Characterization and single cell testing of Pt/C electrodes prepared by electrodeposition

Electrodes for proton exchange membrane fuel cells (PEMFC) have been prepared by the electrodeposition method. For this task, the electrodeposition of platinum is carried out on a carbon black substrate impregnated with an ionomer, proton conducting, medium. Before electrodeposition, the substrate is submitted to an activation process to increase the hydrophilic character of the surface to a few microns depth.Electrodeposition of platinum takes place inside the generated surface hydrophilic layer, resulting in a continuous phase covering totally or partially carbon substrate grains. Cross sectional images show a decay profile of platinum towards the interior of the substrate, reflecting a deposition process limited by diffusion of PtCl₆²⁻ through the porous substrate. Electrodes with different platinum loads have been prepared, and membrane electrode assemblies (MEA) have been mounted with the electrodeposited electrodes as cathode and other standard components (commercial anode and Nafion^R 117 membrane). The electrochemically active surface area determined from hydrogen underpotential deposition charge, is lower on the electrodeposited electrodes than on standard electrodes. However, single cell testing shows higher mass specific activity on electrodeposited cathodes with low and intermediate Pt load (below 0.05 mg Pt cm⁻²).     

SrCo1−xSbxO3−δ perovskite oxides as cathode materials in solid oxide fuel cells

The SrCo_1−xSb_xO_3−δ (x = 0.05, 0.1, 0.15 and 0.2) system was tested as possible cathode for solid oxide fuel cells (SOFCs). X-ray diffraction results show the stabilization of a tetragonal P4/mmm structure with Sb contents between x = 0.05 and x = 0.15. At x = 0.2 a phase transition takes place and the material is defined in the cubic Pm-3m space group. In comparison with the undoped hexagonal SrCoO₃ phase, the obtained compounds present high thermal stability without abrupt changes in the expansion coefficient. In addition, a great enhancement of the electrical conductivity was observed at low and intermediate temperatures (T ≤ 800 °C). The sample with x = 0.05 displays the highest conductivity value that reaches 500 S cm⁻¹ at 400 °C and is over 160 S cm⁻¹ in the usual working conditions of a cathode in SOFC (650-900 °C). Moreover, the impedance spectra of the SrCo_1−xSb_xO_3−δ/Ce_0.8Nd_0.2O_2−δ/SrCo_1−xSb_xO_3−δ (x ≥ 0.05) symmetrical cells reveal polarization resistances below 0.09 Ω cm² at 750 °C which are much smaller than that displayed by the pristine SrCoO_3−δ sample. The composition with x = 0.05 shows the lowest ASR values ranging from 0.009 to 0.23 Ω cm² in the 900-600 °C temperature interval with an activation energy of 0.82 eV.     

Optimal operation of batch enantiomer crystallization: From ternary diagrams to predictive control

In this work, the modeling and control of batch crystallization for racemic compound forming systems is addressed in a systematic fashion. Specifically, a batch crystallization process is considered for which the initial solution has been pre‐enriched in the desired enantiomer to enable crystallization of only the preferred enantiomer. A method for determining desired operating conditions (composition of the initial pre‐enriched solution and temperature to which the mixture must be cooled for maximum yield) for the batch crystallizer based on a ternary diagram for the enantiomer mixture in a solvent is described. Subsequently, it is shown that the information obtained from the ternary diagram, such as the maximum yield attainable from the process due to thermodynamics, can be used to formulate constraints for an optimization‐based control method to achieve desired product characteristics such as a desired yield. The proposed method is demonstrated for the batch crystallization of mandelic acid in a crystallizer with a fines trap that is seeded with crystals of the desired enantiomer. The process is controlled with an optimization‐based controller to minimize the ratio of the mass of crystals obtained from nuclei to the mass obtained from seeds while maintaining the desired enantioseparation. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1618–1637, 2018     

Preparation and characterisation of SOFC anodic materials based on Ce–Cu

Ce–Cu mixed oxide precursors with varing Ce:Cu atomic ratio have been prepared by freeze-drying and microemulsion coprecipitation methods. Nanostructured particles having different properties have been obtained. Physicochemical properties have been studied with X-ray diffraction, UV–vis spectroscopy, nitrogen adsorption–desorption, mercury intrusion porosimetry, ICP-AES, conductivity measurement and thermal expansion coefficient. All samples show fluorite structure with slight copper surface enrichment for samples having high copper content. Microemulsion method allows the introduction of a large quantity of copper into the cerium oxide structure, obtaining a nanostructured mixed oxide of high surface area. On the other hand, freeze-drying samples does not show evidence of copper incorporation to the lattice of cerium oxide. All materials have a thermal expansion coefficient similar to other components of SOFC.     

Optimization of C:N ratio and minimal initial carbon source for poly(3‐hydroxybutyrate) production by Bacillus megaterium

BACKGROUND: The aim of this research was the optimization of poly(3‐hydroxybutyrate)—P(3HB)—production in submerged cultures of Bacillus megaterium in a mineral medium using sucrose as carbon source and nitrogen as the limiting substrate. Small‐scale experiments were carried out in shake flasks at 30 °C and 160 rpm in order to evaluate the best initial sucrose concentration and carbon:nitrogen ratio to maximize biomass accumulation and biopolymer production. An objective function in terms of residual sucrose and P(3HB) production was proposed in order to optimize the amount of carbon source used and the production of P(3HB). RESULTS: High production of P(3HB) was obtained, with approximately 70% (CDW) accumulation in cells without nitrogen limitation and strongly correlated with the pH of the culture. Scaling‐up the system to cultures in a bioreactor, with or without pH control, a reduction of P(3HB) accumulation (around 30% CDW) was observed when compared with shaker cultures, suggesting a possible role of oxygen limitation as a stress signaling for P(3HB) synthesis. CONCLUSIONS: Results of our experiments showed that Bacillus megaterium was able to produce P(3HB) at one of the highest production rates so far reported for this bacterium, making this microorganism very interesting for industrial applications. Comparisons of shaker and bench‐scale bioreactor experiments show both the importance of pH and aeration strategies. It is likely that complex aeration strategies linked to cell metabolism will be necessary for further developments using this bacterium. Copyright © 2009 Society of Chemical Industry     

Ammonia as efficient fuel for SOFC

Ammonia is a possible candidate as the fuel for SOFCs. In this work, the influence on the performance of a tubular SOFC running on ammonia is studied. Analysis of open circuit voltages (OCVs) on the cell indicated the oxidation of ammonia within a SOFC is a two-stage process: decomposition of the inlet ammonia into nitrogen and hydrogen, followed by oxidation of hydrogen to water. For comparison, cell was also tested with hydrogen as the fuel and air as oxidant at different temperatures showing a similar behaviour. The performance of the cell tested under various conditions shows the high potential of ammonia as fuel for SOFCs.     

Comparative analysis of the electroactive area of Pt/C PEMFC electrodes in liquid and solid polymer contact by underpotential hydrogen adsorption/desorption

Because of the different experimental conditions found in literature for the measurement of the electroactive area of Pt/C electrodes of proton exchange membrane fuel cells (PEMFC) by means of underpotential hydrogen adsorption (H_UPD) voltammetry, specially concerning sweep rate and temperature, it was found necessary to perform an analysis of these parameters. With this aim, the electroactive area of PEMFC electrodes has been measured by means of H_UPD voltammetry at different sweep rates and temperatures, in liquid electrolyte and solid polymer contact. Both configurations show that H_UPD adsorption and desorption charges are strongly dependent on sweep rate voltage and temperature. The most common behaviour observed is a maximum in H_UPD desorption charge, typically in the 100–10 mV s⁻¹ sweep rate range, whereas H_UPD adsorption charge shows continuous increase with decreasing sweep rate. The decrease of desorption charge at low sweep rates is attributed to adsorbing species related with carbon support reactivity. These processes are also responsible for the increase in desorption H_UPD charge at low sweep rate. At high sweep rate, both adsorption and desorption H_UPD charges decrease due to limiting diffusion of protons through the microporous electrode. As a consequence, it is found that the closest approximation to the real electroactive area (i.e. the area accessible to protons) corresponds to the maximum in the H_UPD desorption charge in the range of 10–100 mV s⁻¹ sweep rate. The influence of measuring temperature is also tested in the range 25 °C–80 °C. A dependence of the adsorption and desorption hydrogen charges is found, due to thermodynamic and kinetics factors. We observe that the processes competing with hydrogen adsorption, i.e. generation and adsorption of carbon species are enhanced with temperature, so a low measuring temperature is found as most appropriate.     

Physico-chemical study of the degradation of membrane-electrode assemblies in a proton exchange membrane fuel cell stack

A proton exchange membrane fuel cell stack integrated by 8-elements has been evaluated in an accelerated stress test. The application of techniques such as TEM analyses of ultramicrotome-sliced sections of some samples and XRD, XPS and TGA of spent electrodes reveal the effects of several degradation processes contributing to reduce the cells performance. The reduction of the Pt surface area at the cathode is favored by the oxidation of carbon black agglomerates in the catalytic layer, the agglomeration of Pt particles and by the partial dissolution of Pt, which migrates towards the anode and precipitates within the membrane. In the light of the TEM, EDAX and XPS results, two combined effects are probably responsible of the increase of the internal resistance of the stack cells: (i) a lower proton conductivity of the membranes due to the high affinity of the sulfonic acid groups for ions originated from Pt crystallites and other peripherical elements such as the silicone elastomeric gaskets and (ii) the increment of electrically isolated islands in the cathode gas diffusion electrodes resulting from carbon corrosion and the degradation of the perfluorinated polymers. Water accumulation and inhomogeneous gas distribution throughout the stack cells originate different degradation rates in them.     

Immobilization of methylene blue on self-assembled iodine monolayers on gold

The immobilization of methylene blue (MB) on iodine-covered Au(111) is studied by electrochemical techniques, scanning tunneling microscopy (STM), Auger Electron Spectroscopy (AES), and Raman spectroscopy. Results show that MB species are efficiently adsorbed on the square root of 3 x square root of 3 R30 degrees I lattice on Au(111). The electrochemical behavior of the adsorbed MB molecules is reversible, indicating a relatively fast electron transfer from the Au(111) surface to the immobilized MB species through the iodine layer. STM images with molecular resolution are consistent with adsorption of MB dimers on a square root of 3 x square root of 3 R30 degrees I lattice placed atop of the Au(111) substrate. Results are compared to those obtained for MB immobilized on Au(111) covered by S(n) (n = 3-8) surface structures.