Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Utilization of electrochemical impedance spectroscopy for monitoring bornite (CU5FeS4) oxidation by Acidithiobacillus ferrooxidans

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

Effects of thickness coating on the electrochemical behaviour of thermal spray Cr3C2-NiCr coatings

Thermally sprayed HVOF coatings are increasingly being used in industrial applications where high wear and corrosion resistance are needed [1,2]. In this paper, electrochemical ac and de experiments were used in order to obtain the corrosion resistance of coated steel with different numbers of Cr3C2-NiCr layers. This work has been performed in order to determine the role of coating thickness in the corrosion behaviour of a steel protected with cermet thermally sprayed coatings. It is known that a thicker layer protects better against corrosion when a metallic coating is evaluated. But cermet coatings, such as Cr3C2-NiCr, contain higher levels of porosity and residual stresses than metallic coatings, which really could influence the corrosion resistance of the deposited layer. Electrochemical measurements, such as Open-Circuit Potential (E-Osubset of), Polarisation Resistance (RP) and Cyclic Voltammetry (CV), were performed in an aerated 3.4 NaCI media (%wt.). Electrochemical Impedance Measurements (EIS) were also done in order to obtain a mechanism that explains the corrosion process. Structural Characterisation was carried out by means of Optical and Scanning Electron Microscopes (OM, SEM) with an Energy Dispersive Spectrometry analyser (EDS). Results show that the corrosion resistance of the complete system is mainly influenced by the substrate behaviour. The application of a higher number of deposited layers did not substantially increase their anticorrosive properties. Stress generation during the spraying deposition process plays an important role in the behaviour of the coated steel against corrosion phenomena. (C) 2002 Elsevier B.V. B.V All rights reserved.

Aplicação de técnicas eletroquímicas no estudo da dissolução oxidativa da covelita (CuS) por Thiobacillus ferrooxidans

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

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks. (C) 2007 Elsevier Ltd. All rights reserved.

Microeletrodos: II. Caracterização eletroquímica

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

Electrochemical study of hydroxychloroquine and its determination in plaquenil by differential pulse voltammetry

Hydroxychloroquine (HCQ) is a halogenated aminoquinoline that presents wide biological activity, often being used as an antimalarial drug. The electrochemical reduction of HCQ was investigated by cyclic voltammetry and chronoamperometry using glassy carbon electrodes. By cyclic voltammetry, in acid medium, only the cathodic peak was observed. The electrochemical behavior of this peak is dependent on pH and the electrodic process occurs through an ErCi mechanism. The electron number (le) consumed in the reduction of HCQ was obtained by chronoamperometry. A method for the electrochemical determination of HCQ in pharmaceutical tablets was developed using differential pulse voltammetry. The detection limit reached was 11.2 mug ml(-1) of HCQ with a relative standard deviation of 0.46%. A spectrophotometric study of HCQ has been also carried out utilizing a band at 343 nm. The obtained detection limit and the relative standard deviation were 0.1 mug ml(-1) and 0.36%, respectively. The electrochemical methods are sufficiently accurate and precise to be applied for HCQ determination, in laboratorial routine, which can be used to determine the drug at low level. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

Gamma phases in Cu-Al alloys and the influence of a square shaped phase in the electrochemical behavior of a Cu-13.6wt% Al alloy

The electrochemical behavior of Cu-xAl alloys, with 11 wt%less than or equal to x less than or equal to 15wt%, in 0.5 M H2SO4 was studied by means of open-circuit potential decay measurements, quasi-stationary and fast cyclic voltammetry, and electrochemical impedance spectroscopy. Some of the alloys (x less than or equal to 14%), when quenched formed martensitic structures. Alloys with greater than or equal to 13% showed a little square-shaped phase when quenched from temperatures around 800 degrees C. It was observed that in sulfuric medium, these formations were dealuminized differently than the martensitic phase. The values of the rest potentials are more influenced by the heat treatment rather than by the alloy composition. An anodic Tafel slope of ca. 60 mV/decade was observed for all the alloys, independently of the heat treatment. This is explained in terms of a competition between two processes: copper oxidation and copper(I) deproportionation. In the cyclic voltammetric experiments it was observed an anodic current peak, related with copper oxidation with a possible formation of some interfacial species, and a cathodic current peak during the reverse potential scan, associated with the reduction of soluble species and/or of the film. The AC Impedance data were interpreted in terms of electric equivalent circuits.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

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

Design of novel iron compounds as potential therapeutic agents against tuberculosis

In the search for new therapeutic tools against tuberculosis two novel iron complexes, [Fe(L-H)3], with 3-aminoquinoxaline-2-carbonitrile N(1),N(4)-dioxide derivatives (L) as ligands, were synthesized, characterized by a combination of techniques, and in vitro evaluated. Results were compared with those previously reported for two analogous iron complexes of other ligands of the same family of quinoxaline derivatives. In addition, the complexes were studied by cyclic voltammetry and EPR spectroscopy. Cyclic voltammograms of the iron compounds showed several cathodic processes which were attributed to the reduction of the metal center (Fe(III)/Fe(II)) and the coordinated ligand. EPR signals were characteristic of magnetically isolated high-spin Fe(III) in a rhombic environment and arise from transitions between m(s) = +/- 1/2 (geff-9) or m(s) = +/- 3/2 (g(eff)similar to 4.3) states. Mossbauer experiments showed hyperfine parameters that are typical of high-spin Fe(III) ions in a not too distorted environment. The novel complexes showed in vitro growth inhibitory activity on Mycobacterium tuberculosis H(37)Rv (ATCC 27294), together with very low unspecific cytotoxicity on eukaryotic cells (cultured murine cell line J774). Both complexes showed higher inhibitory effects on M. tuberculosis than the "second-line" therapeutic drugs. (C) 2010 Elsevier B.V. All rights reserved.

Altering the adsorptive and electronic properties of Pt through poly(vinyl alcohol) adsorption

In the present paper we investigated the effect of adsorbed PVA on Pt electrodes on classic electrochemical processes such as hydrogen UPD, oxygen reduction and CO electro-oxidation. Upon adsorption PVA blocks roughly 50% of the hydrogen sites and can not be removed from the Pt surface through cycling in the potential range of 0.05-1.0 V vs. RHE. Potentiodynamic experiments under controlled hydrodynamic conditions provided by rotating disk electrode experiments showed a negative impact of the adsorbed PVA on the oxygen reduction reaction (ORR). Cyclic-voltammetry results revealed that not even CO was able to remove PVA from the Pt surface. Regarding the oxidation of CO, the adsorbed polymer positively shifted the CO oxidation peak potential, therefore higher potentials are required to free the Pt surface from CO poisoning. In situ Fourier transform infrared spectroscopy evidenced that the presence of PVA shifted the linearly bound CO frequency toward higher wavenumbers, a process found to be independent of the Pt surface orientation. In situ electrochemical X-ray absorption spectroscopy results showed that PVA also impacted the electronic properties of platinum by decreasing the occupancy of the Pt conducting 5d band. Our findings clearly support the efforts toward understanding the nature of the interaction between polymers and metallic surfaces as well as the impact on technological applications (e.g. in PEMFCs). © 2013 Elsevier Ltd. All rights reserved.

Electrochemical studies based on local interfacial ph changes of gold nanoparticles immobilized on polystyrene brushes

The electrochemical behavior of polystyrene modified with gold nanoparticle (Au NPs) was investigated in terms of pH-responsive polymer brush. A pH-responsive of modified polymer brush from tethered polystyrene was prepared and used for selective gating transport of anions andcations across the thin-film. An ITO-coated glass electrode was used as substrate and applied to study the switchable permeability of the polymer brush triggered by changes in pH of the aqueous environment. The pH-sensitive behavior of the polymer brush interface has been demonstrated by means of cyclic voltammetry (CV) and Localized Surface Plasmon Resonance (LSPR). CV experiments showed at ph values of 4 and 8 induces swelling and shrinking of the grafted polymer brushes, respectively, and this behavior is fast and reversible. LSPR measurements showed a blue shift of 33 nm in the surface resonance band changes by local pH. The paper brings an easy methodology to fabrication a variety of nanosensors based on the polymer brushes-nanoparticle assemblies. © 2013 by ESG.