Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

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

Electrochemical behavior of metallic chromium in chloride media

The electrochemical behavior of metallic chromium in aqueous solutions containing chloride ions at different pH was studied by means of open-circuit potential vs. time measurements, cyclic voltammetry and electrochemical impedance spectroscopy. The composition of the surface oxides was analyzed by XPS. For solutions with pH<3 the formation of a passive layer occurs via a dissolution/precipitation process while for pH>3 the mechanism changes. XPS analysis revealed that Cr2O3 basically constitutes the passive layer.

Electrochemical oxidation of methanol on Pt nanoparticles dispersed on RuO2

Pt-modified RuO2 was prepared by a sol-gel procedure on titanium substrates in the form of thin films of similar to2-mum thickness. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that these films actually consist of Pt nanoparticles dispersed in RuO2 and that neither metallic Ru nor Pt-Ru alloy are present on the surface. Electrodes with different Pt:Ru nominal compositions were prepared and their electrocatalytic activity for the oxidation of methanol was investigated by potential sweeps and chronoamperometry. The results obtained show an enhancement effect for methanol oxidation that can be interpreted as associated to the formation of hydrous oxides on the RuO2 surface.

Electrochemical behavior of the N-nosyl-protected amino acids in N,N-dimethylformamide

The electrochemical reduction of serine, glycine, and leucine protected by the 4-nitrobenzenesulfonyl, group in N,N-dimethylformamide at mercury cathode occurs at two steps. The first one at -0.8 V vs. SCE, after a one-electron transfer, leads the anion radical formation that dimerizes and adsorbs at electrode. In the second step at -1.4 V, an instable dianion forms which then cleaves. The mechanism is discussed.

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at similar to 0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO3 during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO3 inside of the TiO2 surface layer seems to be constant. (c) 2006 Elsevier Ltd. All rights reserved.

Electrochemical study of perchlorate reduction at tin electrodes

The electrochemical behaviour of tin in de-aerated sodium perchlorate was studied using potentiodynamic and potentiostatic techniques. Tin behaviour in sodium perchlorate has been complicated unexpectedly by the reduction of the perchlorate anion. It is shown that the reduction process takes place within a potential region comprising the negative side of the double layer region and the positive side of the hydrogen region (-0.7 less than or equal to E less than or equal to -1.3 V). The presence of oxide on the electrode surface favours the reduction reaction, which may occur in two steps: the formation of basic tin(II) chloride followed by its reduction, producing chloride.

Electrochemical studies with a Cu-5wt.%Ni alloy in 0.5 M H2SO4

The electrochemical behavior of the annealed Cu-5wt.%Ni alloy in 0.5 M H2SO4 was studied by means of open-circuit potential (E-OCP) measurements, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and quasi-stationary linear potential sweep. The hydrodynamics of the system was also studied. This material is constituted by a single a, phase. The anodic behavior of a Cu-Ni alloy in H2SO4 consists fundamentally on the electrodissolution of Cu, its main component, and the formation of a sulfur-containing passive layer. The presence of Ni decreases the rate of Cu oxidation, mostly at high positive potentials. The impedance spectra, obtained for the unrotating electrode, can be interpreted in terms of a simple charge-transfer reaction across a surface layer. When the electrode is rotated, the occurrence of an inductive loop evidenced the existence of an adsorbed layer. All the resistance estimated from the proposed equivalent circuits diminished with the electrode rotation rate, emphasizing the influence of ion transport in the overall electrode process. The system presented two anodic Tafel slopes: 40 mV dec(-1) for E < 255 mV and 67 mV dec(-1) for E > 275 mV. A Tafel slope of 40 mV dec(-1) evidences that copper dissolution can be interpreted in terms of the mechanism proposed by Mattsson and Bockris. The second Tafel suggests that at potentials more positive than 275 mV, copper dissolves according to a mechanism that considers the disproportionation of adsorbed Cu(1) species. (C) 2003 Elsevier Ltd. All rights reserved.

Electrochemical impedance spectroscopy characterization of passive film formed on implant Ti-6Al-7Nb alloy in Hank's solution

The influence of potential on electrochemical behavior of Ti-6Al-7Nb alloy under simulate physiological conditions was investigated by electrochemical impedance spectroscopy (EIS). The experimental results were compared with those obtained by potentiodynamic polarization curves. All measurements were carried out in Hank's aerated solution at 25degreesC, at pH 7.8 and at different potentials (corrosion potential, 0 mV(SCE), 1000 mV(SCE), and 2000 mV(SCE)). The EIS spectra exhibited a two-step or a two-time constant system, suggesting the formation of a two-layer oxide film on the metal surface. The high corrosion resistance, displayed by this alloy in electrochemical polarization tests, is due to the dense inner layer, while its osseointegration ability can be ascribed to the presence of the outer porous layer. (C) 2004 Kluwer Academic Publishers.

Synthesis, characterization and electrochemical study of layered double hydroxides intercalated with 2-thiophenecarboxylate anions

The synthesis, characterization, and electrochemical study of the Zn(II)-Al(III) and Zn(II)-Cr(III) Layered Double Hydroxides (LDHs) containing 2-thiopenecarboxylate as the interlayer anions are described. The LDHs were prepared by the constant pH coprecipitation technique followed by hydrothermal treatment for 72 h. The materials were analyzed by PXRD, FT-IR, C-13 CP-MAS, EDX, TEM, and CV. The presence of the organic heterocyclic anions was confirmed by FT-IR and the related solid-state C-13 NMR data strongly suggested that these were dimerised during coprecipitation. Accordingly, the basal spacing found by the X-ray technique was similar to 15.3 Angstrom, a distance coincident with the formation of bilayers of the intercalated anions. The structural organization of all the new materials was greatly enhanced by hydrothermal treatment, as shown by PXRD. The improved organization of the bilayered structures had a strong influence in the electrochemical behaviour of clay-modified electrodes produced with these materials, such as the diminished resistance to the ionic flow through the LDHs films. (C) 2003 Elsevier Ltd. 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.

REDUCTION OF THE AMIDO-BONDED (2-PICOLINAMIDO)PENTAAMMINERUTHENIUM(III) FOLLOWED BY FORMATION OF CIS-(2-PICOLINAMIDE)TETRAAMMINERUTHENIUM(II)

[(NH3)(5)Ru-III(2-NCpy)], obtained from electrochemical oxidation of the Ru(II) complex, undergoes hydrolysis to the amido-bonded [Ru-III(NHC(O)-2-py)]. The electrochemical reduction of this latter complex to Ru(II) is followed by an aquation reaction to form [R(II)(NH3)(5)(OH2)] and free picolinamide and a chelation reaction to form cis-[R(II)-(NH3)(4)(2-pica)] with the displacement of one cis ammonia.

The electrochemical cleavage of the nitrobenzoyl group from butyl nitrobenzoates in N,N-dimethylformamide

The applicability of the nitrobenzoyl group [NO2C6H4CO-] to protecting the functional hydroxyl group was investigated through study of the electrochemical behaviour of the butyl 4-, 3- and 2-nitrobenzoate compounds. These isomers are reduced in two cathodic steps. The first, at potentials of ca. -0.9 V vs. SCE, is attributed to the formation of rather stable anion radicals, involving one-electron transfer. The second, at potentials of ca. -1.7 V vs. SCE, occurs with a two-electron transfer in an ECE process, in which the dianion produced undergoes scission of the C-O bond giving n-butanoate ions with high yields (similar to 80%)

Film formation and surface growth on tin electrodes in bicarbonate solutions: an impedance spectroscopy study

The electrochemical behaviour of potentiodynamically formed thin anodic films of polycrystalline tin in aqueous sodium bicarbonate solutions (pH approximate to 8.3) were studied using cyclic voltammetry and electrochemical impedance spectroscopy. Different equivalent circuits corresponding to various potential regions were employed to account for the electrochemical processes taking place under each condition. (C) 2004 Elsevier Ltd. All rights reserved.

Synthesis and electrochemical behavior of single-crystal magnetite nanoparticles

Water-dispersed magnetite nanoparticle synthesis from iron(II) chloride in dimethyl sulfoxide (DMSO)-water solution at different DMSO-water ratios in alkaline medium was reported. TEM and XRD results suggest a single-crystal formation with mean particle size in the range 4-27 nm. Magnetic nanoparticles are formed by the oxidative hydrolysis reaction from green rust species that leads to FeOOH formation, followed by autocatalysis of the adsorbed available Fe(II) on the FeOOH surfaces. The available hydroxyl groups seem to be dependent on the DMSO-water ratio due to strong molecular interactions presented by the solvent mixture. Goethite phase on the magnetite surface was observed by XRD data only for sample synthesized in the absence of DMSO. In addition, cyclic voltammetry with carbon paste electroactive electrode (CV-CPEE) results reveal two reduction peaks near 0 and +400 mV associated with the presence of iron(III) in different chemical environments related to the surface composition of magnetite nanoparticles. The peak near +400 mV is related to a passivate thin layer surface such as goethite on the magnetite nanoparticle, assigned to the intensive hydrolysis reaction due to strong interactions between DMSO-water molecules in the initial solvent mixture that result in a hydroxyl group excess in the medium. Pure magnetite phase was only observed in the samples prepared at 30% (30W) and 80% (80W) water in DMSO in agreement with the structured molecular solvent cluster formation. The goethite phase present on the, magnetite nanoparticle surface like a thin passivate layer only was detectable using CV-CPEE, which is a very efficient, cheap, and powerful tool for surface characterization, and it is able to determine the passivate oxyhydroxide or oxide thin layer presence on the nanoparticle surface.

Electrochemical Behavior of Cu-9% Al-5% Ni-2% Mn Alloy in Chloride Media

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)