Activity of platinum-tin catalysts prepared by the Pechini-Adams method for the electrooxidation of ethanol

Pt-Sn electrocatalysts of different compositions were prepared and dispersed on carbon Vulcan XC-72 using the Pechini-Adams method. The catalysts were characterized by energy dispersive X-ray analysis and X-ray diffraction. The electrochemical properties of these electrode materials were also examined by cyclic voltammetry and chronoamperometric experiments in acid medium. The results showed that the presence of Sn greatly enhances the activity of Pt towards the electrooxidation of ethanol. Moreover, it contributes to reduce the amount of noble metal in the anode of direct alcohol fuel cells, which remains one of the challenges to make the technology of direct alcohol fuel cells possible. Electrolysis of ethanol solutions at 0.55 V vs. RHE allowed to determine by liquid chromatography acetaldehyde and acetic acid as the main reaction products. CO(2) was also analyzed after trapping it in a NaOH solution indicating that the cleavage of the C-C bond in the ethanol molecule did occur during the adsorption process. In situ IR reflectance spectroscopy helped to investigate in more details the reaction mechanism through the identification of the reaction products as well as the presence of some intermediate adsorbed species, such as linearly bonded carbon monoxide. (C) 2009 Elsevier B.V. All rights reserved.

Ethanol electrooxidation on Pt-Sn and Pt-Sn-W bulk alloys

Ethanol oxidation has been studied on Pt-Sn and Pt-Sn-W electrodes prepared in an arc-melting furnace. Different electrochemical techniques like cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activity of these materials. The electro-oxidation process was also investigated by in situ infrared reflectance spectroscopy in order to determine adsorbed intermediates and reaction products. Experimental results indicated that Pt-Sn and Pt-Sn-W alloys are able to oxidize ethanol mainly to acetaldehyde and acetic acid. Adsorbed CO was also detected, demonstrating the viability of splitting the C-C bond in the ethanol molecule during the oxidation process. The adsorbed CO was further oxidized to CO2.This reaction product was clearly detected by SNIFTIRS. Pt-Sn-W catalyst showed a better electrochemical performance than Pt-Sn that, in it turn, is better than Pt-alone.

PtSnCe/C electrocatalysts for ethanol oxidation: DEFC and FTIR ""in-situ"" studies

The ethanol oxidation reaction (EOR) was investigated using PtSnCe/C electrocatalysts in different mass ratios (72:23:5, 68:22:10 and 64:21:15) that were prepared by the polymeric precursor method. Transmission electron microscopy (TEM) showed that the particles ranged in size from approximately 2 to 5 nm. Changes in the net parameters observed for Pt suggest the incorporation of Sn and Ce into the Pt crystalline network with the formation of an alloy between Pt, Sn and/or Ce. Among the PtSnCe catalysts investigated, the 68:22:10 composition showed the highest activity toward ethanol oxidation, and the current time curves obtained in the presence of ethanol in acidic media showed a current density 50% higher than that observed for commercial PtSn/C (E-Tek). During the experiments performed on single direct ethanol fuel cells, the power density for the PtSnCe/C 68:22:10 anode was nearly 40% higher than the one obtained using the commercial catalyst. Data from Fourier transform infrared (FTIR) spectroscopy showed that the observed behavior for ethanol oxidation may be explained in terms of a double mechanism. The presence of Sn and Ce seems to favor CO oxidation, since they produce an oxygen-containing species to oxidize acetaldehyde to acetic acid. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Study of ethanol electro-oxidation in acid environment on Pt(3)Sn/C anode catalysts prepared by a modified polymeric precursor method under controlled synthesis conditions

A carbon-supported binary Pt(3)Sn catalyst has been prepared using a modified polymeric precursor method under controlled synthesis conditions This material was characterized using X-ray diffraction (XRD). and the results indicate that 23% (of a possible 25%) of Sn is alloyed with Pt, forming a dominant Pt(3)Sn phase. Transmission election microscopy (TEM) shows good dispersion of the electrocatalyst and small particle sizes (3 6 nm +/- 1 nm) The polarization curves for a direct ethanol fuel cell using Pt(3)Sn/C as the anode demonstrated Improved performance compared to that of a PtSn/C E-TEK. especially in the intrinsic resistance-controlled and mass transfer regions. This behavior is probably associated with the Pt(3)Sn phase. The maximum power density for the Pt(3)Sn/C electrocatalyst (58 mW cm(-2)) is nearly twice that of a PtSn/C E-TEK electrocatalyst (33 mW cm(-2)) This behavior is attributed to the presence of a mixed Pt(9)Sn and Pt(3)Sn alloy phase in the commercial catalysts (C) 2009 Elsevier B V All rights reserved

Electrochemical Determination of Inorganic Contaminants in Automotive Fuels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrocatalytic activity under oscillatory regime: The electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase

Despite the considerable progress in the understanding of the mechanistic aspects of the oscillatory electro-oxidation of C1 molecules, there are apparently no systematic studies concerning the impact of surface modifiers on the oscillation dynamics. Herein we communicate on the oscillatory electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase, and compare the results with those obtained on a polycrystalline platinum electrode. Overall, the obtained results were very reproducible, robust and allowed a detailed analysis on the correlation between the catalytic activity and the oscillation dynamics. The presence of Sn in the intermetallic electrode promotes drastic effects on the oscillatory dynamics. The decrease in the mean electrode potential and in the oscillation frequency, as well as the pronounced increase in the number oscillations (and also in the oscillation time), was discussed in connection with the substantial catalytic enhancement of the Pt3Sn towards the electro-oxidation of formic acid. The self-organized potential oscillations were used to probe the electrocatalytic activity of the Pt3Sn electrode and compare it with that for polycrystalline Pt. The presence of Sn resulted in a significant decrease (2-11 times, depending on the applied current) of the rate of surface poisoning. © 2012 Elsevier B.V.

Long-Lasting Oscillations in the Electro-Oxidation of Formic Acid on PtSn Intermetallic Surfaces

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)