Self-cleaning cellulose acetate/crystalline nanocellulose/polyvinylidene fluoride/Mg0.975Ni0.025SiO3membrane for removal of diclofenac sodium and methylene blue dye in water.

Recalcitrant pollutants present in wastewater, without an effective treatment, have several effects on aquatic ecosystems and human health due to their chemical structure and persistence. Therefore, it is crucial the development of efficient technologies to eliminate such pollutants in water. Nano-photocatalysts are considered a promising technology for water remediation; however, one common drawback is the difficulty of recovering it after water processing. One effective strategy to overcome such problem is its immobilization into substrates such as polymeric membranes. In this study, a polymeric membrane with embedded Mg0.975Ni0.025SiO3is proposed to remove model pollutants diclofenac sodium and methylene blue dye by synergetic adsorption and photocatalytic processes. Mg0.975Ni0.025SiO3was synthesized by the combustion method. The matrix polymeric blend consisting of a blend of cellulose acetate, crystalline nanocellulose and polyvinylidene fluoride was obtained by the phase inversion method. The composite membranes were characterized by FTIR, x-ray diffraction, and scanning electron microscopy. With pollutant solutions at pH 7, the pollutant adsorption capacity of the membranes reached up to 30% and 45% removal efficiencies for diclofenac sodium and methylene blue, respectively. Under simulated solar irradiation photocatalytic removal performances of 70% for diclofenac sodium pH 7, and of 97% for methylene blue dye at pH 13, were reached. The membrane photocatalytic activity allows the membrane to avoid pollutant accumulation on its surface, given a self-cleaning property that allows the reuse of at least three cycles under sunlight simulator irradiation. These results suggest the high potential of photocatalytic membranes using suitable and economical materials such as cellulosic compounds and magnesium silicates for water remediation.

Efficient solar removal of acetaminophen contaminant from water using flexible graphene composites functionalized with Ni@TiO2:W nanoparticles.

This work presents the morphological, structural and photocatalytic properties of flexible graphene composites decorated with Ni@TiO2:W nanoparticles (TiNiW NPs) with an average size of 27 ± 2 nm. The TiNiW NPs were immobilized on the surface of a flexible graphene composite using a PVA-based slurry-paste (FG/TiNiW composite). The SEM study showed that the TiNiW NPs remained exposed on the surface of the FG/TiNiW composite, which benefited its photocatalytic activity. The photocatalytic performance for the degradation of acetaminophen (ACT) was evaluated using both the TiNiW powders and the FG/TiNiW composite, obtaining maximum degradation efficiencies of 100 and 86%, respectively, after 3 h under natural solar irradiation. The degradation of ACT was caused mainly by the reactive oxygen species such as OH radicals and h+, which was confirmed by scavenger experiments. Photoluminescence, XPS and absorbance experiments revealed that oxygen vacancy defects were created by i) doping the TiNiW NPs with W and by ii) introducing graphene into the composites. These defects enhanced the absorbance of light in the range of 400-800 nm, which in turn, promoted the photocatalytic degradation of ACT. Moreover, the reuse experiments confirmed that both the TiNiW NPs and FG/TiNiW composite were very stable for the degradation of ACT, since degradation efficiencies >82% were obtained after 4 reuse cycles for both photocatalysts. The experimental findings of this work demonstrate that the flexible TiO2/graphene composites are a feasible option for the removal of pharmaceutical contaminants from water using natural solar irradiation.

Luminescence concentration quenching mechanism in Gd2O3:Eu3+.

Luminescence concentration quenching in Gd2O3:Eu(3+) nanocrystals results from strong interactions among O(2-) ions and Eu(3+) ions. Because all synthesized Gd2O3:Eu(3+) nanocrystals present the same cubic crystalline phase regardless of Eu(3+) concentration, it is possible to study the optical properties as a function of the dopant concentration. The emission intensities and lifetime curves for Gd2O3:Eu(3+) were analyzed by a simple rate equation model to study the interaction between the O(2-) ions and Eu(3+) ions. The rate equation model considers that such interaction is driven by the following energy transfer processes: the direct energy transfer (O(2-) → Eu(3+)), back-transfer (Eu(3+) → O(2-)), and direct energy migration (Eu(3+) → Eu(3+)). The exact solution of this model agrees with the experimental results, luminescence concentration quenching is reproduced and the corresponding energy transfer rates are reported. Quantitative results suggest that the direct energy transfer and direct energy migration processes are the main responsible for the luminescence concentration quenching, whereas the back-transfer process promotes the Eu(3+) emission.

Structural and chemical characterization of Yb2O3-ZrO2 system by HAADF-STEM and HRTEM.

ZrO2:Yb3+ nanocrystalline phosphors with high concentrations of ytterbium ions were prepared using the sol-gel method. X-ray diffraction, high-angle annular-dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy (HRTEM) were used to characterize the nanocrystalline phosphors annealed at 1000 degrees C. Unit-cell distortion and changes in the crystalline structure of the monoclinic zirconia to tetragonal zirconia, and subsequently cubic zirconia, were observed with increased Yb concentration. Yb ions were randomly distributed into the lattice of the crystalline structure. No segregation of Yb2O3 phase was observed. The substitution of Zr atoms by Yb atoms on different crystalline phases was confirmed by the experimental results and theoretical simulations of HRTEM and HAADF-STEM.

Thermoluminescence properties of undoped and Dy3+ doped ZrO2 nanophosphor under beta-ray irradiation.

The thermoluminescence (TL) of undoped and Dy3+ doped ZrO2 nanocrystals under beta-ray irradiation is reported. The TL glow curves are the result of the overlapping of four TL peaks produced partly by the intrinsic defect of highly asymmetrical monoclinic structure and partly due to defects produced during the synthesis process. The introduction of dopant ions induces changes in the glow curve due to the enhancement of high temperature peaks intensity. The results show that both undoped and doped ZrO2 nanocrystalline phosphor present good TL efficiency as well as good dose response which qualify them as a potential beta-ray dosimeter.

A new blue, green and red upconversion emission nanophosphor: BaZrO3:Er,Yb.

Strong Blue, green, and red upconversion emission of Er3+ in nanocrystalline BaZrO3:(Yb3+Er3+) is observed. Powder samples were obtained by a facile hydrothermal process at 100 degrees C. The as synthesized nanocrystallites preserve a stable cubic perovskite phase under subsequent annealing treatment up to 1000 degrees C. No other phase or segregation of other compounds was detected. Crystallites sizes were around 115 nm and well faceted. Under IR excitation in the range between 900 and 1050 nm the Er3+ blue emission was almost not present in single Er3+ doped BaZrO3, whereas it became easily observable when Yb3+ was added as codopant. Besides, both green and red upconversion emission or upconverted signal of Er3+ are enhanced by around three orders of magnitude in comparison with the single Er3+ doped BaZrO3. The strong blue emission presents dependence on both excitation power and excitation wavelength. This is the first time that upconversion emission is observed in BaZrO3. A possible mechanism for the upconversion process that leads to the observed blue, green and red emissions under NIR excitation is suggested based on the experimental results.

Structural and spectroscopic characterization of ZrO2:Eu3+ nanoparticles.

ZrO2:Eu3+ nanocrystals were prepared by the sol-gel technique. The structural and luminescence properties of europium doped zirconia with 0.5 to 2 mol% were studied by Mössbauer spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), High Resolution Transmission Electron Microscopy (HRTEM) and photoluminescence (PL) under UV excitation. Structural characterization shows a crystallite size between 16 to 55 nm and monoclinic and tetragonal zirconia phases as the main crystalline structure. XRD patterns shown that the content of the active ions stabilizes the tetragonal structure of ZrO2 at 1000 degrees C, being 100% for 2 mol% Eu2O3 doped sample. Such results are in agreement with HRTEM and Raman spectroscopy. The Mössbauer spectra of the ZrO2:Eu3+ samples show a single peak near zero velocity which is attributed to Eu+3. Luminescence characterization shows the typical emission band centered at 595 and 611 nm. Change in the structure of such band was observed and explained in terms of crystalline phase change. The dependence between the fluorescence emission and the crystalline structure is discussed.

Strong visible cooperative up-conversion emission in ZrO2:Yb3+ nanocrystals.

Blue, green, and red emission was observed under infrared excitation in ZrO2:Yb3+ nanocrystals prepared by the sol-gel process. The structural characterization was performed by using XRD and HRTEM, suggesting that the crystalline phase of the nanoparticles is controlled by the active ion concentration being mainly tetragonal for 2 mol% of dopant and mainly monoclinic for 0.5 mol%. The blue emission was explained in terms of the cooperative deexcitation of an Yb-Yb pair, while the green and red bands were associated with the up-conversion of traces of Er ion. The number of photons involved in the luminescence process is analyzed in order to confirm that cooperative emission is produced by the interaction of an Yb pair and that the green and red emission are the results of energy transfer between Yb-Er ions. The high efficiency of all bands is explained in terms of the high surface area of the nanoparticles.