Waldir Avansi

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 (α-Ag(2)WO(4)) 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 α-Ag(2)WO(4) 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 α-Ag(2)WO(4) 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 [WO(6)] clusters in the lattice, while EXAFS analyses confirmed that W atoms are coordinated by six O atoms. FE-SEM images suggest that the α-Ag(2)WO(4) microcrystals grow by aggregation and the Ostwald ripening process. PL properties of α-Ag(2)WO(4) microcrystals decrease with an increase in the optical band-gap values (3.19-3.23 eV). Finally, we observed that large hexagonal rod-like α-Ag(2)WO(4) microcrystals prepared by the SC method exhibited a major PL emission intensity relative to α-Ag(2)WO(4) microcrystals prepared by the CP and CH methods.

Presence of excited electronic state in CaWO4 crystals provoked by a tetrahedral distortion: An experimental and theoretical investigation

By combining experimental techniques such as x-ray diffraction, Fourier transform Raman, ultraviolet-visible, x-ray absorption near edge structure, extended x-ray absorption fine structure spectroscopy, and theoretical models, a general approach to understand the relationship among photoluminescence (PL) emissions and excited electronic states in CaWO4 crystals is presented. First-principles calculations of model systems point out that the presence of stable electronic excited states (singlet) allow us to propose one specific way in which PL behavior can be achieved. In light of this result, we reexamine prior experiments on PL emissions of CaWO4.

A novel ozone gas sensor based on one-dimensional (1D) α-Ag2WO4 nanostructures

This paper reports on a new ozone gas sensor based on α-Ag₂WO₄ nanorod-like structures. Electrical resistance measurements proved the efficiency of α-Ag₂WO₄ nanorods, which rendered good sensitivity even for a low ozone concentration (80 ppb), a fast response and a short recovery time at 300 °C, demonstrating great potential for a variety of applications.

Potentiated electron transference in α-Ag2WO4 microcrystals with Ag nanofilaments as microbial agent.

This study is a framework proposal for understanding the antimicrobacterial effect of both α-Ag2WO4 microcrystals (AWO) synthesized using a microwave hydrothermal (MH) method and α-Ag2WO4 microcrystals with Ag metallic nanofilaments (AWO:Ag) obtained by irradiation employing an electron beam to combat against planktonic cells of methicillin-resistant Staphylococcus aureus (MRSA). These samples were characterized by X-ray diffraction (XRD), FT-Raman spectroscopy, ultraviolet visible (UV-vis) measurements, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). The results reveal that both AWO and AWO:Ag solutions have bacteriostatic and bactericidal effects, but the irradiated sample is more efficient; i.e., a 4-fold of the MRSA planktonic cells as compared to the nonirradiated sample was observed. In addition, first principles calculations were performed to obtain structural and electronic properties of AWO and metallic Ag, which provides strong quantitative support for an antimicrobacterial mechanism based on the enhancement of electron transfer processes between α-Ag2WO4 and Ag nanoparticles.

Structural and electronic analysis of the atomic scale nucleation of Ag on α-Ag2WO4 induced by electron irradiation.

In this work, we utilise a combination of theory, computation and experiments to understand the early events related to the nucleation of Ag filaments on α-Ag2WO4 crystals, which is driven by an accelerated electron beam from an electron microscope under high vacuum. The growth process and the chemical composition and elemental distribution in these filaments were analysed in depth at the nanoscale level using TEM, HAADF, EDS and XPS; the structural and electronic aspects were systematically studied in using first-principles electronic structure theory within QTAIM framework. The Ag nucleation and formation on α-Ag2WO4 is a result of the order/disorder effects generated in the crystal by the electron-beam irradiation. Both experimental and theoretical results show that this behavior is associated with structural and electronic changes of the [AgO2] and [AgO4] clusters and, to a minor extent, to the [WO6] cluster; these clusters collectively represent the constituent building blocks of α-Ag2WO4.

Synthesis of BiVO4via oxidant peroxo-method: insights into the photocatalytic performance and degradation mechanism of pollutants

This paper reports the synthesis of monoclinic bismuth vanadate (BiVO4) by the oxidant peroxide method with crystallization under hydrothermal conditions, and its catalytic performance on the photodegradation of pollutants under visible light. The as-synthesized BiVO4 materials were characterized by means of X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy, Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) and scanning electron microscopy (SEM). Hydrothermal treatment above 80 °C was required to obtain pure monoclinic BiVO4 phase by releasing V5+ ions from vanadium peroxo complexes. With the increase in hydrothermal reaction temperature, the particle size decreased. All BiVO4 samples presented large size and shape distribution and band gap of approximately 2.40 eV. The as-prepared BiVO4 catalysts showed high photoactivity for decomposition of model pollutants, methylene blue (MB) and rhodamine B (RhB) dyes, under exposure to visible light. The photodegradation mechanism was evaluated by adding scavengers, DMSO and KBrO3, which were used to probe ˙OH radical and conduction band (CB) electrons, respectively. It was observed that photodegradation of MB and RhB dyes is caused by the action of ˙OH radicals, and that BiVO4 CB electrons do not have reduction potential sufficiently high to reduce dissolved oxygen to O2−˙. It was proven that the indirect mechanism, i.e. ˙OH radical formation, plays the major role on the BiVO4-assisted photodegradation process.

Generation of copper nanoparticles induced by fs-laser irradiation in borosilicate glass

Glasses containing metallic nanoparticles are promising materials for technological applications in optics and photonics. Although several methods are available to generate nanoparticles in glass, only femtosecond lasers allow controlling it three-dimensionally. In this direction, the present work investigates the generation of copper nanoparticles on the surface and in the bulk of a borosilicate glass by fs-laser irradiation. We verified the formation of copper nanoparticles, after heat treatment, by UV-Vis absorption, transmission electron microscopy and electron diffraction. A preferential growth of copper nanoparticles was observed in the bottom of the irradiated region, which was attributed to self-focusing in the glass.

Ion-sensing properties of 1D vanadium pentoxide nanostructures

The application of one-dimensional (1D) V2O5·n H2O nanostructures as pH sensing material was evaluated. 1D V2O5·n H2O nanostructures were obtained by a hydrothermal method with systematic control of morphology forming different nanostructures: nanoribbons, nanowires and nanorods. Deposited onto Au-covered substrates, 1D V2O5·n H2O nanostructures were employed as gate material in pH sensors based on separative extended gate FET as an alternative to provide FET isolation from the chemical environment. 1D V2O5·n H2O nanostructures showed pH sensitivity around the expected theoretical value. Due to high pH sensing properties, flexibility and low cost, further applications of 1D V2O5·n H2O nanostructures comprise enzyme FET-based biosensors using immobilized enzymes.

Relationship between crystal shape, photoluminescence, and local structure in SrTiO 3 synthesized by microwave-assisted hydrothermal method

This paper describes the effect of using different titanium precursors on the synthesis and physical properties of SrTiO3 powders obtained by microwave-assisted hydrothermal method. X-ray diffraction measurements, X-ray absorption near-edge structure (XANES) spectroscopy, field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HRTEM) were carried out to investigate the structural and optical properties of the SrTiO3 spherical and cubelikeshaped particles. The appropriate choice of the titanium precursor allowed the control of morphological and photoluminescence (PL) properties of SrTiO3 compound. The PL emission was more intense in SrTiO3 samples composed of spherelike particles. This behavior was attributed to the existence of a lower amount of defects due to the uniformity of the spherical particles.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

We report herein for the first time a facile synthesis method to obtain SrTi1−xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 °C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (Egap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.