Nanosized Pt/IrO2 electrocatalyst prepared by modified polyol method for application as dual function oxygen electrode in unitized regenerative fuel cells

A new generation of highly efficient and non-polluting energy conversion and storage systems is vital to meeting the challenges of global warming and the finite reality of fossil fuels. In this work, nanosized Pt/IrO₂ electrocatalysts are synthesized and investigated for the oxygen evolution and reduction reactions in unitized regenerative fuel cells (URFCs). The catalysts are prepared by decorating Pt nanoparticles (2–10 nm) onto the surface of a nanophase IrO₂ (7 nm) support using an ultrasonic polyol method. The synthesis procedure allows deposition of metallic Pt nanoparticles on Ir-oxide without causing any occurrence of metallic Ir. The latter is significantly less active for oxygen evolution than the corresponding oxide. This process represents an important progress with respect to the state of the art in this field being the oxygen electrocatalyst generally obtained by mechanical mixing of Pt and IrO₂. The nanosized Pt/IrO₂ (50:50 wt.%) is sprayed onto a Nafion 115 membrane and used as dual function oxygen electrode, whereas 30 wt.% Pt/C is used as dual function hydrogen electrode in the URFC. Electrochemical activity of the membrane-electrode assembly (MEA) is investigated in a single cell at room temperature and atmospheric pressure both under electrolysis and fuel cell mode to assess the perspectives of the URFC to operate as energy storage device in conjunction with renewable power sources.     

High Temperature Operation of a Solid Polymer Electrolyte Fuel Cell Stack Based on a New Ionomer Membrane

Polymer electrolyte fuel cell stacks assembled with Johnson Matthey Fuel Cells and SolviCore MEAs based on the Aquivion™ E79‐03S short‐side chain (SSC), chemically stabilised perfluorosulphonic acid membrane developed by Solvay Solexis were investigated at CNR‐ITAE in the EU Sixth Framework ‘Autobrane' project. Electrochemical experiments in fuel cell short stacks were performed under practical automotive operating conditions at pressures of 1–1.5 bar abs. over a wide temperature range, up to 130 °C, with varying levels of humidity (down to 18% R. H.). The stacks using large area (360 cm²) MEAs showed elevated performance in the temperature range from ambient to 100 °C (cell power density in the range of 600–700 mWcm^–2) with a moderate decrease above 100 °C. The performances and electrical efficiencies achieved at 110 °C (cell power density of about 400 mWcm^–2 at an average cell voltage of about 0.5–0.6 V) are promising for automotive applications. Duty‐cycle and steady‐state galvanostatic experiments showed excellent stack stability for operation at high temperature. A performance comparison of Aquivion^TM and Nafion^TM‐based MEAs under practical operating conditions showed a significantly better capability for the Solvay Solexis membrane to sustain high temperature operation.     

Catalytic features of Ni/Ba–Ce0.9–Y0.1 catalyst to produce hydrogen for PCFCs by methane reforming

Methane reforming in steam (SR), auto-thermal (ATR) and partial oxidation (POX) conditions over Ni/Ba–Ce_0.9–Y_0.1 catalyst was investigated in the temperature range 500–700 °C. Catalyst presents a satisfying activity in POX condition only. BCY carrier was not stable in the presence of CO₂ and, irrespective of reaction conditions, it reacts with CO₂ giving rise to the formation of BaCO₃ and CeO₂. The very low activity observed in SR conditions was due to the negative role exerted by water strongly absorbed on catalyst surface, limiting so the accessibility and reduction state of Ni active sites. In POX condition catalyst is active and satisfying H₂ yield can be reached by operating at T = 700 °C. A significant reduction of coke formation was observed by operating in POX at 700 °C. On the contrary, in ATR condition at the same reaction temperature huge amount of filamentous coke was observed.     

Performance comparison of long and short-side chain perfluorosulfonic membranes for high temperature polymer electrolyte membrane fuel cell operation

A new Aquivion™ E79-03S short-side chain perfluorosulfonic membrane with a thickness of 30 μm (dry form) and an equivalent weight (EW) of 790 g/equiv recently developed by Solvay-Solexis for high-temperature operation was tested in a pressurised (3 bar abs.) polymer electrolyte membrane (PEM) single cell at a temperature of 130 °C. For comparison, a standard Nafion™ membrane (EW 1100 g/equiv) of similar thickness (50 μm) was investigated under similar operating conditions. Both membranes were tested for high temperature operation in conjunction with an in-house prepared carbon supported Pt electrocatalyst. The electrocatalyst consisted of nanosized Pt particles (particle size ∼2 nm) dispersed on a high surface area carbon black. The electrochemical tests showed better performance for the Aquivion™ membrane as compared to Nafion™ with promising properties for high temperature PEM fuel cell applications. Beside the higher open circuit voltage and lower ohmic constraints, a higher electrocatalytic activity was observed at high temperature for the electrocatalyst-Aquivion™ ionomer interface indicating a better catalyst utilization.     

Fire behavior and smoke emission of phosphate–based inorganic fire‐retarded polyester resin

The fire behavior and the smoke emission of an unsaturated polyester resin modified by the addition of three phosphorus‐based fire‐retardant materials (ammonium polyphosphate (APP), silane‐coated APP, and melamine pyrophosphate) at two concentration levels (20% w/w, 35% w/w) have been investigated. Scanning electron microscopy, Fourier transform infrared spectroscopy and optical microscopy analysis have been performed to verify the dispersion and the action mechanism of additives within the resin. Results from cone calorimetric tests demonstrated that the incorporation of the fire retardants at 35% w/w has a strong effect on flammability and smoke suppressant properties with respect to both the neat resin and the loaded systems at 20% (w/w). In particular, the smoke formation and smoke parameters are reduced by 50% and 80%, respectively, leading to the conclusion that APP can be used single‐handedly without combination with specific smoke suppressors. Copyright © 2011 John Wiley & Sons, Ltd.     

Catalytic activity of Ni-Co supported metals in carbon dioxides methanation

This work deals with the catalytic performance of nickel-cobalt supported on ceria-doped gadolinia (GDC) catalyst in the single and in the simultaneous methanation of carbon monoxide and carbon dioxide. The catalysts have been prepared by impregnation method, starting from metal salts precursors. Samples have been characterized by x-ray diffraction (XRD), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), hydrogen temperature programmed reduction (TPR-H₂), transmission electronic microscopy (TEM), and scanning electron microscopy (SEM/EDX) technique. The temperature examined for methanation tests ranged from 200°C-600°C. The results show that the prepared and optimized catalysts possess the main characteristics of materials suitable for SOECs (solid oxide electrolyzer cells) applications: high metal content (50% wt/wt with respect to the support), high activity, and high stability. The catalytic performance of bimetallic catalysts highlights that the cobalt does not improve the activity of the nickel catalysts.     

Prony methods in NMR spectroscopy

The Prony method and a modified Prony method (MPM), developed to improve the performance of this technique at low signal-to-noise ratio, are described and applied to analysis of magnetic resonance spectroscopy (MRS) signals. Furthermore, the way in which results from MPM can be used as prior information in a Bayesian model is also described. First, analysis on simulated data is used to establish the methods' limits of reliability. Their performance with respect to peak identification and quantification of nuclear magnetic resonance parameters are then assayed on real data. Results of application of the methods to ¹H-MRS signals from cultured cells are discussed and compared with those deriving from application of fast Fourier transform. © 1997 John Wiley & Sons, Inc. Int J Imaging Syst Technol, 8, 565–571, 1997     

A GC–MS study of the addition reaction of aryl amines with acrylic monomers

Previous studies have shown that the interaction of carboxylic acid groups with the amine functionalities of aryl amines, especially secondary and tertiary aryl amines, can lead to the free-radical polymerization of acrylic monomers such as methyl methacrylate. In this study, the Michael addition reaction of primary and secondary aryl amines with acrylic monomers such as acrylic acid (AA) was investigated. Equivalent amounts of either p-toluidine (PT) or N-phenylglycine (NPG) and AA were combined in polar solvents such as ethanol. The reactions were conducted at ambient (23°C) or near-ambient (37–60°C) temperatures. Samples (about 3–5 mg) of these products were then trimethylsilylated with a solution consisting of 0.4 mL of bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 0.4 mL of acetonitrile by heating for 30 min at 140°C under N₂. These derivatives were characterized by gas chromatography–mass spectrometry (GC–MS). The GC–MS analyses suggest that 1 mol of the primary amine PT had reacted with 2 mol of AA to yield the expected N-p-tolyliminodipropionic acid. Similarly, the secondary amine NPG added to 1 mol of AA yielded the corresponding mixed iminodiacid, N-phenyliminoacetic–propionic acid. It would appear that the Michael reaction of primary and secondary amines with acrylic monomers may offer a general, facile synthetic route to a variety of tertiary amines. Aryl amino acids of the type synthesized in this study may find use in a number of dental applications, e.g., as surface-active adhesive agents and as polymerization initiators or activators. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 67:1545–1551, 1998     

Experimental Evidence of Leaks in Elastic Pipes

Several studies have been carried out in recent decades to establish a relationship between total head and leaks. In literature, the leakage governing equations have been analysed in light of pipe materials, water head, leak dimension or shape. Most of these contributions questioned the classical Torricelli equation, demonstrating through experimental evidence that the classical orifice law can give unsatisfactory results. Nevertheless, starting from the Torricelli equation, other exponential or linear governing equations have been proposed as mathematical models able to reproduce the leakages in water distribution systems (WDSs). To investigate the validity of the proposed governing equations, an experimental campaign was carried out by means of a water distribution network composed of approximately 500 m of polyethylene pipes. The experiments were designed to investigate the effects of leak area and pipe rigidity on discharge. Furthermore, the effect of leak size enlargement with water head was analysed. Finally, the proposed research contributes to the population of a database for estimating the coefficients of head-discharge relationships.