Degradation of dipyrone via advanced oxidation processes using a cerium nanostructured electrocatalyst material

This work studied the degradation of dipyrone, via electrochemical processes and via electro-Fenton reaction using a 4% CeO2/C gas diffusion electrode (GDE) prepared via modified polymeric precursor method. This material was used to electrochemically generate H2O2 through oxygen reduction. The mean crystallite sizes estimated by the Scherrer equation for 4% CeO2/C were 4 nm for CeO2-x (0 4 4) and 5 nm for CeO2 (1 1 1) while using transmission electron microscopy (TEM) the mean nanoparticle size was 5.4 nm. X-ray photoelectron spectroscopy (XPS) measurements revealed nearly equal concentrations of Ce(III) and Ce(IV) species on carbon, which contained high oxygenated acid species like CO and OCO. Electrochemical degradation using Vulcan XC 72R carbon showed that the dipyrone was not removed during the two hour electrolysis in all applied potentials by electro-degradation. Besides, when the Fenton process was employed the degradation was much similar when using cerium catalysts but the mineralization reaches just to 50% at -1.1 V. However, using the CeO2/C GDE, in 20 min all of the dipyrone was degraded with 26% mineralization at -1.3 V and when the Fenton process was employed, all of the dipyrone was removed after 5 min with 57% mineralization at -1.1 V. Relative to Vulcan XC72R, ceria acts as an oxygen buffer leading to an increase in the local oxygen concentration, facilitating H2O2 formation and consequently improving the dipyrone degradation © 2013 Elsevier B.V. All rights reserved.

The electro-oxidation of carbon monoxide and ethanol on supported Pt nanoparticles: The influence of the support and catalyst microstructure

The sluggish kinetics of ethanol oxidation on Pt-based electrodes is one of the major drawbacks to its use as a liquid fuel in direct ethanol fuel cells, and considerable efforts have been made to improve the reaction kinetics. Herein, we report an investigation on the effect of the Pt microstructure (well-dispersed versus agglomerated nanoparticles) and the catalyst support (carbon Vulcan, SnO2, and RuO2) on the rate of the electrochemical oxidation of ethanol and its major adsorbed intermediate, namely, carbon monoxide. By using several structural characterization techniques such as X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy, along with potentiodynamic and potentiostatic electrochemical experiments, we show that by altering both the Pt microstructure and the support, the rate of the electrochemical oxidation of ethanol can be improved up to a factor of 12 times compared to well-dispersed carbon-supported Pt nanoparticles. As a result of a combined effect, the interaction of Pt agglomerates with SnO2 yielded the highest current densities among all materials studied. The differences in the activity are discussed in terms of structural and electronic properties as well as by mass transport effects, providing valuable insights to the development of more active materials. © 2013 Springer-Verlag Berlin Heidelberg.

Photoelectrocatalytic oxidation of hair dye basic red 51 at W/WO 3/TiO2 bicomposite photoanode activated by ultraviolet and visible radiation

We prepared a W/WO3/TiO2 bicomposite photoanode by simple electrochemical anodization of W foil, followed by cathodic electrodeposition of TiO2 and annealing at 450 C for 30 min. This photoanode shows good photoactivity under irradiation with UV and visible light. In optimized conditions, it promotes complete photoelectrocatalytic oxidation of 3.33 × 10-5 mol L-1 basic red 51 solution (which is used in hair dye) at 0.1 mol L-1 Na2SO4, pH 2.0, under a current density of 1.25 mA cm-2 and ultraviolet and visible radiation-total organic carbon removal is 94 and 88%, respectively. This effect paves the way for the sustainable solar-assisted remediation of water bodies contaminated with organic components of hair dyes. © 2013 Elsevier Ltd. All rights reserved.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. All rights reserved.

Deposition of Al2O3 by resistive evaporation and thermal oxidation of Al to be applied as a transparent FET insulating layer

Alumina thin films have been obtained by resistive evaporation of Al layer, followed by thermal oxidation by means of annealing in appropriate atmosphere (air or O2-rich), with variation of annealing time and temperature. Optical and structural properties of the investigated films reveal that the temperature of 550 °C is responsible for reasonable oxidation, which is accelerated up to 8 times for O2-rich atmosphere. Results of surface electrical resistivity and Raman spectroscopy are in good agreement with these findings. Surprisingly, X-ray and Raman data suggest also the crystallization of Si nuclei at glass substrate-alumina interface, which would come from the soda-lime glass used as substrate. © 2013 Elsevier Ltd and Techna Group S.r.l.

Tribocorrosion behaviour of anodic treated titanium surfaces intended for dental implants

Tribocorrosion plays an important role in the lifetime of metallic implants. Once implanted, biomaterials are subjected to micro-movements in aggressive biological fluids. Titanium is widely used as an implant material because it spontaneously forms a compact and protective nanometric thick oxide layer, mainly TiO2, in ambient air. That layer provides good corrosion resistance, and very low toxicity, but its low wear resistance is a concern. In this work, an anodizing treatment was performed on commercial pure titanium to form a homogeneous thick oxide surface layer in order to provide bioactivity and improve the biological, chemical and mechanical properties. Anodizing was performed in an electrolyte containing β-glycerophosphate and calcium acetate. The influence of the calcium acetate content on the tribocorrosion behaviour of the anodized material was studied. The concentration of calcium acetate in the electrolyte was found to largely affect the crystallographic structure of the resulting oxide layer. Better tribocorrosion behaviour was noticed on increasing the calcium acetate concentration. © 2013 IOP Publishing Ltd.

Caracterização eletroquímica de filmes anódicos de titânio grau 2 visando aplicações biomédicas

Pós-graduação em Engenharia Mecânica - FEG

Síntese, caracterização e avaliação eletroquímica de nanopartículas intermetálicas ordenadas PtSb e PtSn

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Estudo eletroquímico e termoanalítico dos sistemas Ir/Hg e Pt - (30%) Ir/Hg

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of the balance between Co(II) and Co(0) oxidation states on the catalytic activity of cobalt catalysts for Ethanol Steam Reforming

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoelectrochemical Hydrogen Generation and Concomitant Organic Dye Oxidation under TiO2 Nanotube

The present work describes the photoelectrochemical hydrogen generation during a photodegradation of an organic compound. For this, it was chosen the reactive black 5 dye as a model of organic pollutant and its oxidation under TiO2 nanotube in a two compartment cell. The photoelectrocatalysis is conducted in 0.1 mol L-1 Na2SO4 pH 6 medium under photoanode biased at +1.0 V (SCE) and activated by UV and visible light using 150W Xe-Arc lamp (Oriel) and 125 W Hg lamp (Osram). The concomitant hydrogen production was monitored at cathodic compartment using a Pt cathode. Using optimized condition of Na2SO4 0.1 mol L-1 pH 6 as supporting electrolyte, applied potential of +1.0V it was verified 100% of discoloration and 72% of TOC removal of 1.0 x 10(-5) mol L-1 Reactive Black 5 dye after 120 min of treatment (rate constant of 10.6 x10(-2) min(-1)). The concomitant hydrogen generation was 44% in this condition.

Long-Lasting Oscillations in the Electro-Oxidation of Formic Acid on PtSn Intermetallic Surfaces

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Magnetocrystalline interactions and oxidation state determination of Mn(2-x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family

Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2-x)V(1+x)O4 (x=0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2-x)V(1+x)O4 (x=0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution K beta X-ray fluorescence spectra. The ionic models found are Mn22+V4+O4, Mn5/32+V4/33.5+O4 and Mn2+V23+O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques. (c) 2013 Elsevier Inc. All rights reserved.

Influence of Lentinus edodes and Agaricus blazei extracts on the prevention of oxidation and retention of tocopherols in soybean oil in an accelerated storage test

This study aimed to evaluate the influence of the methanol extracts of mushrooms Lentinus edodes and Agaricus blazei on the retention of tocopherols in soybean oil, when subjected to an accelerated storage test. The following treatments were subjected to an accelerated storage test in an oven at 60 A degrees C for 15 days: Control (soybean oil without antioxidants), TBHQ (soybean oil + 100 mg/kg of TBHQ), BHT (soybean oil + 100 mg/kg of BHT), L. edodes (soybean oil + 3,500 mg/kg of L. edodes extract) and A. blazei (soybean oil + 3,500 mg/kg of A. blazei extract). The samples were analyzed for tocopherols naturally present in soybean oil and mass gain. The results showed, the time required to reach a 0.5% increase in mass was 13 days for TBHQ and 15 days for A. blazei. The content of tocopherols for TBHQ was 457.50 mg/kg and the A. blazei, 477.20 mg/kg.

Treatment of Reticulated Vitreous Carbon by Dielectric Barrier Discharge Plasma for Electrodes Production

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)