The effect of ultra-low proton concentration on the electrocatalytic reduction of nitrate over platinum

The electrocatalytic reduction of NO3- (aq) over platinum has been investigated in sulfuric acid solutions with proton concentrations between 1 mM and 50 mM. Cyclic voltammetry indicates that for [H+] < 10 mM, NO3- (aq) is reduced in two distinct regions of potential: one reduction peak occurs at approximately 0.1 V vs. RHE and one occurs at -0.13 V vs. RHE. This second reduction peak has never before been observed, and is not present for proton concentrations >10 mM, where hydrogen electroreduction prevails below 0.0 V vs. RHE. Chronoamperometry shows that the kinetics of the two reduction peaks are distinct, suggesting that the two reduction peaks may correspond to the evolution of different products. Results are discussed in the context of tuning the product selectivity of the electrocatalytic reduction of NO3- (aq). (C) 2007 Elsevier B.V. All rights reserved.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 Elsevier Ltd. All rights reserved.

Electropolymerization studies of PAni/(poly)luminol over platinum electrodes

This work presents a cyclic voltammetry study of the polyaniline/polyluminol copolymer on platinum electrodes. The results show that under determined conditions it is possible to obtain the copolymer deposited on a metallic surface. The luminol presence clearly affects the oxidation of aniline in the nucleation process and, additionally, changes the cyclic voltammetric characteristics of the obtained material. In this aspect, the copolymer presents hybrid characteristics when compared to the polyaniline and polyluminol separately obtained and seems to present intermediary conductivity.

On the apparent lack of preferential site occupancy and electrooxidation of CO adsorbed at low coverage onto stepped platinum surfaces

We report time evolution studies of low coverage CO adsorption (surface hydrogen site blocking < 40%) and oxidative stripping on stepped Pt(776) and Pt(554) surfaces. It was observed that there is no preferential site occupancy for CO adsorption on step or terrace. It is proposed that CO adsorption onto these surfaces is a random process, and after CO adsorption there is no appreciable shift from CO-(111) to CO-(110) sites. This implies that after adsorption, CO molecules either have a very long residence time, or that the diffusion coefficient is much lower than previously thought. After CO electrooxidation the sites released included both terrace (111) and step (110) orientations. For surface hydrogen site blocking > 40%, the lateral interactions might play a role in the preferential CO site occupancy. (C) 2011 Elsevier B.V. All rights reserved.

Spatiotemporal Pattern Formation in the Oscillatory Electro-Oxidation of Sulfide on a Platinum Disk

Spatiotemporal pattern formation in the electrocatalytic oxidation of sulfide on a platinum disk is investigated using electrochemical methods and a charge-coupled device (CCD) camera simultaneously. The system is characterized by different oscillatory regions spread over a wide potential range. An additional series resistor and a large electrode area facilitate observation of multiple regions of kinetic instabilities along the current/potential curve. Spatiotemporal patterns on the working electrode, such as fronts, pulses, spirals, twinkling eyes, labyrinthine stripes, and alternating synchronized deposition and dissolution, are observed at different operating conditions of series resistance and sweep rate.

The impact of water concentration on the catalytic oxidation of ethanol on platinum electrode in concentrated phosphoric acid

The electro-oxidation of ethanol on platinum in phosphoric acid opens the door to promote the oxidation reaction at higher temperatures. However, the effect of the presence of water is not well understood. In this work, the electro-oxidation of ethanol on platinum was studied in concentrated phosphoric acid containing different concentrations of water at room temperature. The results show that effect of bulk water on the rate electro-oxidation is highest at 0.60 V and decreases for increasing potentials. This was suggested as due to the increasing formation of oxygenated species on the electrode surface with potential, which in turn is more efficient than the increase of water content in the electrolyte. Altogether, these results were interpreted as an evidence of a Langmuir-Hinshelwood step involving oxygenated species as one of the adsorbed partners. (C) 2009 Elsevier B.V. All rights reserved.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response. (C) 2009 Elsevier Ltd. All rights reserved.

Voltammetric characterization of stepped platinum single crystal surfaces vicinal to the (110) pole

Platinum stepped surfaces vicinal to the (1 1 0) crystallographic pole have been investigated voltammetrically in 0.1 M HClO(4) and 0.1 M H(2)SO(4) solutions. Changes in the voltammetric profile with the step density suggest the existence of two types of surface sites, that has been ascribed to linear and bidimensional domains. This result indicates the existence of important restructuring processes that separate the real surface distribution from the nominal one. The electronic properties of the surfaces have been characterized with the CO charge displacement method and the potential of zero total charge has been calculated as a function of the step density. (c) 2009 Elsevier B.V. All rights reserved.

Produção científica nacional sobre clusters turísticos

Este estudo tem como objetivo analisar a produção científica nacional acerca de clusters turísticos. Trata-se de uma pesquisa de caráter bibliográfico e documental que pode ser definida como Revisão de Literatura. O material analisado refere-se a artigos publicados em periódicos científicos, trabalhos apresentados em eventos e teses e dissertações na área de turismo e paralelas. Foram analisados trabalhos referentes à: 1) identificação de clusters; 2) elaboração de modelos para identificação e avaliação de clusters turísticos; 3) análise de articulações entre atores do cluster, 4) competitividade dos clusters; 5) avaliação do desempenho de clusters; e 6) regiões turísticas. Conclui-se que a produção científica nessa área, embora de caráter recente, vem se intensificando. Recomenda-se que os pesquisadores da área se empenhem na construção de arcabouços teóricos e instrumentos estruturados de coleta de dados.

Atratividade em clusters comerciais: um estudo comparativo de dois clusters da cidade de São Paulo

O presente trabalho teve como objetivo a identificação de atributos relacionados à atratividade de clientes em clusters comerciais, na percepção de consumidores. Partindo-se da atratividade de clientes para lojas, desenvolveu-se um construto de avaliação de atratividade de clientes para clusters comerciais. Por meio de estudo descritivo-quantitativo junto a 240 consumidores, em dois reconhecidos clusters comerciais, utilizando-se a técnica de PLS-PM (Partial Least Squares Path Modeling), avaliou-se a relação entre a atratividade de clientes (variável reflexiva) e as dimensões do mix varejista de clusters comerciais (variáveis latentes), a partir do tratamento de indicadores de efeitos observáveis. Como principais resultados, observou-se que: (1) atratividade está associada significativamente às variáveis latentes, sugerindo robustez do modelo; (2) condições de compra e preços são dimensões com maior associação à atratividade de clientes, embora lojas, produtos e atendimento apresentem relevância; e (3) localização apresentou-se como dimensão menos correlacionada à atratividade de clientes para ambos os clusters.

Competitividade de clusters comerciais: estudo sobre uma aglomeração de pequenas lojas de veículos no município de São Paulo

O presente trabalho teve por objetivo identificar se a aglomeração de lojas de veículos existente na Avenida Marechal Tito / Avenida São Miguel (zona leste do município de São Paulo) forma um cluster comercial varejista, a partir dos fundamentos da performance competitiva de clusters descritos por Zaccarelli et al. (2008). Este é um estudo descritivo de natureza quantitativa, executado a partir de amostragem não-probabilística fundamentada no critério de acessibilidade dos pesquisadores junto aos proprietários e gestores de 128 lojas de automóveis, das quais 85,94% são microempresas, 12,50% são de pequeno porte e 1,56% são de médio porte. Constatou-se que a localidade ainda se encontra em um estágio inicial de cluster comercial varejista, pois apesar de haver forte concorrência entre os lojistas naquela concentração geográfica, com ausência de posições privilegiadas e substituição seletiva dos participantes não competitivos, a cooperação entre eles é incipiente, bem como não há nenhuma iniciativa voltada para o aumento da competitividade do aglomerado como um todo.

Proposta de avaliação estratégica de clusters turísticos: o caso de Paranapiacaba – SP

O artigo tem como objetivo utilizar a contribuição do conceito de cluster para avaliação estratégica e apresentar uma proposta de análise das oportunidades do setor turístico, considerando todos os agentes envolvidos na criação,comercialização e divulgação dos serviços/produtos turísticos, que possibilitem atender as necessidades exigidas pela demanda e o desenvolvimento sustentável da população receptora. Utilizando como foco o distrito de Paranapiacaba, na cidade de Santo André/SP, foi feita uma pesquisa descritiva, em que inicialmente foram utilizados dados secundários e, em seguida, foi realizada a coleta de dados primários por meio de entrevistas programadas e observação direta em campo dos agentes envolvidos. Os resultados obtidos indicam a necessidade da consolidação de uma entidade supra-empresarial que exerça a governança e que seja capaz de agregar os interesses dos diversos setores, além de garantir a implantação de uma série de ações que venham contribuir para a criação de vantagens competitivas.