989 resultados para Aromatic amines electro-oxidation


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

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Silver nanoparticles (Ag) were deposited on multi-walled carbon nanotube by eletroless. The hybrid Ag/MWCNT was used in the modification of glassy carbon electrode (GC) surface. The electrochemical characterization confirmed the presence of Ag in the nanocomposite has been showed that the synthesis was successful. The GC electrode modified with Ag/MWCNT film was evaluated for electro-oxidation of benzene. The electrochemical behavior presented an improvement on the catalytic surface in relation to non-modified GC electrode. The anodic peak current increased the magnitude in three times when compared with the CG electrode modified only with MWCNT

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Interest in the electronic properties of carbon nanotubes has increased in recent years. These materials can be used in the development of electrochemical sensors for the measurement and monitoring of analytes of environmental interest, such as pharmaceuticals, dyes, and pesticides. This work describes the use of homemade screen-printed electrodes modified with multi-walled carbon nanotubes (MWCNT) for the electrochemical detection of the fungicide thiram. The electrochemical characteristics of the proposed system were evaluated using cyclic voltammetry, with investigation of the electrochemical behavior of the sensor in the presence of the analyte, and estimation of electrochemical parameters including the diffusion coefficient, electron transfer coefficient (α), and number of electrons transferred in the catalytic electro-oxidation. The sensor response was optimized using amperometry. The best sensor performance was obtained in 0.1 mol L-1 phosphate buffer solution at pH 8.0, where a detection limit of 7.9 x 10-6 mol L-1 was achieved. Finally, in order to improve the sensitivity of the sensor, square wave voltammetry (SWV) was used for thiram quantification, instead of amperometry. Using SWV, a response range for thiram from 9.9 x 10-6 to 9.1 x 10-5 mol L-1 was obtained, with a sensitivity of 30948 µA mol L-1, and limits of detection and quantification of 1.6 x 10-6 and 5.4 x 10-6 mol L-1, respectively. The applicability of this efficient new alternative methodology for thiram detection was demonstrated using analyses of enriched soil samples.

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Pós-graduação em Química - IQ

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The mechanism of electrochemical oxidation of surface reformed CuA1Ag alloys having different composition of heat treatment, in 0.5 M NaOH was studied by means of cyclic polarization, constant potential electrolysis, ICP, AA, SEM and EDX. The surface reformation consisted of a repetitive triangular potential sweep (RTPS) between H 2 and O 2 evolution at 100 mV s -1 in the working solution itself, performed in order to increase the electrode roughness and obtain a quasi-stationary I/E profile in which the potentiodynamic behaviour of copper and silver was clearly revealed. The alloys suffer aluminum dealloying after such an RTPS. The quasi-stationary cyclic polarization curve exhibits a multiplicity of current peaks which have been related to the electrochemical reactions involving the pure alloying elements. Complex potential perturbation programmes in regions having different anodic and cathodic limits allowed the study of the mechanism of the electrochemical oxidation of the surface reformed alloys and the compare with that corresponding to the pure metals. The basic differences between the electro-oxidation processes of the surface reformed CuA1Ag alloys with respect to those established for the high purity alloying metals are the splitting of the peaks corresponding to the formation of the Cu(I) and Ag(I) species. © 1991.

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

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Pós-graduação em Ciências Biológicas (Biologia Celular e Molecular) - IBRC

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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In this work the influence of variations in the borohydrate reduction method on the properties of PtRu/C electrocatalysts was investigated. The electrocatalysts were prepared using 1:1 ; 2:1; 5:1; 50:1 and 250:1 molar ratios of NaBH4 to metals. The reduction was also performed by dripping or by fast addition of the solution. The results showed that PtRu nanoparticles obtained by fast addition had the smallest crystallite sizes. It was also noted that the catalytic activity increased as the borohydrate:metal molar ratio increased. The PtRu/C electrocatalyst (50:1) obtained by fast addition presented the best catalytic activity for ethanol electro-oxidation.

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The class of electrochemical oscillators characterized by a partially hidden negative differential resistance in an N-shaped current potential curve encompasses a myriad of experimental examples. We present a comprehensive methodological analysis of the oscillation frequency of this class of systems and discuss its dependence on electrical and kinetic parameters. The analysis is developed from a skeleton ordinary differential equation model, and an equation for the oscillation frequency is obtained. Simulations are carried out for a model system, namely, the nickel electrodissolution, and the numerical results are confirmed by experimental data on this system. In addition, the treatment is further applied to the electro-oxidation of ethylene glycol where unusually large oscillation frequencies have been reported. Despite the distinct chemistry underlying the oscillatory dynamics of these systems, a very good agreement between experiments and theoretical predictions is observed. The application of the developed theory is suggested as an important step for primary kinetic characterization.

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In this study we address the problem of the response of a (electro)chemical oscillator towards chemical perturbations of different magnitudes. The chemical perturbation was achieved by addition of distinct amounts of trifluoromethanesulfonate (TFMSA), a rather stable and non-specifically adsorbing anion, and the system under investigation was the methanol electro-oxidation reaction under both stationary and oscillatory regimes. Increasing the anion concentration resulted in a decrease in the reaction rates of methanol oxidation and a general decrease in the parameter window where oscillations occurred. Furthermore, the addition of TFMSA was found to decrease the induction period and the total duration of oscillations. The mechanism underlying these observations was derived mathematically and revealed that inhibition in the methanol oxidation through blockage of active sites was found to further accelerate the intrinsic non-stationarity of the unperturbed system. Altogether, the presented results are among the few concerning the experimental assessment of the sensitiveness of an oscillator towards chemical perturbations. The universal nature of the complex chemical oscillator investigated here might be used for reference when studying the dynamics of other less accessible perturbed networks of (bio)chemical reactions.

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Herein, it was investigated for the first time the electro-oxidation of ethanol on Pt and PtRu electrodeposits in acidic media by using in situ surface enhanced infrared absorption spectroscopy with attenuated total reflection (ATR-SEIRAS). The experimental setup circumvents the weak absorbance signals related to adsorbed species, usually observed for rough, electrodeposited surfaces, and allows a full description of the CO coverage with the potential for both catalysts. The dynamics of adsorption-oxidation of CO was accessed by ATR-SEIRAS experiments (involving four ethanol concentrations) and correlated with expressions derived from a simple kinetic model. Kinetic analysis suggests that the growing of the CO adsorbed layer is nor influenced by the presence of Ru neither by the concentration of ethanol. The results suggest that the C-C scission is not related to the presence of Ru and probably happens at Pt sites.