Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

On the apparent lack of preferential site occupancy and electrooxidation of CO adsorbed at low coverage onto stepped platinum surfaces

We report time evolution studies of low coverage CO adsorption (surface hydrogen site blocking < 40%) and oxidative stripping on stepped Pt(776) and Pt(554) surfaces. It was observed that there is no preferential site occupancy for CO adsorption on step or terrace. It is proposed that CO adsorption onto these surfaces is a random process, and after CO adsorption there is no appreciable shift from CO-(111) to CO-(110) sites. This implies that after adsorption, CO molecules either have a very long residence time, or that the diffusion coefficient is much lower than previously thought. After CO electrooxidation the sites released included both terrace (111) and step (110) orientations. For surface hydrogen site blocking > 40%, the lateral interactions might play a role in the preferential CO site occupancy. (C) 2011 Elsevier B.V. All rights reserved.

Open Circuit Interaction of Formic Acid with Oxidized Pt Surfaces: Experiments, Modeling, and Simulations

We report in this work the study of the interaction between formic acid and an oxidized platinum surface under open circuit conditions. The investigation was carried out with the aid of in situ infrared spectroscopy, and results analyzed in terms of a mathematical model and numerical simulations. It has been found that during the first seconds of the interaction a small amount of CO(2) is produced and absolutely no adsorbed CO was observed. A sudden drop in potential then follows, which is accompanied by a steep increase first of CO(2) production and then by adsorbed CO. The steep transient was rationalized in terms of an autocatalytic production of free platinum sites which enhances the overall rate of reaction. Modeling and simulation showed nearly quantitative agreement with the experimental observations and provided further insight into some experimentally inaccessible variables such as surface free sites. Finally, based on the understanding provided from the combined experimental and theoretical approach, we discuss the general aspects influencing the open circuit transient.

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Ethanol oxidation reactions using SnO(2)@Pt/C as an electrocatalyst

This paper presents a study on the ethanol oxidation reaction using SnO(2)@Pt/C core-shell structures as electrocatalysts. All the materials used, including Pt/C and PtSn/C E-tek, were 20% (w/w) metal on carbon. The formation of core-shell nanoparticles (SnO(2)@Pt/C) was measured by UV-vis spectrophotometry. X-ray diffraction measurements showed Pt (shell) diffraction patterns without influence from the SnO(2) core and without any shift in 2 theta values for Pt. The diameters of the core-shell particle structures, measured using high-resolution transmission electron microscopy images, were in the range of 3-16 nm. The electrochemical profile for SnO(2)@Pt/C in an acidic medium (H(2)SO(4) at a concentration of 0.5 mol L(-1)) was almost the same as the typical electrochemical behavior for Pt in an acidic medium. Furthermore, the onset potential for the ethanol oxidation reaction using SnO(2)@Pt/C was almost the same as that for PtSn/C E-tek (0.23 V versus the reversible hydrogen electrode). However, the mass current peak densities for ethanol oxidation were 50% higher on SnO(2)@Pt/C than on PtSn/C E-tek. In the polarization curve, the mass current density for ethanol oxidation was higher at all potentials for SnO(2)@Pt/C when compared to Pt/C and PtSn/C E-tek. At 0.5 V, the current mass density for ethanol oxidation on SnO(2)@Pt was 2.3 times of that for the same process on the commercial material. The electrocatalytic activity of SnO(2)@Pt/C for ethanol oxidation was associated with an increase in the electrochemically active surface area. However, an electronic effect should also be considered because the Pt shell changes its electronic structure in the presence of the foreign core. (C) 2010 Elsevier B.V. All rights reserved.

Environmental temperature and cloacal and surface temperatures of broiler chicks in first week post-hatch

Adequate environmental temperature during the brooding period is very important to future broiler performance. Thus, the objective of this study was to investigate the extent to which environmental temperature affects the body weight and cloacal and surface (back, head, wing, and shank) temperatures. The study also investigated the sensible heat loss by radiation of broiler chicks reared at three environmental temperatures (35, 25, and 20 degrees C) up to 7 days of life. The results showed that chicks raised at low environmental temperature (20 degrees C) had lower body weight at 7 days of age. Birds kept at 20 degrees C also had significantly lower cloacal and surface temperatures than did other birds. The most marked difference was seen in the shanks. These findings revealed that body weight declined in chicks reared at 20 degrees C, and radiant heat loss (W) was nine times higher than for the birds kept at 35 degrees C at 7 days of age.

Coupling Surface-Enhanced Resonance Raman Scattering and Electronic Tongue as Characterization Tools to Investigate Biological Membrane Mimetic Systems

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

Electrocatalysis on noble metal and noble metal alloys dispersed on high surface area carbon

In this work, a simple route to prepare carbon supported Pt/C, Pt:Ru/C, Pt:Mo/C and Pt:Ru:Mo/C catalysts is reported. The electrochemical properties of the several carbon materials used as substrates in the absence and in the presence of supported platinum and platinum alloys catalysts were investigated using cyclic voltammetry and employing the thin porous coating electrode technique. The activity of the dispersed catalysts composed of Pt/C with respect to the oxygen reduction and of alloy/C with respect to methanol oxidation was investigated using steady state polarization measurements. The performance with respect to the oxygen reduction reaction of the Pt/C catalyst prepared on heat-treated Vulcan carbon substrate is equivalent to that reported in the literature for the state-of-the-art electrocatysts. Pt:Ru:Mo/C samples prepared in this work presented the higher catalytic effect for methanol electro-oxidation.

Synthesis of slightly < 111 >-oriented 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) ceramic prepared from fine powders

Slightly < 111 >-oriented 0.65Pb(Mg1/3Nb2/3)03-0.35PbTiO(3) ceramic was prepared using fine powders obtained by means of an alternative and promising chemical oxide precursor method. High quality samples with improved structural, microstructural, dielectric and ferroelectric properties were obtained. The dielectric constant value (epsilon similar to 2577) measured at 1 kHz is compared to unpoled < 112 > grain-oriented ceramics while the remanent polarization (P-r similar to 19-1 mu cm(-2)) is compared with random grain-oriented ceramics. These results point out the viability to produce ferroelectric PMN-PT ceramics of very good quality using powder precursors prepared from this chemical method. (c) 2007 Elsevier B.V. All rights reserved.

Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves

In Vitro Evaluation of Surface Roughness and Microhardness of Restorative Materials Submitted to Erosive Challenges

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

Thermal and electrochemical study of solid-state reaction of mercury with Pt-20% Rh alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influence of Surface Treatment on the Shear Bond Strength of Ceramics Fused to Cobalt-Chromium

Purpose: To evaluate the influence of surface treatment on the shear bond strength between a Co-Cr alloy and two ceramics.Materials and Methods: Forty-eight metal cylinders were made (thickness: 4 mm, height: 3.7 mm) according ISO TR 11405. The 48 metallic cylinders were divided into four groups (n = 12), according to the veneering ceramic (StarLight Ceram and Duceram Kiss) and surface treatments: air-particle abrasion with Al(2)O(3) or tungsten drill (W). Gr1: StarLight + Al(2)O(3); Gr2: StarLight + W; Gr3: Duceram + Al(2)O(3); and Gr4: Duceram + W. The specimens were aged using thermal cycling (3000 x, 5 to 55 degrees C, dwell time: 30 seconds, transfer time: 2 seconds). The shear test was performed with a universal testing machine, using a load cell of 100 kg (speed: 0.5 mm/min) and a specific device. The bond strength data were analyzed using ANOVA and Tukey's test (5%), and the failure modes were analyzed using an optical microscope (30x).Results: The means and standard deviations of the shear bond strengths were (MPa): G1 (57.97 +/- 11.34); G2 (40.62 +/- 12.96); G3 (47.09 +/- 13.19); and G4 (36.80 +/- 8.86). Ceramic (p = 0.03252) and surface treatment (p = 0.0002) significantly affected the mean bond strength values.Conclusions: Air-particle abrasion with Al(2)O(3) improved the shear bond strength between metal and ceramics used.

Carbon-supported Pt-Co catalysts prepared by a modifled polyol process as cathodes for PEM fuel cells

In this work, carbon-supported Pt70Co30 nanoparticles were prepared by a polyol process using a long-chain diol as reducer (hexadecanediol) and oleic acid and oleylamine as stabilizers. Depending on the synthesis conditions, Pt70Co30/C nanocatalysts with very small particle size (1.9 +/- 0.2 nm) and narrow distribution homogeneously dispersed on the carbon support and having a high degree of alloying without the need of thermal treatments were obtained. The as-prepared catalyst presents an excellent performance as proton exchange membrane fuel cells (PEMFC) cathode material. In terms of mass activity (MA), the Pt70Co30/C electrocatalysts produced single fuel cell polarization response superior to that of commercial catalyst. To analyze alloying effects, the result of thermal treatment at low temperatures (200-400 degrees C) was also evaluated and an increase of average crystallite size and a lower degree of alloying, probably associated to cobalt oxidation, were evidenced.

The influence of thermal treatment on the preparation of PNM and PMN-PT thin films

Ferroelectric thin films belong to a class of materials with great technological importance in optic fibers, micro-electromechanical systems, and microprocessors and computers memories.The (1-x)PbMg1/3Nb2/3O3(x)PbTiO3 (PMN-PT) thin films, with x=0, 0.1, 0.35 and 0.5, were prepared by Pechini's process and deposited by spin-coating on Si(100), Pt/Ti/SiO2/Si(100) and quartz substrates. The goal of the present paper is to verify the thermal treatment influence on the perovskite phase formation, which is desirable for these applications. The phase formation was analyzed by X-ray diffraction. The film's surface was characterized by atomic force microscopy to analyze the roughness and the homogeneity. The results of this study indicate that the optimum conditions for obtaining the perovskite phase using a Pt/Ti/SiO2/Si(100) substrate, were drying each deposited layer at 140 degreesC (heating plate), and a final thermal treatment at 600 degreesC for 3 h in a closed system with a lead-rich atmosphere. (C) 2003 Elsevier B.V. All rights reserved.