Cluster Coordination and Photoluminescence Properties of alpha-Ag2WO4 Microcrystals

In this paper, we report our initial research to obtain hexagonal rod-like elongated silver tungstate (alpha-Ag2WO4) microcrystals by different methods [sonochemistry (SC), coprecipitation (CP), and conventional hydrothermal (CH)] and to study their cluster coordination and optical properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier transform infrared (FT-IR), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The shape and average size of these alpha-Ag2WO4 microcrystals were observed by field-emission scanning electron microscopy (FE-SEM). The optical properties of these microcrystals were investigated by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) measurements. XRD patterns and Rietveld refinement data confirmed that alpha-Ag2WO4 microcrystals have an orthorhombic structure. FT-IR spectra exhibited four IR-active modes in a range from 250 to 1000 cm(-1). XANES spectra at the W L-3-edge showed distorted octahedral [WO6] clusters in the lattice, while EXAFS analyses confirmed that W atoms are coordinated by six O atoms. FE-SEM images suggest that the alpha-Ag2WO4 microcrystals grow by aggregation and the Ostwald ripening process. PL properties of alpha-Ag2WO4 microcrystals decrease with an increase in the optical band-gap values (3.19-3.23 eV). Finally, we observed that large hexagonal rod-like alpha-Ag2WO4 microcrystals prepared by the SC method exhibited a major PL emission intensity relative to alpha-Ag2WO4 microcrystals prepared by the CP and CH methods.

Effects of laser focusing and fluence on the analysis of pellets of plant materials by laser-induced breakdown spectroscopy

The effects of laser focusing and fluence on LIBS analysis of pellets of plant leaves was evaluated. A Q-switched Nd:YAG laser (5ns, 10Hz, 1064nm) was used and the emission signals were collected by lenses into an optical fiber coupled to a spectrometer with Echelle optics and ICCD. Data were acquired from the accumulation of 20 laser pulses at 2.0 mu s delay and 5.0 mu s integration time gate. The emission signal intensities increased with both laser fluence and spot size. Higher sensitivities for Ca, K, Mg, P, Al, B, Cu, Fe, Mn, and Zn determinations were observed for fluences in the range from 25 to 60Jcm(-2). Coefficients of variation of site-to-site measurements were generally lower than 10% (n=30 sites, 20 laser pulses/site) for a fluence of 50Jcm(-2) and 750 mu m spot size. For most elements, there is an indication that accuracy is improved with higher fluences. (C) 2012 Elsevier B.V. All rights reserved.

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 degrees C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 C for 2 h. The degree of structural order disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Single-wall carbon nanotube interactions with copper-oxamato building block of molecule-based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]2- anions (where opba is orthophenylenebis (oxamato)) and single-wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright (c) 2012 John Wiley & Sons, Ltd.

Electrooxidation of ethanol on Pt and PtRu surfaces investigated by ATR surface-enhanced infrared absorption spectroscopy

Herein, it was investigated for the first time the electro-oxidation of ethanol on Pt and PtRu electrodeposits in acidic media by using in situ surface enhanced infrared absorption spectroscopy with attenuated total reflection (ATR-SEIRAS). The experimental setup circumvents the weak absorbance signals related to adsorbed species, usually observed for rough, electrodeposited surfaces, and allows a full description of the CO coverage with the potential for both catalysts. The dynamics of adsorption-oxidation of CO was accessed by ATR-SEIRAS experiments (involving four ethanol concentrations) and correlated with expressions derived from a simple kinetic model. Kinetic analysis suggests that the growing of the CO adsorbed layer is nor influenced by the presence of Ru neither by the concentration of ethanol. The results suggest that the C-C scission is not related to the presence of Ru and probably happens at Pt sites.

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy by mechanical spectroscopy

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy were obtained using the mechanical spectroscopy technique. The sample with heat treatment at 1170K for 30 minutes and water quenched with subsequent aging treatment at 670 K for 3 hours (TNZ + WQ + 670 K/3 h), was characterized through decay of free oscillations of the sample in the flexural vibration mode. The spectra of anelastic relaxation (internal friction and frequency) in the temperature range from 300 K to 625 K not revealed the presence of relaxation process. As shown in the literature, the hcp structure usually does not exhibit any relaxation due to the symmetry of the sites in the crystalline lattice, but if there is some relaxation, this only occurs in special cases such as low concentration of zirconium or saturation of the stoichiometric ratio of oxygen for zirconium. Dynamical elastic modulus obtained for TNZ + WQ + 670 K/3 h alloy was 87 GPa at room temperature, which is higher than the value for Ti-13Nb-13Zr alloy (64 GPa) of the literature. This increment may be related to the change of the proportion of α and β phases. Besides that, the presence of precipitates in the alloy after aging treatment hardens the material and reduces its ductility.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Bilipid membrane phase characterization by reflectance anisotropy spectroscopy (RAS)

In this work we propose the use of experimental and theoretical reflectance anisotropy spectra (RAS) as a new tool to identify structural and dynamical aspects of the bilipid membrane and its various constituent molecules. The role of geometric details at the atomic level and macroscopic quantities, such as the membrane curvature and tilt for the different gel phases, in the theoretical RAS spectra (using Kohn-Sham density functional theory (KS-DFT)) are presented. Then the results are compared to the experimentally measured spectra taken from other techniques.

Positron annihilation spectroscopy techniques applied to the study of an HPGe detector.

Doppler Broadening Spectroscopy of the large Ge crystal of an HPGe detector was perforrned using positrons from pair production of 6.13 MeV ϒ-rays from the 19F(p,αϒ) 16O reaction. Two HPGe detectors facing opposite sides of the Ge crystal acting as target provided both coincidence and singles spectra. Changes in the shape of the annihilation peak were observed when the high voltage applied to the target detector was switched on or off, amounting to somewhat less than 20% when the areas of equivalent energy intervals in the corresponding normalized spectra are compared.