Ethanol oxidation reactions using SnO(2)@Pt/C as an electrocatalyst

This paper presents a study on the ethanol oxidation reaction using SnO(2)@Pt/C core-shell structures as electrocatalysts. All the materials used, including Pt/C and PtSn/C E-tek, were 20% (w/w) metal on carbon. The formation of core-shell nanoparticles (SnO(2)@Pt/C) was measured by UV-vis spectrophotometry. X-ray diffraction measurements showed Pt (shell) diffraction patterns without influence from the SnO(2) core and without any shift in 2 theta values for Pt. The diameters of the core-shell particle structures, measured using high-resolution transmission electron microscopy images, were in the range of 3-16 nm. The electrochemical profile for SnO(2)@Pt/C in an acidic medium (H(2)SO(4) at a concentration of 0.5 mol L(-1)) was almost the same as the typical electrochemical behavior for Pt in an acidic medium. Furthermore, the onset potential for the ethanol oxidation reaction using SnO(2)@Pt/C was almost the same as that for PtSn/C E-tek (0.23 V versus the reversible hydrogen electrode). However, the mass current peak densities for ethanol oxidation were 50% higher on SnO(2)@Pt/C than on PtSn/C E-tek. In the polarization curve, the mass current density for ethanol oxidation was higher at all potentials for SnO(2)@Pt/C when compared to Pt/C and PtSn/C E-tek. At 0.5 V, the current mass density for ethanol oxidation on SnO(2)@Pt was 2.3 times of that for the same process on the commercial material. The electrocatalytic activity of SnO(2)@Pt/C for ethanol oxidation was associated with an increase in the electrochemically active surface area. However, an electronic effect should also be considered because the Pt shell changes its electronic structure in the presence of the foreign core. (C) 2010 Elsevier B.V. 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

Ethanol oxidation reaction on PtCeO(2)/C electrocatalysts prepared by the polymeric precursor method

This paper presents a study of the electrocatalysis of ethanol oxidation reactions in an acidic medium on Pt-CeO(2)/C (20 wt.% of Pt-CeO(2) on carbon XC-72R), prepared in different mass ratios by the polymeric precursor method. The mass ratios between Pt and CeO(2) (3:1, 2:1, 1:1, 1:2, 1:3) were confirmed by Energy Dispersive X-ray Analysis (EDAX). X-ray diffraction (XRD) structural characterization data shows that the Pt-CeO(2)/C catalysts are composed of nanosized polycrystalline non-alloyed deposits, from which reflections corresponding to the fcc (Pt) and fluorite (CeO(2)) structures were clearly observed. The mean crystallite sizes calculated from XRD data revealed that, independent of the mass ratio, a value close to 3 nm was obtained for the CeO(2) particles. For Pt, the mean crystallite sizes were dependent on the ratio of this metal in the catalysts. Low platinum ratios resulted in small crystallites. and high Pt proportions resulted in larger crystallites. The size distributions of the catalysts particles, determined by XRD, were confirmed by Transmission Electron Microscope (TEM) imaging. Cyclic voltammetry and chronoamperometic experiments were used to evaluate the electrocatalytic performance of the different materials. In all cases, except Pt-CeO(2)/C 1:1, the Pt-Ceo(2)/C catalysts exhibited improved performance when compared with Pt/C. The best result was obtained for the Pt-CeO(2)/C 1:3 catalyst, which gave better results than the Pt-Ru/C (Etek) catalyst. (C) 2009 Elsevier B.V. All rights reserved.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

The role of HBF(4) in electro-catalysis: Arsenic contamination and anion adsorption

We present in this work a comprehensive investigation of the role played by dissolved tetrafluoroboric acid on the electrochemical response of a polycrystalline platinum electrode in acidic media. HBF(4) from two different suppliers was employed and characterized in terms of the amount of arsenic contamination by Inductively Coupled Plasma-Optical Emission Spectroscopy. The effect of different amounts of HBF(4) on the voltammetric profile of the Pt vertical bar HClO(4)(aq) interface was investigated by means of electrochemical quartz crystal nanobalance (EQCN). Despite the comparable cyclic voltammograms, the presence of arsenic in one of the two HBF(4) used resulted in dramatic variations in the mass change profile, which evidences the deposition/dissolution of arsenic prior to the surface oxidation. For the arsenic-free HBF(4), its effect on the mass change profile was mainly associated to anion adsorption. The impact of dissolved HBF(4) on the electro-oxidation of formic acid was rationalized in terms of two contributions: current enhancement at low potentials due to the arsenic-assisted formic acid electro-oxidation and inhibition at high potentials due to anion adsorption. (C) 2011 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.

Fuel ethanol price drivers in the Atlantic basin : Brazil & the U.S. traders perspectives

Como a oportunidade de exportação de etanol combustível é muito recente, o agronegócio carece de literatura para formação de gestores e estrategistas. Este trabalho tem como objetivo descrever o mecanismo de formação de preços de etanol tanto no Brasil como nos Estados Unidos da America. Decupei as variáveis que impactam na formação de preços, custo de produção de etanol de cana-de-açúcar, custo da logística e desidratação no Caribe, custo do etanol de milho e fiz algumas análises de cenários de formação de preços das principais variáveis e consegui organizar este conhecimento em um gráfico que contém no eixo superior preço do etanol hidratado na usina no Brasil e no eixo inferior o preço do bushel de milho em Chicago cujas interceções nas retas da taxa do dólar e do preço do gás natural, fornecem no eixo Y o preço do produto no porto de Nova York, ficando uma visualização simples das possibilidades da janela de exportação. A metodologia permite assumir diferentes cenários de oferta, demanda e preços e estabelecer diferentes estratégias de comercialização.

Brazil and the USA: rethinking the future of ethanol for stronger mutual wns

A produção de etanol e a dominação da indústria, historicamente, tem sido uma fonte de discórdia para seus dois principais produtores. Os EUA com seu etanol de milho e o Brasil com sua etanol de cana, são os dois maiores produtores mundiais de etanol (1º EUA; 2º Brasil) e tem competido pela participação de mercado mundial há décadas. A partir de Dezembro de 2011, os EUA levantaram as tarifas e os subsídios que foram instalados para proteger sua indústria de etanol, o que muda o campo de jogo da produção mundial de etanol para o futuro. Atualmente em todo o mundo, o etanol é usado em uma proporção muito menor comparativamente a outros combustíveis. Esta pesquisa analisa o nível potencial de colaboração entre os EUA e o Brasil, facilitando um diálogo entre os stakeholders em etanol. A pesquisa consiste principalmente de conversas e entrevistas, com base em um conjunto de perguntas destinadas a inspirar conversas detalhadas e expansivas sobre os temas de relações Brasil-EUA e etanol. Esta pesquisa mostra que o etanol celulósico, que é também conhecido como etanol de segunda geração, oferece mais oportunidades de parceria entre os EUA e o Brasil, como há mais oportunidades para pesquisa e desenvolvimento em conjunto e transferência de tecnologia nesta área. Enquanto o etanol de cana no Brasil ainda é uma indústria próspera e crescente, o milho e a cana são muito diferentes geneticamente para aplicar as mesmas inovações exatas de um etanol de primeira geração, por outro. As semelhanças entre os processos de fermentação e destilação entre as matérias-primas utilizadas nos EUA e no Brasil para o etanol de segunda geração torna o investimento conjunto nesta área mais sensível. De segunda geração é uma resposta para a questão "alimentos versus combustíveis". Esta pesquisa aplica o modelo de co-opetição como um quadro de parceria entre os EUA e o Brasil em etanol celulósico. A pesquisa mostra que enquanto o etanol pode não ser um forte concorrente com o petróleo no futuro imediato, ele tem melhores perspectivas de ser desenvolvido como um complemento ao petróleo, em vez de um substituto. Como os EUA e o Brasil tem culturas de misturar etanol com petróleo, algo da estrutura para isso já está em vigor, a relação de complementaridade seria fortalecido através de uma política de governo clara e de longo prazo. A pesquisa sugere que apenas através desta colaboração, com toda a partilha de conhecimentos técnicos e estratégias econômicas e de desenvolvimento, o etanol celulósico será um commodity negociado mundialmente e uma alternativa viável a outros combustíveis. As entrevistas com os interessados em que esta pesquisa se baseia foram feitas ao longo de 2012. Como a indústria de etanol é muito dinâmica, certos eventos podem ter ocorrido desde esse tempo para modificar ou melhorar alguns dos argumentos apresentados.

How to indirectly assess transaction costs to evaluate market integration: evidence from the international ethanol market

Mercados são instituições criadas para facilitar uma atividade de comercialização. Isto é possível porque um mercado é constituído por instituições que foram desenhadas para reduzir os custos de transação associados a este processo de troca. A partir dessas duas ideias, esta tese possui três objetivos principais. (i) Analisar por que a literatura de análise de cointegração tem mensurado estes custos de forma imprecisa. A principal razão é certa confusão entre os conceitos de custos de transação, de transporte e de comercialização. (ii) Propor um procedimento para mensurar indiretamente os custos de transação de mercado variáveis combinando os modelos de cointegração com mudança de regime e a estrutura teórica oferecidas pela Nova Economia Institucional. Este procedimento é aplicado para quantificar quanto custa comercializar etanol no mercado internacional usando suas atuais instituições. (iii) Por fim, usando os mesmos modelos e a mesma estrutura teórica, esta dissertação contesta a hipótese de que já existe um mercado internacional de etanol bem desenvolvido, tal qual a literatura tem assumido. De forma semelhante, também é avaliada a hipótese de que a remoção das barreiras comerciais norte-americanas para o etanol brasileiro seria uma condição suficiente para o desenvolvimento deste mercado internacional. Os testes aplicados rejeitam ambas as hipóteses.