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Nanocrystalline titania (TiO2) is one of the most investigated crystalline nanostructured systems in the field of materials science. The technological applications of this material are related to its optoelectronic and photocatalytic properties, which in turn are strongly dependent on the crystal phase (i.e., anatase, brookite, and rutile), particle size, and surface structure. However, systematic comparative studies of all its crystal phases are scarce in literature due to difficulties in providing a controlled synthesis, which is primarily important in obtaining the brookite phase. In this report, the synthesis of TiO2 nanoparticles in the anatase, brookite, and rutile structures was explored, using amorphous TiO2 as a common precursor under microwave-assisted hydrothermal conditions. The influence of parameters such as temperature, acidity, and precursor concentration on phase crystallization were investigated. The TiO2 materials (amorphous and crystalline phases as well as commercial Degussa P25) were systematically characterized using Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV-visible reflectance spectroscopy, and dynamic and electrophoretic light scattering. The bactericidal activity and photocatalytic antibacterial effectiveness of each material were evaluated through the determination of the minimum inhibitory and bactericidal concentrations, and via the mortality kinetic method under ultraviolet (UV) illumination under similar conditions with two bacterial groups of unique cellular structures: Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus). The results are discussed with particular emphasis on the relationship between the synthesis parameters (acidity, precursor concentration, temperature and reaction time) and the bactericidal properties.
Assuntos
Micro-Ondas , Staphylococcus aureus , Catálise , Escherichia coli , TitânioRESUMO
Mixed-halide organic-inorganic hybrid perovskites are considered promising light-absorbing materials in the development of solar cells related to the obtained high-power conversion efficiency. Current efforts are focused on the study of the energy-conversion mechanisms, where the nonradiative recombination pathway is the least explored. In this work, a combination of optical and photoacoustic spectroscopies is used to determine the visible spectral light-into-heat conversion efficiency of lead-based mixed-halide organic-inorganic hybrid perovskites in a semicomplete n-i-p mesoscopic perovskite solar cell (PSC). A remarkable average conversion efficiency of about 87% has been found for the nonradiative combination in the perovskite, with the estimated composition ${{\rm FA}_{0.71}}{{\rm MA}_{0.29}}{{\rm PbI}_{2.9}}{{\rm Br}_{0.1}}$FA0.71MA0.29PbI2.9Br0.1 in the wavelength range of 400 to 800 nm. As a result, 13% of the incident light is transformed in radiative recombination processes and/or photodegradation of the material. Furthermore, the extinction coefficient and refractive index of the material are reported, and it was found that the optical constants and the optical absorption in the short-wavelength range are significantly smaller than previously reported for${{\rm MAPbI}_3}$MAPbI3.
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Correction for 'The effect of recombination under short-circuit conditions on the determination of charge transport properties in nanostructured photoelectrodes' by J. Villanueva-Cab et al., Phys. Chem. Chem. Phys., 2016, 18, 2303-2308.
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We report on the commonly unaccounted for process of recombination under short-circuit conditions in nanostructured photoelectrodes with special attention to the charge collection efficiency. It is observed that when recombination under short circuit conditions is significant, small perturbation methods overestimate the charge-collection efficiency, which is related to the inaccurate determination of the electron diffusion coefficient and diffusion length.
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The first stages of the synthesis of ZnO nanoparticles by forced hydrolysis of ZnCl2 with NaOH and water in ethanol have been investigated using UV-Vis spectrophotometry. At sufficiently low water concentrations, focusing of the nanoparticle size distribution was observed during the nucleation and growth phase, followed by a defocusing phase when coarsening becomes significant. During nucleation and growth, only the smaller particles grow while the larger particles have an essentially zero growth rate, indicating that the growth rate decreases rapidly with particle size. As the average particle size remains nearly constant in this regime, the absorbance increase with time can be used to determine the nucleation rate. The nucleation rate was found to depend on both the water concentration and the reactant concentrations. The results are discussed in terms of a mechanism where water determines the precursor formation kinetics thus controlling the nucleation rate.
Assuntos
Cloretos/química , Nanopartículas/química , Compostos de Zinco/química , Óxido de Zinco/química , Etanol/química , Hidrólise , Cinética , Nanopartículas/ultraestrutura , Tamanho da Partícula , Hidróxido de Sódio/química , Espectrofotometria Ultravioleta , Água/químicaRESUMO
We report on the synthesis of phase-pure TiO(2) nanoparticles in anatase, rutile and brookite structures, using amorphous titania as a common starting material. Phase formation was achieved by hydrothermal treatment at elevated temperatures with the appropriate reactants. Anatase nanoparticles were obtained using acetic acid, while phase-pure rutile and brookite nanoparticles were obtained with hydrochloric acid at a different concentration. The nanomaterials were characterized using x-ray diffraction, UV-visible reflectance spectroscopy, dynamic light scattering, and transmission electron microscopy. We propose that anatase formation is dominated by surface energy effects, and that rutile and brookite formation follows a dissolution-precipitation mechanism, where chains of sixfold-coordinated titanium complexes arrange into different crystal structures depending on the reactant chemistry. The particle growth kinetics under hydrothermal conditions are determined by coarsening and aggregation-recrystallization processes, allowing control over the average nanoparticle size.