715 resultados para ELECTROCHEMISTRY


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In this work, the impact of global and/or local strain engineering techniques on tri-gate p- and nMuGFETs performance is experimentally evaluated. Multiple gate structures were analyzed through basic and analog performance parameters for four different splits processed with different strain-engineering techniques (unstrained, uniaxial, biaxial and uniaxial+biaxial stress). While n-channel devices with narrow fins present a worse analog behavior, biaxial stress promotes the electron mobility for larger devices increasing the voltage gain. Besides the voltage gain, the transconductance, output conductance and Early Voltage are also evaluated. Although pMuGFETs are less affected by the strain engineering, they present better analog behavior for all studied devices.

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Polymeric sensors with improved resistance to organic solvents were produced via the layer-by-layer thin film deposition followed by chemical cross-linking. According to UV-vis spectroscopy, the mass loss of polyaniline/poly(vinyl alcohol) and polyaniline/novolac-type resin based films deposited onto glass slides was less than 20% when they were submitted to successive immersions (up to 3,000 immersion cycles) into commercially available ethanol and gasoline fuel samples. Polyallylamine hydrochloride/nickel tetrasulfonated phthalocyanine films presented similar stability. The electrical responses assessed by impedance spectroscopy of films deposited onto Au-interdigitated microelectrodes were relatively unaffected after continuous or cyclic immersions into both fuels. After these studies, an array including these polymeric sensors was employed to detect adulteration in ethanol and gasoline samples. After principal component analysis, it was possible to conclude that the proposed sensor array is capable to discriminate with remarkable reproducibility ethanol samples containing different amounts of water or else gasoline samples containing different amounts of ethanol. In both examples, more than 90% of data variance was retained in the first principal component. For each type of sample, ethanol and gasoline, it was found a linear correlation between one of the principal components and the sample's composition. These findings allow one to conclude that these films present great potential for the development of reliable and low-cost sensors for fuel analysis in liquid phase.

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In this study, a novel material for the electrochemical determination of bisphenol A using a nanocomposite based on multi-walled carbon nanotubes modified with antimony nanoparticles has been investigated. The morphology, structure, and electrochemical performance of the nanocomposite electrodes were characterised by field emission gun scanning electron microscopy, energy-dispersive X-ray spectroscopy, and cyclic voltammetry. A scan rate study and electrochemical impedance spectroscopy showed that the bisphenol A oxidation product is adsorbed on nanocomposite electrode surface. Differential pulse voltammetry in phosphate buffer solution at pH 6, allowed the development of a method to determine bisphenol A levels in the range of 0.5-5.0 mu mol L-1, with a detection limit of 5.24 nmol L-1 (1.19 mu g L-1). (C) 2012 Elsevier Ltd. All rights reserved.

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A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

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This paper describes the experimental study of the oscillatory electro-oxidation of glycerol on platinum under galvanostatic control. The system was investigated in both acidic and alkaline media and for different glycerol concentrations. In acidic supporting electrolyte, the oscillatory behavior is rather simple and the main features such as period, amplitude and waveform are barely affected by the glycerol concentration. A more complex picture including the presence of different temporal patterns and strong dependence with glycerol concentration emerges in alkaline medium. In both media, the composite oscillations visit two clearly discernible potential windows, and potential oscillations in alkaline media are observed only when the working electrode is kept stationary. The mechanistic implications of our findings are discussed in connection with available data obtained under close-to-equilibrium conditions. (C) 2012 Elsevier Ltd. All rights reserved.

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Nafion membranes series N117 doped with ammonium, at different cation fractions (H+/NH4+), were investigated for ionic transport and water vapor uptake, for several water activities and temperatures. Ammonium cations change both properties of the polymer in a similar manner. Membrane ionic conductivity and water vapor uptake (lambda) decrease as the ammonium concentration increases in the polymer. Ionic transport activation energies are calculated and the transport mechanism of ammonium ions in Nafion is discussed. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.040203jes] All rights reserved.

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The effect of support on the properties of rhodium and cobalt-based catalysts for ethanol steam reforming was studied in this work, by comparing the use of magnesia, alumina and Mg-Al oxide (obtained from hydrotalcite) as supports. It was found that metallic rhodium particles with around 2.4-2.6 nm were formed on all supports, but Mg-Al oxide led to the narrowest particles size distribution; cobalt was supposed to be located on the support, affecting its acidity. Rhodium interacts strongly with the support in the order: alumina> Mg-Al oxide > magnesia. The magnesium-containing catalysts showed low ethene selectivity and high hydrogen selectivity while the alumina-based ones showed high ethene selectivity, assigned to the Lewis sites of alumina. The Mg-Al oxide-supported rhodium and cobalt catalyst was the most promising sample to produce hydrogen by ethanol reforming, showing the highest hydrogen yield, low ethene selectivity and high specific surface area during reaction. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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Cobalt ferrite is a ferrimagnetic magnetostrictive ceramic that has potential application in magnetoelastic and magnetoelectric transducers. In this work, CoFe2O4 was obtained using a conventional ceramic method and Bi2O3 was used as additive in order to obtain liquid-phase sintered samples. Bi2O3 was added to the ferrite in amounts ranging from 0.25 mol% to 0.45 mol% and samples were sintered at 900 degrees C and 950 degrees C. It was observed the presence of Bi-containing particles in the microstructure of the sintered samples and the magnetostriction results indicated microstructural anisotropy. It was verified that it is possible to get dense cobalt ferrites, liquid-phase sintered, with relative densities higher than 90% and with magnetostriction values very close to samples sintered without additives.

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Carbon supported Pt-Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 degrees C and 90 degrees C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt3Sn1/C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

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The aim of this study is to develop a new enzymeless electroanalytical method for the indirect quantification of creatinine from urine sample. This method is based on the electrochemical monitoring of picrate anion reduction at a glassy carbon electrode in an alkaline medium before and after it has reacted with creatinine (Jaffe's reaction). By using the differential pulse voltammetry technique under the optimum experimental conditions (step potential, amplitude potential, reaction time, and temperature), a linear analytical curve was obtained for concentrations of creatinine ranging from 1 to 80 mu mol L-1, with a detection limit of 380 nmol L-1. This proposed method was used to measure creatinine in human urine without the interference of most common organic species normally present in biological fluids (e.g., uric acid, ascorbic acid, glucose, and phosphocreatinine). The results obtained using urine samples were highly similar to the results obtained using the reference spectrophotometric method (at a 95% confidence level). (C) 2012 Elsevier B.V. All rights reserved.

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2-Methylisoborneol (MIB) and geosmin (GSM) are sub products from algae decomposition and, depending on their concentration, can be toxic: otherwise, they give unpleasant taste and odor to water. For water treatment companies it is important to constantly monitor their presence in the distributed water and avoid further costumer complaints. Lower-cost and easy-to-read instrumentation would be very promising in this regard. In this study, we evaluate the potentiality of an electronic tongue (ET) system based on non-specific polymeric sensors and impedance measurements in monitoring MIB and GSM in water samples. Principal component analysis (PCA) applied to the generated data matrix indicated that this ET was capable to perform with remarkable reproducibility the discrimination of these two contaminants in either distilled or tap water, in concentrations as low as 25 ng L-1. Nonetheless, this analysis methodology was rather qualitative and laborious, and the outputs it provided were greatly subjective. Also, data analysis based on PCA severely restricts automation of the measuring system or its use by non-specialized operators. To circumvent these drawbacks, a fuzzy controller was designed to quantitatively perform sample classification while providing outputs in simpler data charts. For instance, the ET along with the referred fuzzy controller performed with a 100% hit rate the quantification of MIB and GSM samples in distilled and tap water. The hit rate could be read directly from the plot. The lower cost of these polymeric sensors allied to the especial features of the fuzzy controller (easiness on programming and numerical outputs) provided initial requirements for developing an automated ET system to monitor odorant species in water production and distribution. (C) 2012 Elsevier B.V. All rights reserved.

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Direct borohydride fuel cells (DBFCs) are attractive energy generators for powering portable electronic devices, mainly due to their high energy density and number of electrons per borohydride ion. However, the lack of a highly efficient electrocatalyst for the borohydride oxidation reaction limits the performance of these devices. The most commonly studied electrocatalysts for this reaction are composed of gold and platinum. Nevertheless, for these metals, the borohydride electrooxidation reaction mechanism (BOR) is not completely understood, and the total oxidation reaction, involving eight electrons per BH4- species, competes with parallel reactions, with a lower number of exchanged electrons and/or with heterogeneous chemical hydrolysis. Considering the above-mentioned issues, this work presents recent advances in the knowledge of the BOR pathways on polycrystalline (bulk) Au and Pt electrocatalysts. It presents the studies of the BOR reaction on Au and Pt electrodes using in situ Fourier Transform Infrared Spectroscopy (FUR), and on-line Differential Electrochemical Mass Spectrometry (DEMS). The spectroscopic and spectrometric data provided physical evidence of intermediate species and the formation of H-2 in the course of the BOR as a function of the electrode potential. These results enabled to advance in the knowledge about the BOR pathways on Au and Pt electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

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A general strategy for electrochemically induced assembly of coordination metallopolymers is demonstrated using the tritopic bridging [Ru-3(mu(3)-O)(CH3COO)(6)(pytpy)(3)](+) cluster complex, where pytpy is the 4'-(4-pyridyl)-2,2':6',2 ''-terpyridine ligand, and iron(III) ions. The concept of such an electrochemically induced coordinative assembly was proven exploring the large difference in the [Fe(pytpy)2 complex formation constants depending on the iron ion oxidation state. Much more stable bridging complexes are formed in the presence of Fe(II) in contrast to Fe(III) ions. The build-up of electrochemically active films on FTO electrodes was confirmed by the growth of the corresponding voltammetric peaks concomitantly with the rise of typical triruthenium cluster and [Fe(pytpy)(2)](2+) complex absorption bands. The metallopolymer was constituted by agglomerates of more or less fused tape like structures, exhibiting large voids and pinholes, as revealed by SEM and AFM images. The adhesion/deposition on FTO was improved by functionalizing the surface with TES-tpy and HOOC-tpy, which increased the surface coverage up to 80%, as estimated by impedance spectroscopy. (C) 2012 Elsevier Ltd. All rights reserved.

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Formation of oriented or aligned micro- and nanofibers using biocompatible materials opens the possibility to obtain engineered tissues that can be used in medicine, environmental engineering, security and defense, among other applications. Pectin, a heteropolysaccharide, is a promising material to be incorporated into the fibers because, besides being biocompatible, this material is also biodegradable and bioactive. In this work, the formation of oriented fibers using solutions containing pectin and polyethylene oxide (biocompatible polymers), and chloroform (as the solvent) is investigated. The injection of solution into an intense electric field defined between two parallel electrodes was used to obtain oriented fibers. This novel approach is a modification of the conventional electrospinning process. The presence of pectin in the fibers was confirmed by FTIR analysis. Fibers with diameters of hundreds of nanometers and several centimeters long can be collected. The incorporation of pectin leads to a higher variation of the diameter of the fibers, and a trend to larger fiber diameters. This behavior can be related to the presence of pectin clusters in the fibers. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.057203jes] All rights reserved.

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The layer-by-layer (LbL) technique combined with field-effect transistor (FET) based sensors has enabled the production of pH-sensitive platforms with potential application in biosensors. A variation of the FET architecture, so called separative extended gate FET (SEGFET) devices, are promise as an alternative to conventional ion sensitive FET (ISFET). SEGFET configuration exhibits the advantage of combining the field-effect concept with organic and inorganic materials directly adsorbed on the extended gate, allowing the test of new pH-sensitive materials in a simple and low cost way. In this communication, poly(propylene imine) dendrimer (PPI) and TiO2 nanoparticles (TiO2-np) were assembled onto gold-covered substrates via layer-by-layer technique to produce a low cost SEGFET pH sensor. The sensor presented good pH sensitivity, ca. 57 mV pH(-1), showing that our strategy has potential advantages to fabricate low cost pH-sensing membranes. (C) 2012 Elsevier B.V. All rights reserved.