Effect of the Pt/Ru intermetallic boundary on the carbon monoxide electrooxidation: Excess electrocatalytic activity

The carbon monoxide oxidation reaction was studied on smooth Pt, Ru and Pt/Ru (Ru partially covered by Pt islands) rotating disc electrodes on acid solution saturated with CO gas (PCO = 1 atm) through steady state measurements. The current density vs. overpotential plot of the Pt/Ru electrode shows a profile qualitatively similar to the sum of both curves corresponding to pure Pt and Ru. On this basis, the excess electrocatalytic activity was defined as the difference between the current densities of the bimetallic electrode and those corresponding to the pure metals, which allowed evaluating the contribution of the intermetallic region to the reaction. It was verified that this property depends on overpotential, defining two ranges of positive excess values, 0.6 - 0.82 and 0.88 - 1.0, separated by the range 0.82 - 0.88, where the contribution of the boundary region is negligible. A simple model was developed, which explains the experimental results on the basis of the spillover of the adsorbed reaction intermediates, while the reaction between adsorbed species on both sides of the intermetallic edge is not feasible.Fil: Rau, Maria Sol. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentin

Resolution of the mechanism of CO electrooxidation on steady state and evaluation of the kinetic parameters for Pt and Ru electrodes

The carbon monoxide oxidation reaction (COOR) was studied on steady-state conditions by chronoamperometry on polycrystalline smooth platinum and ruthenium rotating disc electrodes in CO-saturated acid solution. The chronoamperometric response did not show current oscillations and therefore the current density (j) vs. overpotential (η) curves on steady state could be obtained. In order to interpret these results, kinetic expressions were derived starting from the mechanism proposed by S. Gilman, which considers two adsorbed reaction intermediates, carbonmonoxide (CO ad) and hydroxyl (OH ad). Analytical expressions as a function of overpotential for the current density, the surface coverage of the adsorbed species (θ CO and θ OH) and the CO and CO 2 pressures at the electrode surface on steady state were obtained. This set of equations was used for the correlation of the experimental polarization curves and the evaluation of the corresponding kinetic parameters. From these values, the dependences of the surface coverage of the adsorbed intermediates on overpotential were simulated, as well as those of the partial pressure of CO and CO 2. Thus, it was demonstrated that the Gilman's mechanism accurately describes the experimental results on steady state of the COOR on these metals.Fil: Rau, Maria Sol. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Gennero, Maria Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentin

Kinetic Study of the Hydrogen Oxidation Reaction on Membrane Coated Electrodes. Part I: Theoretical Aspects

A generalized theoretical analysis of the kinetics of the hydrogen oxidation reaction under the Volmer-Heyrovsky-Tafel mechanism on an electrode covered by polymeric films is presented. The treatment includes the diffusion of the molecular hydrogen through the electrolyte solution, as well as through the different layers and interfaces. On the light of the resulting expressions, the applicability of the Levich-Koutecky diagrams for the determination of the kinetic current densities was critically analyzed.Fil: Marozzi, Carlos Alberto. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin

Unexpected Behavior of the Hydrogen Oxidation Reaction on Palladium in Alkaline Solution: A Feasible Kinetic Explanation

The hydrogen oxidation reaction was studied on a thin film palladium electrode supported on a gold substrate in alkaline solution. The hydrogen absorption process was analyzed by open circuit potential transient and the current - overpotential dependences were obtained by chronoamperometry at different rotation rates in a solution saturated with hydrogen. The results obtained show anunexpected profile at low overpotentials, where current decreases as rotation rate increases. A kinetic mechanism was proposed to interpret this behavior and the corresponding equations were derived. They were used to correlate the results, with a good agreement between the experimental and fitted curves.Fil: Montero, María de Los Angeles. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin

Kinetics of passivation and pitting corrosion of polycrystalline copper in borate buffer solutions containing sodium chloride

The pitting corrosion of copper in borate buffer containing sodium chloride is studied by using potentiostatic and potentiodynamic techniques complemented with scanning electron microscopy and EDAX. The breakdown potential shifts towards more negative values as the sodium chloride concentration increases. During pitting both soluble Cu(I) and Cu(II) species are detected. The first stage of pitting is explained through the competition between the passive layer formation and the nucleation and growth of the CuCl layer in equilibrium with Cu(I)-chloride complexes in solution. When salt nuclei reach the metal surface, pit growth under charge-transfer control is found. In the following stage the kinetics of pit growth changes to a diffusion controlled process when the thick CuCl layer is completed. Secondary breakdown of the salt layer results in copper dissolution through Cu(II) soluble species. The corresponding overall process is discussed in terms of a sum of nucleation and growth processes. The reaction model reproduces the potentiostatic current transients of copper in weakly alkaline borate buffer containing sodium chloride.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Kinetics of passivation and pitting corrosion of polycrystalline copper in borate buffer solutions containing sodium chloride

The pitting corrosion of copper in borate buffer containing sodium chloride is studied by using potentiostatic and potentiodynamic techniques complemented with scanning electron microscopy and EDAX. The breakdown potential shifts towards more negative values as the sodium chloride concentration increases. During pitting both soluble Cu(I) and Cu(II) species are detected. The first stage of pitting is explained through the competition between the passive layer formation and the nucleation and growth of the CuCl layer in equilibrium with Cu(I)-chloride complexes in solution. When salt nuclei reach the metal surface, pit growth under charge-transfer control is found. In the following stage the kinetics of pit growth changes to a diffusion controlled process when the thick CuCl layer is completed. Secondary breakdown of the salt layer results in copper dissolution through Cu(II) soluble species. The corresponding overall process is discussed in terms of a sum of nucleation and growth processes. The reaction model reproduces the potentiostatic current transients of copper in weakly alkaline borate buffer containing sodium chloride.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Estudio de la reacción de electrooxidación de acido fórmico sobre Iridio usando una celda de flujo

Estudios recientes de la reacción de electrooxidación de ácido fórmico (FAO) mediante la determinación simultanea de la dependencia corriente-potencial en estado estacionario y del cubrimiento de monóxido de carbono adsorbido COad, han permitido aportar nueva evidencia para la comprensión de los procesos elementales involucrados en las misma [1-3]. Se ha observado que la FAO sobre Pd [3] presenta un comportamiento cinético marcadamente diferente a los observados sobre Pt [1] y Rh [3]. En este contexto, en el presente trabajo se estudia la FAO sobre iridio, metal que se caracteriza por la adsorción de oxhidrilo OHad a bajos potenciales.Fil: Montero, María de Los Angeles. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaFil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Instituto de Química Aplicada del Litoral. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Química Aplicada del Litoral.; ArgentinaXXII Congreso Argentino de Fisicoquímica y Química InorgánicaLa PlataArgentinaAsociación Argentina de Investigación FisicoquímicaUniversidad Nacional de la Plata. Facultad de Ingenierí

Kinetics of passivation and pitting corrosion of polycrystalline copper in borate buffer solutions containing sodium chloride

The pitting corrosion of copper in borate buffer containing sodium chloride is studied by using potentiostatic and potentiodynamic techniques complemented with scanning electron microscopy and EDAX. The breakdown potential shifts towards more negative values as the sodium chloride concentration increases. During pitting both soluble Cu(I) and Cu(II) species are detected. The first stage of pitting is explained through the competition between the passive layer formation and the nucleation and growth of the CuCl layer in equilibrium with Cu(I)-chloride complexes in solution. When salt nuclei reach the metal surface, pit growth under charge-transfer control is found. In the following stage the kinetics of pit growth changes to a diffusion controlled process when the thick CuCl layer is completed. Secondary breakdown of the salt layer results in copper dissolution through Cu(II) soluble species. The corresponding overall process is discussed in terms of a sum of nucleation and growth processes. The reaction model reproduces the potentiostatic current transients of copper in weakly alkaline borate buffer containing sodium chloride.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA)Facultad de Ciencias Exacta

Exchange current density, electrocatalytic activity and volcano curve for the hydrogen electrode reaction: theoretical analysis

The use of the exchange current density as a parameter for the characterization of the electrocatalytic activity in the volcano curve for the hydrogen electrode reaction was critically analyzed from the point of view of its evaluation and its kinetic interpretation. The methods usually employed in its calculation were first described and then analyzed in order to interpret the different values obtained from the extrapolation of Tafel regions and from the evaluation of the equilibrium polarization resistance. It was demonstrated that the use of Butler-Volmer type equations is inadequate and instead a general expression is proposed, derived in the framework of the Volmer-Heyrovsky-Tafel mechanism. The method proposed for the evaluation of the exchange current density was illustrated with several examples, being the different behaviours analyzed and discussed.Fil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Chialvo, Abel Cesar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin

Hydrogen evolution reaction on a smooth iron electrode in alkaline solution at different temperatures

The hydrogen evolution reaction (HER) has been studied on a rotating polycrystalline smooth iron disc electrode in the temperature range 20 ≤ T/°C ≤ 60 in 2 M NaOH. It has been demonstrated that only for |η| ≥0.1 V can the polarisation curve be considered as that corresponding to the HER, due to the corrosion process that takes place at low overpotentials. The experimental results were adequately correlated by the Vollmer-Heyrovsky-Tafel mechanism with a Langmuirian adsorption, considering αv ≠ αH. On this basis, two sets of kinetic parameters were found for each of the three elementary steps and the corresponding apparent activation energies were also evaluated. These results allowed the calculation of the experimental kinetic parameters, Tafel slope and extrapolated exchange current density, for all the temperatures studied.Fil: Gennero, Maria Rosa. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; ArgentinaFil: Chialvo, Abel Cesar. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentin