Solvothermal synthesis and photocatalytic performance of Mn4+-doped anatase nanoplates with exposed {001} facets

The photocatalytic activity of TiO2 and manganese doped TiO2 nanoplates with various manganese atomic percentages, in the range of 2-7%, was studied. The undoped and doped nanoplates with exposed {001} facets were produced by a solvothermal method. The crystal structure as well as the shape of the TiO2 and Mn4+/TiO2 anatase nanoparticles was determined with X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Both techniques revealed that the nanocrystals are in the form of plates. Moreover, the anisotropic peak broadening of the X-ray diffraction patterns was studied using the Rietveld refining method. Chemical analysis of the photocatalyst that was carried out with X-ray photoelectron spectroscopy (XPS) showed the presence of manganese ions in the TiO2 anatase matrix. The Density Functional Theory (DFT) calculations exhibited a decrease in the energy gap and an increase in the density of the electronic stated inside the gap for the doped TiO2. These observations were in agreement with the results of the UV-visible diffuse reflectance spectroscopy (DRS) that demonstrated an adsorption shift towards the visible region for the same samples. The photocatalytic activity of the synthesized catalysts was investigated by the photocatalytic oxidation of the gaseous nitric oxide (NO) and decomposition of the gaseous acetaldehyde (CH3CHO) under visible light irradiation. The optimal concentration of dopant that improves the photocatalytic activity of the nanoplates was determined. © 2014 Elsevier B.V

Reversed-phase high-performance liquid chromatography–fluorescence detection for the analysis of glutathione and its precursor γ-glutamyl cysteine in wines and model wines supplemented with oenological inactive dry yeast preparations

El pdf del artículo es la versión pre-print.A reversed-phase high-performance liquid chromatography-fluorescence detection methodology involving a pre-column derivatization procedure using 2,3-naphtalenedialdehyde in the presence of 5 and 0. 5 mM of dithiothreitol to determine total and reduced glutathione (GSH) and γ-glutamyl-cysteine (γ-glu-cys) in musts and wines has been set up and validated. The proposed method showed good linearity (R 2 >99% for reduced and total GSH, and R 2 >98% for γ-glu-cys) in synthetic wines, over a wide range of concentration (0-10 mg L -1). The limits of detection for reduced GSH in synthetic and real wines were almost the same (0. 13 and 0. 15 mg L -1, respectively) and slightly higher for γ-glu-cys (0. 24 mg L -1). The application of the method allowed knowing, for the first time, the amount of total and reduced GSH and γ-glu-cys released into synthetic wines by oenological preparations of commercial inactive dry yeast (IDY). In addition, the evolution of these three compounds during the winemaking and shelf life (0-9 months) of an industrially manufactured rosé wine supplemented with a GSH-enriched IDY showed that although GSH is effectively released from IDY, it is rapidly oxidized during alcoholic fermentation, contributing to the higher total GSH content determined in wines supplemented with GSH-enriched IDYs compared to control wines. © 2011 Springer Science+Business Media, LLC.IAO and JJRB acknowledge CAM and CSIC for their respective research grants. This work has been founded by PET2007-0134 project.Peer Reviewe

Tuning the photocatalytic selectivity of TiO2 anatase nanoplates by altering the exposed crystal facets content

TiO2 anatase nanoplates were fabricated by a solvothermal method using titanium isopropoxide as a titanium precursor and HF as a capping agent in order to enhance the formation of the {001} crystal facets of the anatase crystal. Two different surface modification procedures were applied in order to remove the adsorbed fluoride anions on the {001} crystal facets of the nanoplates. The first procedure was by calcining the as-prepared TiO2 anatase nanoplates up to 600°C and the second one was by washing them with a NaOH aqueous solution. Importantly, the surface modification procedure leads to the formation of two different morphologies of the TiO2 anatase nanoplates which exhibited tunable photocatalytic selectivity in air pollutants purification. The calcined nanoplates became larger and their {101} crystal facets expanded by shrinking the {001} crystal facets. In contrast the washed nanoplates maintained their shape which was formed by the solvothermal method. All samples that were calcined or washed, exhibited high photonic efficiency for air pollutants oxidation. The calcined TiO2 anatase nanoplates exhibited the best photocatalytic activity in oxidizing the NO gas to NO2 and NO3- whereas the washed TiO2 anatase nanoplates, preserving the initial morphology, exhibited the best photocatalytic activity in decomposing acetaldehyde. The dominant exposed {101} or {001} crystal facets of the TiO2 anatase nanoplates is the key factor in tuning the adsorption selectivity of the air pollutants. © 2013 Elsevier B.V