crystallinity of the TiO2 film is crucial in determining its hydrophilicity, in good agreement with the AFM study. The results also indicated that, after irradiation, the samples treated at 500 °C preserve their hydrophilicity for a significant time compared to previous studies.