Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.

Candida albicans inactivation and cell membrane integrity damage by microwave irradiation

In indicating the microwave irradiation for disinfecting dentures it is necessary to see how this procedure influences Candida albicans integrity and viability. The aim of this study was to evaluate the ability of microwaves to inactivate C. albicans and damage cell membrane integrity. Two 200-ml C. albicans (ATCC 10231) suspensions were obtained. A sterile denture was placed in a beaker containing the Experimental (ES) or the Control suspension (CS). ES was microwaved at 650 W for 6 min. Suspensions were optically counted using methylene blue dye uptake as indicative of membrane-damaged cells; spread on Agar Sabouraud dextrose (ASD) for viability assay; or spectrophotometrically measured at 550 nm. Cell-free solutions were submitted to content analyses of protein (Bradford and Pyrogallol red methods); Ca++ (Cresolftaleine complexone method); DNA (spectrophotometer measurements at 260 nm) and K + (selective electrode technique). Data were analysed by Student's t- or Wilcoxon z-tests (α = 0.05). All ES cells demonstrated cell membrane damage. Viable cells were non-existent in the ES ASD plates. No significant difference in optical density between ES and CS was observed (P = 0.272). ES cells released significantly high protein (P < 0.001, Bradford; P = 0.005, Pyrogallol red), K+ (P < 0.001), Ca++ (P = 0.012) and DNA (P = 0.046) contents. Microwaves inactivated C. albicans and damaged cell membrane integrity. © 2007 The Authors.

Desenvolvimento e teste de nanocatalisadores a base de Pd para a redução de oxigênio

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determination of mercury in river water by diffusive gradients in thin films using P81 membrane as binding layer

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

Aplicações de um potencial reativo no estudo da interação entre moléculas e superfícies bidimensionais

In materials science, the search for technological improvements have become one of the main subject of study of researchers. This is especially true in the case of materials with reduced sizes, in the nanometer scale. Important phenomena to be studied in these cases are the desorption and adsorption on two-dimensional materials, such as graphene. These phenomena are of great importance in the study of interactions between organic films, synthesis or catalysis of reactions on surfaces and even in the creation of nanoscale devices [1, 2, 3, 4]. Between the most important topics related to these phenomena are the storage of gases in low-dimensional systems and the study of nanostructured fuel cells or batteries. In this context we used two different parametrizations for the reactive force field ReaxFF to study the potential barriers and reaction barriers of our system. First we made a study about the Reaction Barriers and Energy Barriers for bonds between graphene and the following atoms: sulfur, fluorine, hydrogen, nitrogen and oxygen. It is important to have this information in order to make it possible to understand how these atoms react with the graphene sheet. Subsequently, we calculate reaction barriers for mixed structures where fluorine is a fixed element bonded to graphene and other element is simultaneously bonded to graphene. This other element (N, O, H or S) is varied in its possible relative positions (ortho, meta and para in relation to fluorine in either: the same side and in the opposite side of the graphene membrane)

Microwave-assisted hydrothermal synthesis of NiO-Ce1-XEuxO2-δ powders for fuel cell catalytic anodes

CeO2-based materials doped with rare earth (TR +3) can be used as alternative to traditional NiO-YSZ anodes in solid oxide fuel cells as they have higher ionic conductivity and lower ohmic losses compared to YSZ. Moreover, they allow fuel cell operation at lower temperatures (500-800°C). In the anode composition, the concentration of NiO acting as catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, promoting internal reform in the cell. In this work, NiO - Ce1-xEuxO2-δ compounds (x = 0.1, 0.2 and 0.3) have been synthesized by microwave-assisted hydrothermal method. The materials were characterized by TG, XRD, TPR and SEM-FEG techniques. The refinement of data obtained by X-ray diffraction showed the presence of ceria doped with europium crystallized in a cubic phase with fluorite structure, in addition to the presence of NiO. The microwave-assisted hydrothermal method showed significant reduction in the average particle size and good mass control of phase compositions compared to other chemical synthesis techniques.

Cell membrane integrity of candida albicans after different protocols of microwave irradiation

To evaluate the ability of low time microwaveexposureto inactivate and damage cell membrane integrity of C. albicans. Materials and Methods: Two 200ml C. albicans suspensions were obtained. Sterile dentures were placed in a beaker containing Experimental (ES) or Control suspensions (CS). ES was microwaved at 650 W for 1, 2, 3, 4 or 5 min. Suspensions were optically counted using Methylene blue dye as indicative of membrane-damaged cells; spread on Agar Sabouraud dextrose (ASD) for viability assay; or spectrophotometrically measured at 550nm. Cell-free solutions were submitted to content analyses of protein (Bradford and Pyrogallol red methods); Ca++ (Cresolphthalein Complexone method); DNA (spectrophotometer measurements at 260nm) and K+ (selective electrode technique). Data were analyzed by Student-t test and linear regression (α=0.05). In addition, flowcytometry analysis of Candida cells in suspensionwas performed using propidium iodide. Results: All ES cells demonstrated cell membrane damage at 3, 4 and 5 min,viable cells were nonexistent at 3, 4 and 5 min ES ASD plates and optical density of ES and CS was not significantly differentfor all exposition times. ES cells released highcontents of protein, K+ , Ca++ and DNA after 2 min exposition when compared to that of the CSs. Similar results were observed with flow cytometry analysiswith regard to the periodsof microwave exposure. Conclusions: Microwave irradiation inactivated C. albicansafter 3min and damaged cell membrane integrity after 2 min exposition.

The effect of alloying in Pt-Sn/C electrocatalysts in the performance of a direct ethanol fuel cell

Work on Pt-Sn-C catalysts for ethanol oxidation showed that a thermal treatment at moderate temperatures leads to a significant increase in activity. The best activity was observed for Pt3Sn1 thermally treated at 200 degrees C and ascribed to a Pt3Sn1 phase plus a cleaning effect. However, electronic effects may be very important and these were not evaluated in the Pt3Sn1 phase. Therefore, in this work we investigated the effect of the degree of alloy on the electronic structure of Pt3Sn1 electrocatalysts by performing electrochemical in situ X-ray absorption (XAS) experiments in the Pt L-III XANES region. Overall, the results show that although the occupancy of the Pt 5d band depends on the degree of alloy other factors, such as the presence of tin oxides/hydroxides in the materials, have to be considered to understand the performance of the DEFC.

Desenvolvimento de conjunto membrana-eletrodos para célula a combustível de metanol direto passiva

Direct methanol fuel cells (DMFCs) without external pumps or other ancillary devices for fuel and oxidant supply are known as passive DMFCs and are potential candidates to replace lithium-ion batteries in powering portable electronic devices. This paper presents the results obtained from a membrane electrode assembly (MEA) specifically designed for passive DMFCs. Appropriated electrocatalysts were prepared and the effect of their loadings was investigated. Two types of gas diffusion layers (GDL) were also tested. The influence of the methanol concentration was analyzed in each case. The best MEA performance presented a maximum power density of 11.94 mW cm^-2.

Investigation of a Pt3Sn/C Electro-Catalyst in a Direct Ethanol Fuel Cell Operating at Low Temperatures for Portable Applications

A 20% Pt3Sn/C catalyst was prepared by reduction with formic acid and used in a direct ethanol fuel cell at low temperatures. The electro-catalytic activity of this bimetallic catalyst was compared to that of a commercial 20% Pt/C catalyst. The PtSn catalyst showed better results in the investigated temperature range (30 degrees-70 degrees C). Generally, Sn promotes ethanol oxidation by adsorption of OH species at considerably lower potentials compared to Pt, allowing the occurrence of a bifunctional mechanism. The bimetallic catalyst was physico-chemically characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. The presence of SnO2 in the bulk and surface of the catalyst was observed. It appears that SnO2 can enhance the ethanol electro-oxidation activity at low potentials due to the supply of oxygen-containing species for the oxidative removal of CO and CH3CO species adsorbed on adjacent Pt active sites.

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

The effect of the relationship between particle size (d), inter-particle distance (x(i)), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x(i)/d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x(i)/d can be always obtained. For y >= 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x(i)/d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x(i)/d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x(i)/d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Oxygen reduction reaction catalyzed by epsilon-MnO2: Influence of the crystalline structure on the reaction mechanism

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

The ethanol electrooxidation at Pt layers deposited on polycrystalline Au

The ethanol electro-oxidation reaction was evaluated using a polycrystalline Au substrate modified with two different amounts of Pt using the galvanic exchange methodology. FTIR results suggest that Pt deposits have a greater ability to break the C-C bond present in the ethanol molecule. However, under potentiostatic conditions both modified Au surfaces undergo faster deactivation in comparison with polycrystalline platinum as indicated by the chronoamperometric results. XPS results indicate the presence of two phases depending on the Pt content. These are: (i) Pt-Au alloy and (ii) segregated Pt. The structural and electronic properties of these phases were related to the differences observed in the catalytic activity.

Densification and enhancement of the grain boundary conductivity of gadolinium-doped barium cerate by ultra fast flash grain welding

Doped barium cerate is a promising solid electrolyte for intermediate temperature fuel cells as a protonic conductor. However, it is difficult to sinter it to high density at a reasonable temperature. Moreover, it presents a high grain boundary resistivity at intermediate temperatures. Flash grain welding was applied to compacted samples, starting from a temperature of 910 degrees C and applying, for a short time, an ac electric polarization of 40 V, 1000 Hz. At that frequency, the resulting current flows through the grain boundaries promoting a welding via a local Joule heating. A large decrease of the grain boundary resistivity was observed by impedance spectroscopy. Scanning electron microscopy observations of polished and etched surfaces revealed highly sintered regions. Attempts were also made to combine flash grain welding with conventional sintering. (C) 2012 Elsevier Ltd. All rights reserved.