Eletrocatálise e poluição ambiental

This work considers mainly the problem of environmental pollution due to the production of energy by burning fossil fuels, particularly in urban vehicles. Electrochemical energy conversion is proposed as a partial solution to this problem, through the use of hydrogen in fuel cells. In both the production of hydrogen by electrolysis and in the electrochemical processes in fuel cells, the key factor is electrocatalysis. The concept of electrocatalysis, the production of catalysts and supported catalysts and their use in practical systems for the conversion of energy is discussed.

Reação de geração de oxigênio em eletrodos de Mn2O3 suportados em aço inoxidável

A study of the kinetics of oxygen evolution in alkaline conditions from ceramic films of Mn2O3 supported on stainless steel was carried out. This study has been done through the determination of transfer coefficients, Tafel slopes and exchange currents using potentiodynamic and quasi-potentiostatic measurements. The activation energy was determined as a function of the overpotential and, additionally, the electrode active surface was estimated. The results are consistent with data already published for other electrodes, implying that the methods used in this work were reliable and precise.

Aspectos relacionados à utilização da equação logística quadrática em processos eletroquímicos

The concepts of dissipation and feedback are contained in the behavior of many natural dynamical systems. They have been used to predict the evolution of populations leading to the formulation of the quadratic logistic equation (QLE). More recently, the QLE has been used to provide a better understanding of physicochemical systems with promising results. Many physical, chemical and biological dynamic phenomena can be understood on the basis of the QLE and this work describes the main aspects of this equation and some recent applications, with emphasis on electrochemical systems. Also, it is illustrated the concept of potential energy as a convenient way of describing the stability of the fixed points of the QLE.

Métodos de preparação de nanopartículas metálicas suportadas em carbono de alta área superficial, como eletrocatalisadores em células a combustível com membrana trocadora de prótons

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.

Efeito dos dióxidos de enxofre e de nitrogênio no desempenho de uma célula a combustível de membrana de intercâmbio de prótons

There is presently much interest in the clean and efficient generation of energy by proton exchange membrane fuel cells (PEMFC), using hydrogen as fuel. The generation of hydrogen by the reforming of other fuels, anaerobic fermentation of residual waters and other methods, often produce contaminants that affect the performance of the cell. In this work, the effect of gaseous SO2 and NO2 on the performance of a H2/O2 single PEMFC is studied. The results show that SO2 decreases irreversibly the performance of the cell under operating conditions, while NO2 has a milder effect that allows the recovery of the system.

Co-eletrodeposição oscilatória de cobre e estanho

It is investigated in the present contribution the oscillatory co-electrodeposition of CuSn on a polycrystalline gold surface in the presence of Triton X-100 surfactant and citric acid as additive, in acidic media. The experiments were conducted under potentiostatic control and the system dynamics characterized in terms of the morphology and stability of the current oscillations. Besides modulations in the frequency and amplitude of the current oscillations, several patterned states were observed, including relaxation-like and mixed mode oscillations. The oscillations were found to be very robust and some time series presented regular motions up to about two hours.

Effect of temperature on the electro-oxidation of ethanol on platinum

We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

Preparation of glasses and glass ceramics of heavy metal oxides containing silver: optical, structural and electrochemical properties

Silver containing heavy metal oxide glasses and glass ceramics of the system WO3-SbPO4-PbO-AgCl with different AgCl contents have been prepared and their thermal, structural and optical properties characterized. Glass ceramics containing metallic silver nanoparticles have been prepared by annealing glass samples at temperatures above the glass transition and analyzed by transmission electron microscopy and energy dispersive X-ray microanalysis. The presence of the metallic clusters has been also confirmed by the observation of a surface plasmon resonance band in the visible range. Cyclic voltammetric measurements indicated the presence of metallic silver into the glasses, even before to perform the thermal treatment.

Princípios fundamentais e modelos de transferência de energia inter e intramolecular

This work outlines the historic development of the concept and main theories of energy transfer, as well as the principal experiments carried out to confirm or refute the proposed theories. Energy transfer in coordination compounds is also discussed with a focus on rare earth systems.

Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Preparação de vidros e vitrocerâmicas de óxidos de metais pesados contendo prata: propriedades ópticas, estruturais e eletroquímicas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The electro-oxidation of carbon monoxide and ethanol on supported Pt nanoparticles: The influence of the support and catalyst microstructure

The sluggish kinetics of ethanol oxidation on Pt-based electrodes is one of the major drawbacks to its use as a liquid fuel in direct ethanol fuel cells, and considerable efforts have been made to improve the reaction kinetics. Herein, we report an investigation on the effect of the Pt microstructure (well-dispersed versus agglomerated nanoparticles) and the catalyst support (carbon Vulcan, SnO2, and RuO2) on the rate of the electrochemical oxidation of ethanol and its major adsorbed intermediate, namely, carbon monoxide. By using several structural characterization techniques such as X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy, along with potentiodynamic and potentiostatic electrochemical experiments, we show that by altering both the Pt microstructure and the support, the rate of the electrochemical oxidation of ethanol can be improved up to a factor of 12 times compared to well-dispersed carbon-supported Pt nanoparticles. As a result of a combined effect, the interaction of Pt agglomerates with SnO2 yielded the highest current densities among all materials studied. The differences in the activity are discussed in terms of structural and electronic properties as well as by mass transport effects, providing valuable insights to the development of more active materials. © 2013 Springer-Verlag Berlin Heidelberg.

Electrocatalytic Activity of Platinum-Niobium Nanoparticles for Ethanol Oxidation

Three nanostructured platinum-niobium supported on Vulcan XC-72R carbon black materials were prepared as catalysts for the ethanol electroxidation: (i) deposition of platinum and niobium on Vulcan XC-72R carbon black, (ii) platinum decorated on a mixture of commercial amorphous Nb2O5/carbon black, and (iii) the same than ii but using crystalline Nb2O5, by reduction of the precursors with sodium borohydride in ethanol. All the catalysts showed platinum crystal sizes in the range of 3-4 nm, with no or little modification of the lattice parameter. The analyses of the electronic structure from the XANES region of the XAS spectra displayed some interactions between platinum and niobium, despite the niobium was primarily in the form of pentoxide in all the catalysts. CO stripping exhibited a promising low onset potential and a large current density, especially in the case of the deposited catalyst. Ethanol electroxidation experiments revealed that the Pt-Nb(2)O(5)crystalline/C generated the largest current. However it was not effective to completely oxidize ethanol, leading to acetic acid as the main product. In this sense, the highest efficiency for the complete oxidation of ethanol was obtained for the deposited catalyst. These results were interpreted in terms of the physico-chemical characteristic displayed by the different catalysts. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.040210jes] All rights reserved.