The oxidation of hydroxylamine on Pt-, and Pd-modified Au electrodes in aqueous electrolytes: Electrochemical and in situ spectroscopic studies

The electrooxidation of hydroxylamine, NH2OH, in 0.1 M phosphate buffer (PB, pH = 7) on Pt-, and Pd-modified Au electrodes prepared by galvanic displacement of underpotential deposited Cu, was investigated by electrochemical techniques and three and in situ vibrational probes, substrate-induced surface enhanced Raman scattering, SI-SERS, surface enhanced infrared absorption, SEIRAS, and Fourier transform infrared reflection-absorption, IRAS, spectroscopies. Analyses of the results obtained made it possible to identify at low overpotentials, solution phase (sol) and adsorbed (ads) nitric oxide, NO, as well as solution phase nitrous oxide, N2O. As the potential was increased, the peak(s) ascribed to NO(ads) gained in intensity and new features associated with NO2−(ads) and NO2−(sol) were clearly discerned. Further excursion toward higher potentials yielded an additional peak assigned to NO2(ads). This behavior is analogous to that found for bare Au electrodes in a potential region in which the metal is at least partially oxidized under otherwise the same experimental conditions.

Bone apposition and surface treatment in dental implants: histomorphometric pilot evaluation in rabbits

The surface of dental implants is an important factor for osseointegration process and different methods of surface treatment have been described. Objective: To investigate the bone apposition in implant surface treated with sandblasting and acid-etching. Material and methods: Ten rabbits were selected and received one implant treated with method I in the left tibia and one implant treated with method II in the right tibia. Then, twenty implants were divided in two groups, according to methods of sandblasting and acid-etching (method I and method II). After 7, 14, 30, 45 and 60 days, tibias were retrieved and submitted to histotechnical procedures. The percentages of bone–implant contact (BIC) and bone area between threads (BABT) were determined throughout histomorphometric analysis and bone apposition was detected in implants of both groups. Results: In BABT measurements, an increase was observed after 45 and 60 days in the method II, compared to method I and no differences were found after 7, 14 and 30 days. In BIC measurements, an increase was detected with method II at 45 days when compared to method I. No differences between groups in BIC values were observed after 7, 14, 30 and 60 days. Conclusion: Our data demonstrated that implants treated with the method II presented increase in the contact between bone and implant after 45 days compared to method I. Moreover, with concern to bone area between threads, it was observed an increased in the method II after 45 and 60 days. However, both groups can be successfully used as a therapeutic strategy to rehabilitation of edentulous patients. Then, further experiments are needed to evaluate, in depth, the putative differential role of each surface treatment.

Ethanol is inefficient to remove endodontic sealer residues of dentinal surface

Endodontic sealer residues on dentinal surface have negative effects on adhesion of adhesives system and/or can cause discoloration of the dental crown. Objective: To evaluate the efficacy of 95% ethanol in removal of residues of epoxy-based (AH Plus), methacrylate-based (Epiphany SE) or calcium-based (Sealapex) sealers on dentinal surface. Material and methods: Thirty-two bovine incisor dental crown fragments (0.5 mm x 0.5 mm) were treated with 17% EDTA and 2.5% NaOCl. The specimens were divided into three experimental groups (n = 10): G1 (AH Plus), G2 (Epiphany SE) and G3 (Sealapex). In each group was applied a coating of one endodontic sealer type and were left undisturbed for 5 minutes. After this period, the specimens were cleaned with 95% ethanol. The control group was composed by two specimens that did not receive any sealer or cleaning treatment. The sealer residues persistence after cleaning with 95% ethanol was evaluated by scanning electron microscopy (x500) and a score system was applied. Data obtained were analyzed by Kruskal-Wallis and Dunn tests (α = 5%). Results: Moderate amount of endodontic sealer residues were observed in all groups, regardless of the endodontic sealer compositions. G1, G2 and G3 presented similar amount of sealer residues on dentinal surface after cleaning with 95% ethanol (p > 0.05). Conclusion: 95% ethanol was inefficiency to remove completely AH Plus, Epiphany SE and Sealapex residues of sealer-contaminated dentin.

Ethanol is inneficient to remove endodontic sealer residues of dentinal surface

Introduction: Endodontic sealer residues on dentinal surface have negative effects on adhesion of adhesives system and/or can cause discoloration of the dental crown. Objective: To evaluate the efficacy of 95% ethanol in removal of residues of epoxy-based (AH Plus), methacrylate-based (Epiphany SE) or calcium-based (Sealapex) sealers on dentinal surface. Material and methods: Thirty-two bovine incisor dental crown fragments (0.5 mm x 0.5 mm) were treated with 17% EDTA and 2.5% NaOCl. The specimens were divided into three experimental groups (n = 10): G1 (AH Plus), G2 (Epiphany SE) and G3 (Sealapex). In each group was applied a coating of one endodontic sealer type and were left undisturbed for 5 minutes. After this period, the specimens were cleaned with 95% ethanol. The control group was composed by two specimens that did not receive any sealer or cleaning treatment. The sealer residues persistence after cleaning with 95% ethanol was evaluated by scanning electron microscopy (x500) and a score system was applied. Data obtained were analyzed by Kruskal-Wallis and Dunn tests (α = 5%). Results: Moderate amount of endodontic sealer residues were observed in all groups, regardless of the endodontic sealer compositions. G1, G2 and G3 presented similar amount of sealer residues on dentinal surface after cleaning with 95% ethanol (p > 0.05). Conclusion: 95% ethanol was inefficiency to remove completely AH Plus, Epiphany SE and Sealapex residues of sealercontaminated dentin.

Characterization of grazing bifurcation in airfoils with control surface freeplay nonlinearity

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

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica

Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).

On the electrical conductivity of Ti-implanted alumina

Ion implantation of metal species into insulators provides a tool for the formation of thin, electrically conducting, surface layers with experimenter-controlled resistivity. High energy implantation of Pt and Ti into alumina accelerator components has been successfully employed to control high voltage surface breakdown in a number of cases. In the work described here we have carried out some basic investigations related to the origin of this phenomenon. By comparison of the results of alumina implanted with Ti at 75 keV with the results of prior investigations of polymers implanted with Pt at 49 eV and Au at 67 eV, we describe a physical model of the effect based on percolation theory and estimate the percolation parameters for the Ti-alumina composite. We estimate that the percolation dose threshold is about 4 x 10(16) cm(-2) and the maximum dose for which the system remains an insulator-conductor composite is about 10 x 10(16) cm(-2). The saturation electrical conductivity is estimated to be about 50 S/m. We conclude that the observed electrical conductivity properties of Ti-implanted alumina can be satisfactorily described by percolation theory. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3697900]

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

Ab initio studies of pristine and oxidized Cu3Au(100) and (111) surfaces

We review the previous literature and our recent work on first-principles studies of Cu3Au(100) and (111) surfaces, with focus on the segregation of atomic species to the surface at pristine conditions and in the presence of oxygen. In particular, the combined use of experimental and theoretical tools to achieve chemical identification at an atomic level of the surface species is emphasized and discussed.

Electrocatalytic Activity of Pd, Pt, and Rh for the Electro-oxidation of Ethanol in Alkaline Electrolyte: An Online DEMS Study

The electro-oxidation of ethanol was investigated on electrodeposited layers of Pd, Pt, and Rh in alkaline electrolyte. The reaction products were monitored by experiments of online differential electrochemical mass spectrometry (DEMS). Potentiodynamic curves for the ethanol electro-oxidation catalyzed by these three different metal electrocatalysts showed similar onset potentials, but the highest Faradaic current peak was observed for the Pt electrocatalyst. Online DEMS experiments evidenced similar amounts of CO2 for the three different materials, but Pd presented the higher production of ethylacetate (acetic acid). This indicated that the electrochemical oxidation of ethanol on the Pd surface occurred to a higher extent. The formation of methane, which was observed for Pt and Rh, after potential excursions to lower potentials, was absent for Pd. On the basis of the obtained results, it was stated that, on Pt and Rh, the formation of CO2 occurs mainly via oxidation of CO and CH (x,ad) species formed after dissociative adsorption of ethanol or ethoxy species that takes place only at low potentials. This indicates that the dissociative adsorption of ethanol or ethoxy species is inhibited at higher potentials on Pt and Rh. On the other hand, on the Pd electrocatalyst, the reaction may occur via nondissociative adsorption of ethanol or ethoxy species at lower potentials, followed by oxidation to acetaldehyde and, after that, by a further oxidation step to acetic acid on the electrocatalyst surface. Additionally, in a parallel route, the acetaldehyde molecules adsorbed on the Pd surface can be deprotonated, yielding a reaction intermediate in which the carbon-carbon bond is less protected, and therefore, it can be dissociated on the Pd surface, producing CO2, after potential excursions to higher potentials.

Electro-oxidation of ethanol on Pt/C, Rh/C, and Pt/Rh/C-based electrocatalysts investigated by on-line DEMS

The ethanol electro-oxidation reaction was studied on carbon-supported Pt, Rh, and on Pt overlayers deposited on Rh nanoparticles. The synthesized electrocatalysts were characterized by TEM and XRD. The reaction products were monitored by on-line DEMS experiments. Potentiodynamic curves showed higher overall reaction rate for Pt/C when compared to that for Rh/C. However, on-line DEMS measurements revealed higher average current efficiencies for complete ethanol electro-oxidation to CO2 on Rh/C. The average current efficiencies for CO2 formation increased with temperature and with the decrease in the ethanol concentration. The total amount of CO2, on the other hand, was slightly affected by the temperature and ethanol concentration. Additionally, the CO2 signal was observed only in the positive-going scan, none being observed in the negative-going scan, evidencing that the C-C bond breaking occurs only at lower potentials. Thus, the formation of CO2 mainly resulted from oxidative removal of adsorbed CO and CHx,ad species generated at the lower potentials, instead of the electrochemical oxidation of bulk ethanol molecules. The acetaldehyde mass signal, however, was greatly favored after increasing the ethanol concentration from 0.01 to 0.1 mol L-1, on both electrocatalysts, indicating that it is the major reaction product. For the Pt/Rh/C-based electrocatalysts, the Faradaic current and the conversion efficiency for CO2 formation was increased by adjusting the amount of Pt on the surface of the Rh/C nanoparticles. The higher conversion efficiency for CO2 formation on the Pt1Rh/C material was ascribed to its faster and more extensive ethanol deprotonation on the Pt-Rh sites, producing adsorbed intermediates in which the C-C bond cleavage is facilitated. (C) 2012 Elsevier B.V. All rights reserved.

Chemical Selectivity during the Electro-Oxidation of Ethanol on Unsupported Pt Nanoparticles

In this paper we present results on the electro-oxidation of ethanol on unsupported (carbon free) platinum nanoparticles, considering the effects of the alcohol concentration. The case of the so-called dual pathway mechanism during the electro-oxidation of ethanol showed to be influenced by the surface coverage of adsorbed carbon monoxide (COad) at unsupported platinum. The influences of adsorbed intermediates were followed by in situ infrared spectroscopy (FTIR) and by electrochemical experiments. Unsupported platinum showed that the reaction leads to the formation of CO2 and acetic acid as main products at low concentrations of ethanol (0.01 to 0.1 mol L-1). At least in this case of 0.01 mol L-1 ethanol, most formation of CO2 occurred via COad (indirect pathway). At higher concentration of ethanol, however, most CO2 was formed via a reactive intermediate such as acetaldehyde (direct pathway). In addition, in this higher concentration of ethanol, the acetic acid was produced via formation of adsorbed acetaldehyde (via acetate) at higher overpotentials. In case of the acetic acid formation, a dual pathway was identified during the electro-oxidation of ethanol at low alcohol concentrations, whereas a parallel pathway occurred without the formation of adsorbed acetate intermediates at low overpotentials. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.101203jes] All rights reserved.

Influence of Modifications to the Pechini Method on the Electroactivity and Stability of Pt-RuOx/C Catalysts

Since electrode electroactivity and stability depend directly on the nature, morphology, and structure of the material, we have investigated how modifications to the Pechini method during the synthesis of Pt-RuOx/C electrocatalysts affected catalyst activity. The structure and stability of the resulting materials were investigated after their submission to a large number of potential scans and to constant potential for a prolonged time period in sulfuric acid 0.5 mol L-1 and methanol 0.1 mol L-1 solution. DMFC tests were accomplished using membrane electrode assemblies (MEAs) prepared by hot-pressing a pretreated Nafion 117 membrane together with the prepared Pt-RuOx anodes and a Pt cathode (from E-TEK), in order to compare the catalytic activity of the materials prepared by different methods. The stability studies demonstrated that the catalyst whose resin/carbon support mixture was agitated in a balls mill before undergoing heat-treatment was more stable than the other prepared catalysts. The catalysts synthesized with the single resin consisting of Pt and Ru and subjected to ultrasound before heat-treatment furnished the highest power density in the single fuel cell. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.011208jes]

Impact of the Manaus urban plume on trace gas mixing ratios near the surface in the Amazon Basin: Implications for the NO-NO2-O-3 photostationary state and peroxy radical levels

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s) < 11 Mm(-1) and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application-Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)-3.0).