RESUMO Neste trabalho, híbridos Ni/Carbono foram preparados em duas etapas (carbonização hidrotérmica e tratamento térmico a 900 °C sob argônio) a partir de diferentes fontes de carbono: glicose, amido e celulose. Eletrocatalisadores PtRu/C foram preparados pelo método da redução por álcool utilizando os híbridos como suportes. Os materiais foram caracterizados por espectroscopia por energia dispersiva de raios-X (EDX), análise termogravimétrica (TGA), espectroscopia no infravermelho com transformada de Fourier (FTIR), isotermas de B.E.T., difração de raios-X (DRX), microscopia eletrônica de transmissão (TEM) e voltametria cíclica em meio ácido. A eletro-oxidação do metanol foi estudada por cronoamperometria. O eletrocatalisador PtRu/C preparado utilizando o híbrido sintetizado a partir da celulose apresentou uma eletroatividade levemente superior aos demais materiais obtidos.

ABSTRACT In this work, Ni/Carbon hybrids were prepared in two steps (hydrothermal carbonization and thermal treatment at 900 °C under argon atmosphere) using different carbon souces: glucose, starch and cellulose. PtRu/C electrocatalysts were prepared by an alcohol-reduction process using the hybrids as support. The materials were characterized by energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), B.E.T isotherms, X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV) in acidic medium. The electro-oxidation of methanol was studied by chronoamperometry. The PtRu/C electrocatalyst prepared using the hybrid synthesized from cellulose showed an electroactivity slightly superior compared to other obtained materials.

PtRu/C electrocatalysts (carbon-supported PtRu nanoparticles) were prepared submitting water/ethylene glycol mixtures containing Pt(IV) and Ru(III) ions and the carbon support to electron beam irradiation. The electrocatalysts were characterized by energy dispersive X ray analysis (EDX), X ray diffraction (XRD) and cyclic voltammetry and tested for methanol electro-oxidation aiming fuel cell application. The obtained PtRu/C electrocatalysts showed superior performance for methanol electro-oxidation at room temperature compared to commercial PtRu/C electrocatalyst.

PtRu/Carbon hybrids were prepared by hydrothermal carbonization process using glucose or starch as carbon sources and reducing agents and platinum and ruthenium salts as catalysts of carbonization process and metals source. The obtained PtRu/Carbon materials were characterized by SEM/EDX, TGA, XRD and cyclic voltammetry. The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique aiming fuel cell application. The catalytic activity was dependent of carbon source and time used in the synthesis.

This article deals with electrocatalysis and electrocatalysts for low temperature fuel cells and also with established means and methods in electrocatalyst research, development and characterization. The intention is to inform about the fundamentals, state of the art, research and development of noble metal electrocatalysts for fuel cells operating at low temperatures.

The purpose of this investigation was to compare catalysts produced by the Bönnemann - colloidal method (PtRu (B1) and PtRu (B2)), and those produced by the spontaneous deposition method (PtRu (SD)). The catalysts produced by both methods had good electrochemical behavior for methanol oxidation for proton exchange membrane fuel cell applications. The structure of the catalyst was examined by transmission electron microscopy (TEM). Energy dispersive spectroscopic analysis (EDS) was used to determine the semi-quantitative composition of the catalysts, and the electrochemical behavior was determined by cyclic voltammetry (CV). The diffractograms of the binary catalysts revealed platinum and ruthenium as the only crystalline phases, as per ICDD data base. The PtRu (B1) catalyst, treated in a reducing atmosphere, has the same structure as PtRu (B2), treated in an oxidising/reducing atmosphere, except that the crystallite size was around 1.7 nm for PtRu (B1) instead of 9.9 nm for PtRu (B2). The catalysts PtRu (B2) and PtRu (SD) showed similar cyclic voltammetric behavior, which was better than that of PtRu (B1). Both methods are suitable for the production of electrocatalysts for fuel cell applications. The colloidal method is more expensive than the deposition method, but the former permits the production of ternary and quaternary catalyst systems with enhanced CO tolerance.

Fuel cells are attracting much interest as efficient and clean energy conversion devices. The main components of low temperature fuel cells are the electrocatalysts used to promote the anodic and cathodic reactions, which are based on platinum and platinum alloys. These electrocatalysts are normally prepared in the form of metal nanoparticles supported on a conductive material, usually high surface area carbon, to improve catalyst utilization and reduce cost. This work presents and comments some methods used presently to produce these electrocatalysts. The performances of the produced electrocatalysts are compared to that of state-of-the-art commercial E-TEK electrocatalysts.

A oxidação eletroquímica do metanol foi estudada sobre ligas de Pt:Mo dispersa em carbono, preparadas utilizando um método recentemente desenvolvido neste laboratório. Análises de EDX confirmaram que a redução simultânea dos sais precursores de Pt e Mo conduzem a presença destes metais nas composições nominais inicialmente calculadas. A adição de Mo sobre Pt causa um aumento da corrente de oxidação, mas não produz um efeito catalítico para oxidação do metanol. A partir dos dados de polarização em várias concentrações de metanol foram obtidos diagramas de Tafel que apresentaram duas inclinações. A técnica de espectroscopia de massa diferencial aplicada "on line" a um experimento voltamétrico foi utilizada para investigar a distribuição de produtos e intermediários formados na oxidação de metanol.

The electrocatalytic oxidation of methanol on Pt:Mo dispersed on carbon prepared using an alternative method recently developed in this laboratory was investigated. The EDX analysis confirmed that the simultaneous reduction of the precursor salts of Pt and Mo leads to the presence of these materials at the nominal composition initially calculated. The addition of Mo to Pt causes an increase of the oxidation currents, but does not improve the catalytic effect for methanol oxidation. Tafel plots for various methanol concentrations showed the presence of two slopes. On line differential electrochemical mass spectrometry (DEMS) was used to investigate the distribution of products and intermediates in methanol oxidation.