Synthesis and Characterization of Ordered Intermetallic Nanostructured PtSn/C and PtSb/C and Evaluation as Electrodes for Alcohol Oxidation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

Hydrogen oxidation on ordered intermetallic electrodes covered with CO

This describes an experimental evaluation of the electrocatalytic activity of the hydrogen oxidation reaction on electrodes of platinum and the ordered intermetallic phases PtSb and PtSn, on which CO has previously been deposited. The experiments were carried out in perchloric acid solution and the analysis based on steady-state polarization curves and Tafel plots derived from chronoamperometric data. Both intermetallics, PtSb and PtSn, performed better than Pt towards the HOR, when their surface was deliberately covered with CO. It is suggested that the intermetallic surfaces have a lower affinity for CO molecules, causing a lower CO coverage on these surfaces, and/or a weaker surface-CO interaction, compared to Pt under the same conditions. (C) 2007 Elsevier B.V. All rights reserved.

The hydrogen evolution reaction on codeposited Ni-hydrogen storage intermetallic particles in alkaline medium

The hydrogen evolution reaction (HER) was studied on Ni-LaNi5 and Ni-MmNi(3.4)Co(0.8)Al(0.8) electrode materials in 1 mol dm(-3) NaOH solution. The steady-state polarization curves and electrochemical impedance spectroscopy experimental data showed a pronounced improvement in HER kinetics when these electrode materials were used. The electrochemical results are in accordance with the Volmer-Heyrovsky mechanism. The kinetic results indicate a more effective improvement in the Heyrovsky step, suggesting an electrocatalytic synergistic effect of the hyper-electronic character of the Ni and the hypo-electronic character of the rare-earth element on the electrode surface. (C) 2000 International Association for Hydrogen Energy. Published by Elsevier B.V. Ltd. All rights reserved.

A surface modification for hydrogen storage intermetallic particles by sol-gel method

A new process for the surface modification of hydrogen storage intermetallic particles used as anode material in secondary batteries is proposed in this article. The copper oxide particles coverage obtained by the sol-gel method is proposed to produce, under operational conditions of a Ni-MH battery, a metallic framework that tolerates the volume changes in charge/discharge cycles and does not inhibit the hydrogen absorption. Furthermore it was noticed an enhancement on the discharge capacity of the electrode material that can be related to a new hydrogen storage phase or to an inhibition of the surface oxidation promoted by the film coverage.

Electrocatalytic activity under oscillatory regime: The electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase

Despite the considerable progress in the understanding of the mechanistic aspects of the oscillatory electro-oxidation of C1 molecules, there are apparently no systematic studies concerning the impact of surface modifiers on the oscillation dynamics. Herein we communicate on the oscillatory electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase, and compare the results with those obtained on a polycrystalline platinum electrode. Overall, the obtained results were very reproducible, robust and allowed a detailed analysis on the correlation between the catalytic activity and the oscillation dynamics. The presence of Sn in the intermetallic electrode promotes drastic effects on the oscillatory dynamics. The decrease in the mean electrode potential and in the oscillation frequency, as well as the pronounced increase in the number oscillations (and also in the oscillation time), was discussed in connection with the substantial catalytic enhancement of the Pt3Sn towards the electro-oxidation of formic acid. The self-organized potential oscillations were used to probe the electrocatalytic activity of the Pt3Sn electrode and compare it with that for polycrystalline Pt. The presence of Sn resulted in a significant decrease (2-11 times, depending on the applied current) of the rate of surface poisoning. © 2012 Elsevier B.V.

Hydrogen oxidation on ordered intermetallic phases of platinum and tin - A combined experimental and theoretical study

Hydrogen oxidation on the surfaces of the intermetallic compounds Pt 3Sn, PtSn and PtSn2 has been studied by the rotating disc electrode technique. Pt3Sn and PtSn were found to be good catalysts, about as good as Pt, while PtSn2 was inactive over the investigated range of potentials. Underpotential deposition of hydrogen is observed only on Pt3Sn. These results are explained by theoretical calculations based on a theory developed within our own group, and by density functional theory. © 2012 Elsevier B.V.

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

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Some properties of intermetallic compounds of Sn with noble metals relevant for hydrogen electrocatalysis

Using density functional theory and a model developed in our own group, we have investigated the suitability of three intermetallic compounds - AuSn, PdSn, and PtSn - as electrode materials for hydrogen oxidation in fuel cells, focusing on their CO tolerance and their catalytic properties. All three metals were found to have lower susceptibility to be poisoned by CO compared to platinum, but only PtSn promises to be a good catalyst for hydrogen oxidation. (C) 2013 Elsevier Ltd. All rights reserved.

A Solid Film Electrode of Intermetallic Ag 2 Hg 3.02 for the Direct Determination of Folic Acid in Fresh and Processed Fruit Juices

AgSIE was used for the direct analysis of folic acid (FA), with a detection limit and lower level of quantitation of 6.8 x10-10 mol L-1 and 2.3 x 10 8 mol L-1. The analysis in fresh and processed fruits was done without any sample pretreatment. In strawberry and acerola juices, FA concentration level values were below the method detection limit. FA was detectable in peach (77.7 0.4 mg L-1 and 64.4 0.5 mgL-1), Persian lime (45.4 0.7 mg L-1), pineapple Hawaii (66.2 0.4 mgL-1), pear pineapple (35.3 0.6 mgL-1), cashew (54.4 0.5 mgL-1) , passion fruit (73.2 0.3 mgL-1), and apple (84.4 0.5 mg L-1 ).

Study of elastic properies of Ti3Al intermetallic compound using the ab initio calculation

The elastic properties of a Ti3Al intermetallic compound were studied using full potential (FP LAPW ) with the APW+lo method. The FP-LAPW is among the most accurate band structure calculations currently available and is based on the density functional theory with general gradient approximation for the exchange and correlation potential. This method provides the structural properties of the ground state as bulk modulus, equilibrium lattice parameter, and equilibrium minimum energy, and the elastic properties as shear modulus, young modulus, Zener coefficient (anisotropy), and Poisson coefficient. The calculated elastic properties are coherent with the elastic properties of the material.

Obtaining NiAl intermetallic compound using different milling devices

NiAl intermetallic compound was synthesized by mechanical alloying technique in planetary and attritor mills. The starting powders consisted of elemental mixtures of Ni and Al at Ni50Al50(at%) composition. In the planetary mill, compound formation occurred gradually during mechanical alloying, while the occurrence of a mechanically induced self-propagating reaction (MSR) can be suggested in the attritor mill. The NiAl obtained in both mill types was partially disordered with long-range order parameter not inferior to 0.66. Quantitative phase analysis using the Rietveld method was performed in as-milled samples, and this method was also employed to estimate changes in crystallite size and lattice strain of the NiAl produced during mechanical alloying. (C) 2011 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

Structure and properties of intermetallic ternary rare earth compounds

The so called material science is an always growing field in modern research. For the development of new materials not only the experimental characterization but also theoretical calculation of the electronic structure plays an important role. A class of compounds that has attracted a great deal of attention in recent years is known as REME compounds. These compounds are often referred to with RE designating rare earth, actinide or an element from group 1 - 4, M representing a late transition metal from groups 8 - 12, and E belonging to groups 13 - 15. There are more than 2000 compounds with 1:1:1 stoichiometry belonging to this class of compounds and they offer a broad variety of different structure types. Although many REME compounds are know to exist, mainly only structure and magnetism has been determined for these compounds. In particular, in the field of electronic and transport properties relatively few efforts have been made. The main focus in this study is on compounds crystallizing in MgAgAs and LiGaGe structure. Both structures can only be found among 18 valence electron compounds. The f electrons are localized and therefor not count as valence electrons. A special focus here was also on the magnetoresistance effects and spintronic properties found among the REME compounds. An examination of the following compounds was made: GdAuE (E = In, Cd, Mg), GdPdSb, GdNiSb, REAuSn (RE = Gd, Er, Tm) and RENiBi (RE = Pr, Sm, Gd - Tm, Lu). The experimental results were compared with theoretic band structure calculations. The first half metallic ferromagnet with LiGaGe structure (GdPdSb) was found. All semiconducting REME compounds with MgAgAs structure show giant magnetoresistance (GMR) at low temperatures. The GMR is related to a metal-insulator transition, and the value of the GMR depends on the value of the spin-orbit coupling. Inhomogeneous DyNiBi samples show a small positive MR at low temperature that depends on the amount of metallic impurities. At higher fields the samples show a negative GMR. Inhomogeneous nonmagnetic LuNiBi samples show no negative GMR, but a large positive MR of 27.5% at room temperature, which is interesting for application.