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.

Electrocatalysis of oxidation of hydrogen on platinum ordered intermetallic phases: Kinetic and mechanistic studies

An experimentally based kinetic and mechanistic study of the hydrogen oxidation reaction (HOR) on platinum and platinum ordered intermetallic materials in acid medium is presented. RDE kinetic data were re-evaluated and complemented by Tafel plots obtained from chronoamperometric measurements. Among the materials evaluated, PtSb and PtSn exhibited markedly improved kinetic current densities and exchange current densities, compared to Pt in the same experimental conditions. It is proposed that the intermetallic phase enhanced the adsorptive characteristic of the surface sites and, as a consequence, improved the kinetics of the adsorption steps (Tafel or Heyrovsky) of the mechanism involved. (c) 2006 Published by Elsevier B.V.

The Fabrication and Characterization of a Nickel Nanoparticle Modified Boron Doped Diamond Electrode for Electrocatalysis of Primary Alcohol Oxidation

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

Electrocatalysis of hydrogen evolution reaction on Pt electrode surface-modified by S-2 chemisorption

Kinetic studies of hydrogen evolution reaction (HER) at the surface of Pt in alkaline conditions, reported in this paper, show that electrocatalytic activity is enhanced after adsorption of S-2 ions. EIS and steady-state polarization curve data pointed to an undoubted improvement in performance with the Pt-S cathode that was attributed to higher adsorbed hydrogen coverage. Experimental findings suggested an increase in the electronic density of the modified surface sites that may strengthen the interaction between H2O and the adsorption site and, consequently, accelerates the Volmer step. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

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.

Electrochemical modified electrodes based on metal-salen complexes

A general view of the electroanalytical applications of metal-salen complexes is discussed in this review. The family of Schiff bases derived from ethylenediamine and ortho-phenolic aldehydes (N,N'-ethylenebis(salicylideneiminato) - salen) and their complexes of various transition metals, such as Al, Ce, Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo, Ni, and V have been used in many fields of chemical research for a wide range of applications such as catalysts for the oxygenation of organic molecules, epoxidation of alkenes, oxidation of hydrocarbons and many other catalyzed reactions; as electrocatalyst for novel sensors development; and mimicking the catalytic functions of enzymes. A brief history of the synthesis and reactivity of metal-salen complexes will be presented. The potentialities and possibilities of metal-Salen complexes modified electrodes in the development of electrochemical sensors as well as other types of sensors, their construction and methods of fabrication, and the potential application of these modified electrodes will be illustrated and discussed.

ZnO-TiO2 composite formed by mixed oxides via polyol

Among the researches on preparation and test of nanostructured materials, titanium dioxide and zinc oxide have been the most frequent studied oxides. In order to extend their properties, composites have been prepared using three different methods: Polyol Method, Sol-gel Process and a combination of the two processes (hybrid process). Recent research showed best properties in composite materials than in pure oxides. In this work is presented the preparation and the structural characterization of ZnO-TiO2 composite nanostructures to be tested for their performance in electrocatalysis and in further trial on photovoltaic cells.

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)

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.

Well-Alloyed PtFe/C Nanocatalysts of Controlled Composition and Same Particle Size: Oxygen Reduction and Methanol Tolerance

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

The Determination of Methanol Using an Electrolytically Fabricated Nickel Microparticle Modified Boron Doped Diamond Electrode

A nickel modified boron doped diamond (Ni-BDD) electrode and nickel foil electrode were used in the determination of methanol in alkaline solutions. The Ni-BDD electrode was electrodeposited from a 1 mM Ni(NO(3))(2) solution (pH 5), followed by repeat cycling in KOH. Subsequent analysis utilised the Ni(OH)(2)/NiOOH redox couple to electrocatalyse the oxidation of methanol. Methanol was determined to limits of 0.3 mM with a sensitivity of 110 nA/mM at the Ni-BDD electrode. The foil electrode was less sensitive achieving a limit of 1.6 mM and sensitivity of 27 nA/mM. SEM analysis of the electrodes found the Ni-BDD to be modified by a quasi-random microparticle array.

Voltammetric determination of persulfate anions using an electrode modified with a Prussian blue film

Prussian blue [PB, iron(III) hexacyanoferrate(II)] films are effective for the electrocatalysis of the persulfate (peroxodisulfate)/sulfate redox system. This has been exploited in the voltammetric determination of persulfate anions using a PB-modified platinum disc electrode. A linear correlation between electrocatalytic current and persulfate concentration was found for the range 5 x 10(-5) to 3 x 10(-3) mol dm(-3), using 0.100 mol dm(-3) potassium chloride as supporting electrolyte at pH 4. This analytical method has the advantages of speed and ease of operation in relation to traditional titrimetric methods for persulfate determination. The applicability of the method to the determination of persulfate in a commercial hair bleaching 'booster' product is demonstrated. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Structural and surface properties of thermally prepared Ti/RhxTi(1-x)Oy electrodes: I - influence of preparation parameters

Electrodes of RhxTi(1-x) O-y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Tidegrees support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H2O)(6)](NO3)(3) precursor dissolved in HNO3 1:2 (v/v) and fired at 430 degreesC for 2 h in a 5 1 min (-1) oxygen stream-furnished stable electrodes having the highest electrochemically active surface area. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Electrooxidation and determination of dopamine using a Nafion (R)-cobalt hexacyanoferrate film modified electrode

The electrocatalysis of dopamine has been studied using a cobalt hexacyanoferrate film (CoHCFe)-modified glassy carbon electrode. Using a rotating disk CoHCFe-modified electrode, the reaction rate constant for dopamine was found to be 3.5 x 105 cm(3) mol(-1) s(-1) at a concentration of 5.0 x 10(-5) mol L-1. When a Nafion (R) film is applied to the CoHCFe-modified electrode surface a high selectivity for the determination of dopamine over ascorbic acid was obtained. The analytical curve for dopamine presented linear dependence over the concentration range from 1.2 x 10(-5) to 5.0 x 10(-4) mol L-1 with a slope of 23.5 mA mol(-1) L and a linear correlation coefficient of 0.999. The detection limit of this method was 8.9 x 10(-6) mol L-1 and the relative standard deviation for five measurements of 2.5 x 10(-4) mol L-1 dopamine was 0.58%.

Methanol oxidation on PtRu/C electrocatalysts prepared by a microemulsion method

PtRu/C nanocatalysts were prepared by a microemulsion method using different values of water/surfactant molar ratio in order to get different particle sizes. Crystallite sizes and structural properties were determined by X-ray diffraction. Particle size and distribution were characterized by transmission electron microscopy and average composition was determined by energy dispersive X-ray analysis. Differential scanning calorimetry measurements indicated the presence of oxides in the as-prepared catalysts. The general electrochemical behavior was evaluated by cyclic voltammetry in 0.5 M sulfuric acid and the electrocatalytic activity towards the oxidation of methanol was studied in 0.5 M methanol acid solutions by potential sweeps and chronoamperometry. copyright The Electrochemical Society.