Operation of polymer electrolyte membrane fuel cells with dry feeds: Design and operating strategies

The operation of polymer electrolyte membrane fuel cells (PEMFCs) with dry feeds has been examined with different fuel cell flow channel designs as functions of pressure, temperature and flow rate. Auto-humidified (or self-humidifying) PEMFC operation is improved at higher pressures and low gas velocities where axial dispersion enhances back-mixing of the product water with the dry feed. We demonstrate auto-humidified operation of the channel-less, self-draining fuel cell, based on a stirred tank reactor; data is presented showing auto-humidified operation from 25 to 115 degrees C at 1 and 3 atm. Design and operating requirements are derived for the auto-humidified operation of the channel-less, self-draining fuel cell. The auto-humidified self-draining fuel cell outperforms a fully humidified serpentine flow channel fuel cell at high current densities. The new design offers substantial benefits for simplicity of operation and control including: the ability to self-drain reducing flooding, the ability to uniformly disperse water removing current gradients and the ability to operate on dry feeds eliminating the need for humidifiers. Additionally, the design lends itself well to a modular design concept. (c) 2005 Elsevier B.V. All rights reserved.

The role of carbon in fuel cells

Carbon possesses unique electrical and structural properties that make it an ideal material for use in fuel cell construction. In alkaline, phosphoric acid and proton-exchange membrane fuel cells (PEMFCs), carbon is used in fabricating the bipolar plate and the gas-diffusion layer. It can also act as a support for the active metal in the catalyst layer. Various forms of carbon - from graphite and carbon blacks to composite materials - have been chosen for fuel-cell components. The development of carbon nanotubes and the emergence of nanotechnology in recent years has therefore opened up new avenues of matenials development for the low-temperature fuel cells, particularly the hydrogen PEMFC and the direct methanol PEMFC. Carbon nanotubes and aerogels are also being investigated for use as catalyst support, and this could lead to the production of more stable, high activity catalysts, with low platinum loadings (< 0.1 Mg cm(-2)) and therefore low cost. Carbon can also be used as a fuel in high-temperature fuel cells based on solid oxide, alkaline or molten carbonate technology. In the direct carbon fuel cell (DCFC), the energy of combustion of carbon is converted to electrical power with a thermodynamic efficiency close to 100%. The DCFC could therefore help to extend the use of fossil fuels for power generation as society moves towards a more sustainable energy future. (c) 2006 Elsevier B.V. All rights reserved.

Simultaneous high-resolution pH and spectrophotometric recordings of oxygen binding in native blood microvolumes, link to supplementary material

Oxygen equilibrium curves have been widely used to understand oxygen transport in numerous organisms. A major challenge has been to monitor oxygen binding characteristics and concomitant pH changes as they occur in vivo, in limited sample volumes. Here we report a technique allowing highly resolved and simultaneous monitoring of pH and blood pigment saturation in minute blood volumes. We equipped a gas diffusion chamber with a broad range fibre optic spectrophotometer and a micro-pH optode and recorded changes of pigment oxygenation along PO2 and pH gradients to test the setup. Oxygen binding parameters derived from measurements in only 15 µl of haemolymph from the cephalopod Octopus vulgaris showed low instrumental error (0.93%) and good agreement with published data. Broad range spectra, each resolving 2048 data points, provided detailed insight into the complex absorbance characteristics of diverse blood types. After consideration of photobleaching and intrinsic fluorescence, pH optodes yielded accurate recordings and resolved a sigmoidal shift of 0.03 pH units in response to changing PO2 from 0-21 kPa. Highly resolved continuous recordings along pH gradients conformed to stepwise measurements at low rates of pH changes. In this study we showed that a diffusion chamber upgraded with a broad range spectrophotometer and an optical pH sensor accurately characterizes oxygen binding with minimal sample consumption and manipulation. We conclude that the modified diffusion chamber is highly suitable for experimental biologists who demand high flexibility, detailed insight into oxygen binding as well as experimental and biological accuracy combined in a single set up.

Séquestration géologique du CO2 par carbonatation minérale dans les résidus miniers

La carbonatation minérale dans les résidus miniers est un moyen sûr et permanent de séquestrer le CO2 atmosphérique. C’est un processus naturel et passif qui ne nécessite aucun traitement particulier et donc avantageux d’un point de vue économique. Bien que la quantité de CO2 qu’il soit possible de séquestrer selon ce processus est faible à l’échelle globale, dans le cadre d’un marché du carbone, les entreprises minières pourraient obtenir des crédits et ainsi revaloriser leurs résidus. À l’heure actuelle, il y a peu d’informations pour quantifier le potentiel de séquestration du CO2 de façon naturelle et passive dans les piles de résidus miniers. Il est donc nécessaire d’étudier le phénomène pour comprendre comment évolue la réaction à travers le temps et estimer la quantité de CO2 qui peut être séquestrée naturellement dans les piles de résidus. Plusieurs travaux de recherche se sont intéressés aux résidus miniers de Thetford Mines (Québec, Canada), avec une approche principalement expérimentale en laboratoire. Ces travaux ont permis d’améliorer la compréhension du processus de carbonatation, mais ils nécessitent une validation à plus grande échelle sous des conditions atmosphériques réelles. L’objectif général de cette étude est de quantifier le processus de carbonatation minérale des résidus miniers sous des conditions naturelles, afin d’estimer la quantité de CO2 pouvant être piégée par ce processus. La méthodologie utilisée repose sur la construction de deux parcelles expérimentales de résidus miniers situées dans l’enceinte de la mine Black Lake (Thetford Mines). Les résidus miniers sont principalement constitués de grains et de fibres de chrysotile et lizardite mal triés, avec de petites quantités d’antigorite, de brucite et de magnétite. Des observations spatiales et temporelles ont été effectuées dans les parcelles concernant la composition et la pression des gaz, la température des résidus, la teneur en eau volumique, la composition minérale des résidus ainsi que la chimie de l’eau des précipitations et des lixiviats provenant des parcelles. Ces travaux ont permis d’observer un appauvrissement notable du CO2 dans les gaz des parcelles (< 50 ppm) ainsi que la précipitation d’hydromagnésite dans les résidus, ce qui suggère que la carbonatation minérale naturelle et passive est un processus potentiellement important dans les résidus miniers. Après 4 ans d’observations, le taux de séquestration du CO2 dans les parcelles expérimentales a été estimé entre 3,5 et 4 kg/m3/an. Ces observations ont permis de développer un modèle conceptuel de la carbonatation minérale naturelle et passive dans les parcelles expérimentales. Dans ce modèle conceptuel, le CO2 atmosphérique (~ 400 ppm) se dissout dans l’eau hygroscopique contenue dans les parcelles, où l’altération des silicates de magnésium forme des carbonates de magnésium. La saturation en eau dans les cellules est relativement stable dans le temps et varie entre 0,4 et 0,65, ce qui est plus élevé que les valeurs de saturation optimales proposées dans la littérature, réduisant ainsi le transport de CO2 dans la zone non saturée. Les concentrations de CO2 en phase gazeuse, ainsi que des mesures de la vitesse d’écoulement du gaz dans les cellules suggèrent que la réaction est plus active près de la surface et que la diffusion du CO2 est le mécanisme de transport dominant dans les résidus. Un modèle numérique a été utilisé pour simuler ces processus couplés et valider le modèle conceptuel avec les observations de terrain. Le modèle de transport réactif multiphase et multicomposant MIN3P a été utilisé pour réaliser des simulations en 1D qui comprennent l’infiltration d’eau à travers le milieu partiellement saturé, la diffusion du gaz, et le transport de masse réactif par advection et dispersion. Même si les écoulements et le contenu du lixivat simulés sont assez proches des observations de terrain, le taux de séquestration simulé est 22 fois plus faible que celui mesuré. Dans les simulations, les carbonates précipitent principalement dans la partie supérieure de la parcelle, près de la surface, alors qu’ils ont été observés dans toute la parcelle. Cette différence importante pourrait être expliquée par un apport insuffisant de CO2 dans la parcelle, qui serait le facteur limitant la carbonatation. En effet, l’advection des gaz n’a pas été considérée dans les simulations et seule la diffusion moléculaire a été simulée. En effet, la mobilité des gaz engendrée par les fluctuations de pression barométrique et l’infiltration de l’eau, ainsi que l’effet du vent doivent jouer un rôle conséquent pour alimenter les parcelles en CO2.

Changes in the storage and sink of carbon dioxide in subsurface atmospheres controlled by climate-driven processes: the case of the Ojo Guareña karst system

A comprehensive environmental monitoring program was conducted in the Ojo Guareña cave system (Spain), one of the longest cave systems in Europe, to assess the magnitude of the spatiotemporal changes in carbon dioxide gas (CO2) in the cave–soil–atmosphere profile. The key climate-driven processes involved in gas exchange, primarily gas diffusion and cave ventilation due to advective forces, were characterized. The spatial distributions of both processes were described through measurements of CO2 and its carbon isotopic signal (δ13C[CO2]) from exterior, soil and cave air samples analyzed by cavity ring-down spectroscopy (CRDS). The trigger mechanisms of air advection (temperature or air density differences or barometric imbalances) were controlled by continuous logging systems. Radon monitoring was also used to characterize the changing airflow that results in a predictable seasonal or daily pattern of CO2 concentrations and its carbon isotopic signal. Large daily oscillations of CO2 levels, ranging from 680 to 1900 ppm day−1 on average, were registered during the daily oscillations of the exterior air temperature around the cave air temperature. These daily variations in CO2 concentration were unobservable once the outside air temperature was continuously below the cave temperature and a prevailing advective-renewal of cave air was established, such that the daily-averaged concentrations of CO2 reached minimum values close to atmospheric background. The daily pulses of CO2 and other tracer gases such as radon (222Rn) were smoothed in the inner cave locations, where fluctuation of both gases was primarily correlated with medium-term changes in air pressure. A pooled analysis of these data provided evidence that atmospheric air that is inhaled into dynamically ventilated caves can then return to the lower troposphere as CO2-rich cave air.

WATER TRANSPORT THROUGH POROUS MEDIA AND IN FLOW CHANNELS OF PROTON EXCHANGE MEMBRANE FUEL CELL

Proton exchange membrane (PEM) fuel cell has been known as a promising power source for different applications such as automotive, residential and stationary. During the operation of a PEM fuel cell, hydrogen is oxidized in anode and oxygen is reduced in the cathode to produce the intended power. Water and heat are inevitable byproducts of these reactions. The water produced in the cathode should be properly removed from inside the cell. Otherwise, it may block the path of reactants passing through the gas channels and/or gas diffusion layer (GDL). This deteriorates the performance of the cell and eventually can cease the operation of the cell. Water transport in PEM fuel cell has been the subject of this PhD study. Water transport on the surface of the GDL, through the gas flow channels, and through GDL has been studied in details. For water transport on the surface of the GDL, droplet detachment has been measured for different GDL conditions and for anode and cathode gas flow channels. Water transport through gas flow channels has been investigated by measuring the two-phase flow pressure drop along the gas flow channels. As accumulated liquid water within gas flow channels resists the gas flow, the pressure drop increases along the flow channels. The two-phase flow pressure drop can reveal useful information about the amount of liquid water accumulated within gas flow channels. Liquid water transport though GDL has also been investigated by measuring the liquid water breakthrough pressure for the region between the capillary fingering and the stable displacement on the drainage phase diagram. The breakthrough pressure has been measured for different variables such as GDL thickness, PTFE/Nafion content within the GDL, GDL compression, the inclusion of a micro-porous layer (MPL), and different water flow rates through the GDL. Prior to all these studies, GDL microstructural properties have been studied. GDL microstructural properties such as mean pore diameter, pore diameter distribution, and pore roundness distribution have been investigated by analyzing SEM images of GDL samples.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

From lattice-gas models to nonlinear diffusion models: A derivation of macroscopic equations and fluctuations

We derive nonlinear diffusion equations and equations containing corrections due to fluctuations for a coarse-grained concentration field. To deal with diffusion coefficients with an explicit dependence on the concentration values, we generalize the Van Kampen method of expansion of the master equation to field variables. We apply these results to the derivation of equations of phase-separation dynamics and interfacial growth instabilities.

Reaction-diffusion lattice gas: Theory and computer results

We report on the study of nonequilibrium ordering in the reaction-diffusion lattice gas. It is a kinetic model that relaxes towards steady states under the simultaneous competition of a thermally activated creation-annihilation $(reaction$) process at temperature T, and a diffusion process driven by a heat bath at temperature T?T. The phase diagram as one varies T and T, the system dimension d, the relative priori probabilities for the two processes, and their dynamical rates is investigated. We compare mean-field theory, new Monte Carlo data, and known exact results for some limiting cases. In particular, no evidence of Landau critical behavior is found numerically when d=2 for Metropolis rates but Onsager critical points and a variety of first-order phase transitions.

CH and C2 radicals characterization in natural gas turbulent diffusion flames

This paper reports the construction of an axisymmetric nonpremixed piloted jet burner, with well-defined initial and boundary conditions, known as the Delft burner, to assess turbulence-chemistry interaction in non-premixed turbulent flames. Detailed experimental information is described, involving hot-wire anemometry, thin-wire thermocouples and chemiluminescence visualization measurements. Radial profile of the axial mean velocity indicates excellent agreement between flow patterns developed within Delft installation and the one described herein. Chemiluminescence emissions from CH and C2 free-radicals were acquired with a CCD camera. Tomography reconstruction analysis was utilised to compare radical emissions and temperature spatial distributions. There was a strong dependence between temperature and CH/C 2 emissions. This is an indication that these radicals can be used in flame front studies.

Dynamic transitions in a two dimensional associating lattice gas model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical lambda-line. The high density liquid phase and the fluid phases are separated by a second critical tau-line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong transition when the critical lambda-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the critical tau-line is crossed by decreasing the temperature at a constant chemical potential.

Analysis of multiple gas solid reactions

Multiple gas solid reactions involving one solid and N gaseous reactants are investigated in this study by using a matched asymptotic expansion technique. Two cases are particularly studied. In the first case all N chemical reaction rates are faster than the diffusion rate. While in the second case only M (M < N) chemical reaction rates are faster than the diffusion rate and the rates of the remaining (N-M) chemical reactions are comparable to that of diffusion. For these two cases the solid concentration profile behaves like a travelling wave. In the first case the wave front velocity is contributed linearly by all gaseous reactants (additive law) while in the second case this law does not hold.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Novel composite membranes for gas separation: Preparation and performance

High performance composite membranes based on molecular sieving silica (MSS) were synthesized using sols containing silicon co-polymers (methyltriethoxysilane and tetraethylorthosilicate). Alpha alumina supports were treated with hydrochloric acid prior to sol deposition. Permselectivity of CO2 over CH4 as high as 16.68 was achieved whilst permeability of CO2 up to 36.7 GPU (10(-6) cm(3) (STP) cm(-2) . s(-1) . cm Hg-1) was measured. The best membrane's permeability was finger printed during various stages of the synthesis process showing an increase in CO2/CH4 permselectivity by over 25 times from initial support condition (no membrane film) to the completion of pore structure tailoring. Transport measurement results indicate that the membrane pretreated with HCl has highest permselectivity and permeation rate. In particular, there is a definite cut-off pore size between 3.3 and 3.4 angstroms which is just below the kinetic diameters of Ar and CH4. This demonstrates that the mechanism for the separation in the prepared composite membrane is molecular sieving (activated diffusion), rather than Knudsen diffusion.

Oxidation of toluene in waste gas streams using mesoporous Ti-hexagonal mesoporous silica

Various mesoporous catalysts with titanium loadings between 0.5 and 4 Ti wt. % and surface areas between 600 and 1,600 m(2)/g were synthesized using the molecular designed dispersion technique. These catalysts were tested using toluene oxidation in a fixed bed reactor at temperatures between 300 and 550degreesC. The reaction products were found to be CO2 and CO with selectivity towards CO2 above 80% for all catalysts. The catalytic activity of the catalysts increases with titanium loading. The total conversion at 550degreesC was not affected by the textural porosity, but increased textural porosity did significantly reduce the ignition temperature by up to 50degreesC. The Thiele modulus was calculated to be much less than one for all these materials indicating that the reaction rate is not diffusion, limited.