In this work, the gas diffusion electrode (GDE) cathode of Vulcan XC72 carbon modified with nanoparticles of WO2.72 (WO2.72 / Vulcan XC72) was used for H2O2 electrogeneration and degradation of 350 mL of Orange II (OII) and Sunset Yellow FCF (SY) azo dyes by electro-Fenton (EF) and photoelectro-Fenton (PEF) processes with different Fe2+ initial content (1.00, 0.50 and 0.25 mmol L-1). The WO2.72 / Vulcan XC72 GDE electrolyzed approximately 3 times more H2O2 than the Vulcan XC72 GDE. Decolorizations and mineralizations of the dye solutions were more efficient at higher concentrations of Fe2+. The decolorization decay showed pseudo-first-order kinetics. The most promising decolorization results obtained at processes of WO2.72 / Vulcan XC72 cathode combined with Pt anode (100% color removal of OII and SY at 30 and 20 min of electrolysis with 1.00 mmol L-1 Fe2+, respectively). The best mineralization achieved in trials of WO2.72 / Vulcan XC72 cathode combined with boron-doped diamond (BDD) anode (82% total organic carbon (TOC) removal of OII by PEF / 1.00 after 3 h and 90% TOC removal of SY by PEF / 0.50 after 4 h). It was found that SY decolorization was faster and mineralization showed a similar yield independent of oxidized dye.

This work describes the preparation of Pt/C, PtxSny/C and PtxSny(CeO2 nanorods/C) nanoparticle catalysts synthesized by the chemical reduction method via sodium borohydride for the ethanol oxidation reaction. Using X-ray diffractogram analysis, it was verified that no alloy formation occurred between platinum (Pt) and tin (Sn). The distribution of the nanoparticles in the support occurs in a more agglomerated form for the materials containing Sn and CeO2 nanorods (NR). The electrocatalyst Pt3Sn1_20%NRCeO2/C was highlighted in CO-stripping experiments because it showed the lowest onset potential for CO oxidation and the highest value for the electrochemically active surface area. The other electrochemical experiments for ethanol oxidation showed similar activities for the Pt3Sn1/C and Pt3Sn1_20%NRCeO2/C electrocatalysts. The observed effect can be associated with defects in the structure of the CeO2 nanorods, the electrochemical active surface area, and the properties of the CeO2 nanorods related to enhancing the generation of oxy-hydroxy species at lower potentials compared to PtSn/C electrocatalysts, which increased the CO oxidation as measured using stripping experiments. For this reason, it is possible to both use less platinum and to obtain behavior close to that of PtSn/C electrocatalysts for ethanol oxidation reaction (EOR).

Different mass ratio proportions of PtSn (m/m) electrocatalysts with 20% metal loading on a carbon support were prepared for use in ethanol:methanol solutions oxidation reactions. PtSn/C (3:1) (91% alloy degree, lattice parameter of 0.399 nm and mean crystallite size 4.8 nm) presented the best activity for oxidation of mixed solutions. The highest normalized current (ethanol:methanol 80:20) was 4.2 mA mgPt-1 (measured after 1800 seconds at 0.5 V). Therefore, the PtSn/C (3:1) electrocatalyst with an atomic ratio of 65:35 enhanced both the electronic effect and bifunctional mechanism in (ethanol:methanol 80:20), which resulted in the formation of CO2 at low potentials, as well as the highest amount of by-products than ethanol and methanol.

Eletrocatalisadores Pd/C, Au/C e PdAu/C com diferentes razões atômicas foram preparados utilizando-se irradiação por feixe de elétrons e testados na oxidação eletroquímica de glicerol em uma célula alcalina a glicerol direto (ADGFC). Os difratogramas de raios X (XRD) evidenciaram a presença de fases ricas em Pd (fcc) e Au (fcc). As análises de voltametria cíclica (CV) e cronoamperometria indicaram que o eletrocatalisador com razão atômica 50:50 demonstrou atividade superior para a oxidação eletroquímica do glicerol a temperatura ambiente. As análises de infravermelho com transformada de Fourier no modo de refletância total atenuada (ATR-FTIR) in situ identificaram como principais produtos da oxidação eletroquímica do glicerol: 1,3-diidroxi-2-propanona, gliceraldeído e glicolato. Os experimentos em célula unitária foram realizados entre 50 e 90 ºC e foi constatado que o melhor desempenho aconteceu a 80 ºC.

Pd/C, Au/C and PdAu/C electrocatalysts with different atomic ratios prepared using electron beam irradiation were tested for glycerol electrooxidation in single alkaline direct glycerol fuel cell (ADGFC). X-ray diffractograms (XRD) of PdAu/C electrocatalysts showed the presence of Pd (fcc) and Au (fcc) phases. Cyclic voltammetry (CV) and chronoamperometry showed that PdAu/C electrocatalyst with Pd:Au atomic ratio of 50:50 demonstrated superior activity for glycerol electrooxidation, at room temperature. In situ Fourier transform infrared spectroscopy by attenuated total reflectance (ATR-FTIR) experiments were performed for the electrocatalysts, identifying oxalate, glycerate ion, 1,3-dihydroxy-2-propanone, glyceraldehyde and glycolate as products of glycerol electrooxidation. Experiments with single ADGFC were carried out from 50 to 90 ºC, using Pd/C electrocatalyst; the best performance was obtained at 80 ºC.

Neste estudo, a reação de oxidação de etanol (EOR) foi investigada usando materiais nanoestruturados ternários compostos de IrPtSn/C nas proporções em massa Ir:Pt:Sn de 60:30:10, 60:20:20 e 60:10:30, preparados pelo método de precursores poliméricos e comparados com o eletrocatalisador de origem comercial PtSn/C E-TEK. A caracterização por difratometria de raios-X foi utilizada para obter informações acerca da estrutura dos materiais e a microscopia eletrônica de transmissão mostrou que os tamanhos médios das partículas variaram de 5 até 7 nm. A atividade eletrocatalítica foi investigada empregando experimentos cronoamperométricos em 0,5 V vs. RHE e através da espectroscopia no infravermelho com transformada de Fourier no modo de refletância total atenuada (FTIR-ATR) in situ. Baseado nos experimentos de FTIR-ATR in situ, observou-se que o melhor material IrPtSn/C 60:20:20 levou à formação de acetaldeído em altas intensidades e CO2 em baixas intensidades. Utilizando-se o material IrPtSn/C 60:20:20, foi possível diminuir a quantidade de platina em ca. 73% em comparação com o eletrocatalisador PtSn/C E-TEK, tendo um aumento de ca. 282% na densidade de corrente nos experimentos cronoamperométricos.

In this work, the ethanol oxidation reaction (EOR) was investigated using ternary nanostructured materials composed of IrPtSn/C in mass proportions of Ir:Pt:Sn at 60:30:10, 60:20:20 and 60:10:30, prepared with a polymeric precursor method and compared with commercial electrocatalyst PtSn/C E-TEK. X-ray diffractometry was used to obtain information about the structure of the material. The transmission electron microscopy showed particle sizes of 5-7 nm. The electrocatalytic activity was investigated using chronoamperometry experiments at 0.5 V vs. RHE and by in situ Fourier transform infrared spectroscopy by attenuated total reflectance (FTIR-ATR) experiments. From in situ FTIR-ATR experiments, it can be seen that using the best material IrPtSn/C 60:20:20, the acetaldehyde was produced at high intensities and CO2 at lower intensities. The use of IrPtSn/C 60:20:20 materials became possible to diminish the Pt fraction to ca. 73% in comparison to the PtSn/C E-TEK electrocatalyst, with an improvement of ca. 282% in the current density of the chronoamperometric experiments.

Este estudo investiga o efeito promotor de anodos eletrocatalisadores do tipo PtSnIr/C (1:1:1), preparados pelo método de precursor polimérico, na reação de oxidação de etanol em uma célula a combustível de etanol direto (DEFC). Todos os materiais usados foram metal 20% m/m com relação a carbono. Análise por espectroscopia fotoelétrica de raios X (XPS) mostrou a presença de Pt, PtOH2, PtO2, SnO2 e IrO2 na superfície do eletrocalisador, indicando uma possível estrutura de partícula revestida. Análise por difratometria de raios X (XRD) indicou Pt e Ir metálicos assim como a formação de uma liga com Sn. Utilizando eletrocatalisadores do tipo PtSnIr/C preparados para este estudo com quantidades de Pt duas vezes menor que em eletrocatalisadores do tipo PtSn/C E-tek, foi possível obter a mesma densidade de potência máxima encontrada para o material comercial. O produto de reação principal foi ácido acético provavelmente devido a presença de óxidos, neste caso o mecanismo bifuncional é predominante, mas um efeito eletrônico não deve ser descartado.

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH2, PtO2, SnO2 and IrO2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded.

The oxygen reduction reaction was studied in alkaline media using manganese oxides obtained from spent batteries as electrocatalysts. Three processes were used to recover manganese oxides from spent batteries. The particles obtained were in the range from 8 to 11 nm. The electrochemical experiments indicated a good electrocatalytic activity toward oxygen reduction using the different samples and showing approximately a direct transference of 4 electrons during the process. Even though all the processes were efficient, the best result was observed for the prepared sample using reactants of low cost.

Cadmium UPD on Au was studied by voltammetric and microgravimetric measurements. In the oxide formation/reduction potential region, a mass increasing/decreasing of 32 ng cm-2 was associated to incorporation/elimination of one oxygen per active site. The modifications promoted in the voltammetric and mass profiles by 10-5 M Cd(ClO4)2 are restricted to potentials more negative than 0.4 V. After a 120 s potential delay at 0.05 V, the positive sweep reveals an anodic peak with charge of 40 muC cm-2 and mass decrease of 22 ng cm-2, associated to Cd ads dissolution. Sulphate or chloride was added to the solution without significant influence, due to the low coverage with Cd or anions.

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

A deposição em subtensão de Cd sobre Pt e Au policristalinos foi estudada por voltametria nos eletrodos estacionário e de disco-anel rotatório. Sobre Pt, os picos de redissolução do Cd ads se sobrepõem àqueles relacionados com a oxidação do Hads, dificultando assim a avaliação precisa das cargas de dessorção. Um modelo proposto para se calcular estas cargas a partir de voltametria no eletrodo estacionário revelou um valor de 285 miC cm-2 para a monocamada completa, o que corresponde a um recobrimento de 90%, com os ad-átomos de Cd apresentando uma valência de eletrossorção de 0,5. Os resultados obtidos com a técnica de coleção do eletrodo rotatório confirmam plenamente estes valores. A diferença entre os tamanhos dos raios atômicos do Cd e da Pt justificam o recobrimento de menos de 100%. Por outro lado, sobre Au, a ausência de Hads simplifica o procedimento para a determinação das cargas de redissolução da monocamada de Cd. Aqui, um valor de apenas 41 miC cm-2 foi calculado, o que corresponde a um recobrimento máximo de 15%, com valência de eletrossorção de 0,5. Os resultados obtidos com os experimentos de coleção estão em perfeita concordância com estes valores.

The underpotential deposition of Cd on polycrystalline Pt and Au was studied by voltammetry at stationary and rotating ring-disc electrodes. On Pt, the Cd ads dissolution peaks overlap those related to the oxidation of Hads, thus hindering the precise evaluation of desorption charges. A model proposed to calculate such charges from voltammetry at stationary electrodes revealed a value of 285 muC cm-2 for the monolayer dissolution, which corresponds to a coverage of 90% with Cd ads presenting an electrosorption valence of 0.5. Rotating ring-disc experiments fully confirmed such values. The misfit between atomic radii of Cd and Pt justifies the less-than-100% coverage. On the other hand, on Au, the absence of Hads simplifies the procedure for determination of dissolution charges for the Cd monolayer. Here, a value of only 41 muC cm-2 was calculated, which corresponds to a maximum coverage of 15%, with the electrosorption valence of 0.5. The results obtained in the collecting experiments with the rotating electrode are in complete agreement with those values.