Platinum is one of the well-known catalytic materials for which the electro-oxidation of carbon monoxide better behaves as a sensitive reaction to the catalyst surface structure. For the electro-catalytic reactions that behave like this, the rate (faradaic current density) is the result of the sum of the activity of the different active sites working with very different efficiencies or abilities. In this scenario, different atomic arrangements on the catalyst surface are expected to play different roles in surface-catalyzed reactions. In this article, the functionalities that surface defects (steps) can play in the adsorption and electrocatalytic oxidation of CO on model platinum surfaces are reviewed. Surface defects are indirectly related to the up catalysis as well as to the inhibition of reaction pathways of CO electro-oxidation under very particular conditions; these surface entities are also indirectly related to restrictions for the mobility of adsorbed CO on the (111) terraced surfaces. We analyze the selective activation and deactivation of surface sites by the pH effect, and typical catalytic properties of extended surfaces and shaped-controlled nanoparticles have been discussed thoroughly. We present a model of most active sites involved in the pathways of CO2 formation from the electro-oxidation of adsorbed CO.

Herein we sinthesize and investigate Ir-based nanocatalysts (dispersed in carbon) in different atomic compositions combining two (IrRh) and three metals (IrRhSn). These materials were evaluated towards the ethanol electrooxidation in acidic electrolyte in presence of three ethanol concentrations using cyclic voltammetry, while the species produced during the reaction were monitored by in situ Fourier transform infrared spectroscopy (FTIR). Results show that IrRh binary electrocatalysts are selective to the production of CO2 from ethanol, but the catalytic activity is poor. This finding is interpreted in terms of a slow adsorption of ethanol that is assumed to be the rate determining step during the electrooxidation of the alcohol. Ternary catalysts, in turn, present higher electrooxidation currents and anticipate the production of CO2. However, the selectivity towards the CO2 pathway is lost and the higher catalityc activity is justified by a growing production of acetic acid, illustrating the influence of Sn on the eletrooxidation of ethanol.

In this work we performed electrochemical (cyclic voltammetry and chronoamperommetry) and spectroelectrochemical studies (in situ Fourier transform infrared (FTIR)) in PdRuRh electrodeposits in acidic media in presence of ethylene glycol (0.5, 1.0 and 2.0 mol L-1). The electrochemical results show that the ethylene glycol oxidation is sensitive to the composition of the catalysts, being PdRuRh 74:09:17 the composition which presents the best catalytic activity. Also, conversely to Pt, these surfaces do not present a self-inhibitory effect when the EG concentration is increased. FTIR results indicate a complex reaction mechanism under these conditions, where glycolic acid, oxalic acid, formic acid and CO2 are detected as electro-oxidation products. The best catalytic activity observed for PdRuRh 74:09:17 can be understood in terms of a higher selectivity towards the production of CO2, which is the oxidation pathway that involves the release of the major number of electrons.

Researchers have developed new catalysts for fuel cells (FC), whose performances are compared after applying different normalization procedures. However, there is not a standard procedure. The current produced from CO electrooxidation was compared for Pt4Ru5Sn1/C and homemade Pt/C nanoparticles (NPs) normalized by different methods and the use of different methods renders different interpretations. Since the whole field aims to maximize the cost-effectiveness, a complementary method to normalize currents and power in terms of the total cost of the nanocatalyst, the Catalyst-based Cost method (CbC), was proposed. CbC considers the cost of all metals employed to build the catalyst, not only those ones with available surfaces. By applying a simple smoothing method on the prices in a time series, we were able to forecast the prices and consequently the power density of a FC. CbC provides tools for industrials forecast the designing of nanomaterials with improved efficiency and low cost.

Neste trabalho, investigou-se pela primeira vez a eletrooxidação de etanol em eletrodepósitos de Pt e PtRu em meio ácido através da técnica de absorção e reflexão de infravermelho em superfície com reflexão total atenuada (ATR-SEIRAS) in situ. O desenho experimental elimina as fracas absorbâncias associadas a espécies adsorvidas, usualmente observadas para superfícies eletrodepositadas (rugosas), e permite que se acompanhe o recobrimento superficial por CO em função do potencial, para ambos os catalisadores. A dinâmica da adsorção-oxidação de CO foi acompanhada por ATR-SEIRAS (para quatro concentrações de etanol) e correlacionada com expressões derivadas de um modelo cinético simples. A análise cinética sugere que o desenvolvimento da camada de CO não é influenciado pela presença de Ru ou pela concentração de etanol. Os resultados apontam que a quebra da ligação C-C independe do recobrimento com Ru e provavelmente acontece em sítios de Pt.

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.

This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and continuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.

Este trabalho descreve a preparação e caracterização de ligas dispersas de Pt-Ru sobre carbono de alta área superficial, as quais foram avaliadas para a oxidação de CO em eletrodos de disco rotatório/camada fina porosa e para a oxidação de hidrogênio em células a combustível de eletrólito polimérico alimentadas com hidrogênio contendo 100 ppm de CO. Tratamentos térmicos (H2, 300 °C) aplicados aos catalisadores melhoram a tolerância a pequenas quantidades de CO e, em alguns casos, reduzem o potencial necessário para promover a oxidação de CO durante a varredura do potencial. Sob condições operacionais em uma célula a combustível na presença de CO, foi observado que os melhores resultados foram obtidos quando a liga Pt-Ru/C foi preparada por redução simultânea dos íons Pt (IV) e Ru (III), diferentemente da redução seqüencial.

This work describes the preparation and characterization of Pt-Ru alloys dispersed on high surface area carbon, which were evaluated for CO oxidation on thin porous coating rotating disk electrodes and for hydrogen oxidation on polymer electrolyte fuel cells fed with hydrogen containing 100 ppm CO. A thermal treatment (H2, 300 ºC) applied to the catalysts improves the tolerance to small quantities of CO and, in some cases, reduces the potential necessary to promote the CO oxidation during a linear potential scan. Under operational conditions in a fuel cell in the presence of CO it was observed that the best results were obtained when the Pt-Ru/C alloy was prepared by simultaneous reduction of the ions Pt (IV) and Ru (III), as opposed to a sequential reduction.