Tailoring mixed proton-electronic conductivity of BaZrO3 by Y and Pr co-doping for cathode application in protonic SOFCs

BaZr_0.8 − xPr_xY_0.2O_3 − δ (BZPYx, 0.1 ≤ x ≤ 0.4) perovskite oxides were investigated for application as cathode materials for intermediate temperature solid oxide fuel cells based on proton conducting electrolytes (protonic-SOFCs). The BZPYx reactivity with CO₂ and water vapor was evaluated by thermogravimetric and X-ray diffraction analyses, and good chemical stability was observed for each BZPYx composition. Conductivity measurements of BZPYx sintered pellets were performed as a function of temperature and p_O2 in humidified atmospheres, corresponding to cathode operating condition in protonic-SOFCs. Different conductivity values and activation energies were measured depending on the Pr content, suggesting the presence of different charge carriers. For all the compositions, the partial electronic conductivity, calculated from conductivity measurements at different p_O2, increased with increasing the temperature from 500 to 700 °C. Furthermore, the larger the Pr content, the larger the electronic conductivity. BaZr_0.7Pr_0.1Y_0.2O_3 − δ and BaZr_0.4Pr_0.4Y_0.2O_3 − δ showed mostly pure proton and electron conductivity, respectively, whereas the intermediate compositions showed mixed proton/electronic conductivity. Among the two mixed proton/electronic conductors, BaZr_0.6Pr_0.3Y_0.2O_3 − δ presented the larger conductivity, which coupled with its good chemical stability, makes this perovskite oxide a candidate cathode materials for protonic-SOFCs.     

Thermal stability and thermodynamic properties of hybrid proton-conducting polyaryl etherketones

The thermal and structural stability of sulfonated cross-linked PEEK (polyether ether ketone) and its silicon-containing class II hybrid derivatives were characterized by combination of mass spectrometry, infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. Thermodynamic properties of the hybrids were determined, including glass-transition temperature, degree of crystallinity, and thermal stability. The decomposition processes of the hybrid polymers could be consistently interpreted and their energetics quantitatively determined. The introduction of inorganic silanol moieties improves the thermal stability compared to sulfonated products.     

Sol-Gel Nanosized Semiconducting Titania-Based Powders for Thick-Film Gas Sensors

Pure, 5 at%, and 10 at% Ta- or Nb-doped TiO₂ nanosized powders were prepared by the sol-gel method. The powders heated to 400°C have the crystalline anatase structure. While the pure TiO₂ powder heated to 850°C has the rutile structure, the addition of Ta and Nb inhibited the anatase-to-rutile phase transformation at this temperature. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired at 650°C and 850°C for 1 h. SEM observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at the nanometric level even at 850°C. Conductance measurements showed that a good gas response is observed only for the nanostructured titania-based films. The CO response of these materials is only slightly affected by humidity.     

Chemically stable anode-supported solid oxide fuel cells based on Y-doped barium zirconate thin films having improved performance

Anode-supported solid oxide fuel cells (SOFCs) based on thin BaZr_0.8Y_0.2O_3 ? δ (BZY) electrolyte films were fabricated by pulsed laser deposition (PLD) on sintered NiO–BZY composite anodes. After in situ reduction of NiO to Ni, the anode substrates became porous, while retaining good adhesion with the electrolyte. A slurry-coated composite cathode made of La_0.6Sr_0.4Co_0.2Fe_0.8O_3 ? δ (LSCF) and BaCe_0.9Yb_0.1O_3 ? δ (BCYb), specifically developed for proton conducting electrolytes, was used to assemble fuel cell prototypes. Depositing by PLD 100 nm thick LSCF porous films onto the BZY thin films was essential to improve the cathode/electrolyte adhesion. A power density output of 110 mW/cm² at 600 °C, the largest reported value for an anode-supported fuel cell based on BZY at this temperature, was achieved. Electrochemical impedance spectroscopy (EIS) measurements were used to investigate the different contributions to the total polarization losses.     

Proton‐conducting electrolytes based on silylated and sulfonated polyetheretherketone: Synthesis and characterization

A derivative of polyetheretherketone (PEEK) having sulfonic acid groups and silicon‐containing substituents covalently bound to the aromatic backbone has been prepared as proton‐exchange membrane material. The polymer 4 (PhSiSPEEK) has been synthesized via (i) sulfonation of PEEK up to 0.9 degree of sulfonation (DS, the number of sulfonic groups per repeat unit), (ii) conversion of sulfonated PEEK 1 (SPEEK09) into sulfonyl chlorinated derivative 2 (PEEKSO₂Cl), (iii) lithiation of 2 and subsequent addition of PhSiCl₃, followed by hydrolysis. The chemical structure of the synthesized polymers has been investigated by ¹H NMR and ¹³C NMR and ATR/FTIR spectroscopy and their thermal stability has been evaluated by thermogravimetric analysis. The presence of inorganic moieties increases the thermal stability of 4 with respect to the sulfonated and not silylated product. Despite its very high DS, PhSiSPEEK is insoluble in water but does not possess the plastic properties needed to be used as an electrolyte membrane. Blend membranes made of SPEEK05 (DS = 0.5) and containing 10 and 25 wt % of 4 (DS = 0.9, degree of silylation DSi = 0.1) have been prepared and characterized by water uptake measurements and electrochemical impedance spectroscopy. The combination of the two functionalized polymers having different properties allows to obtain proton‐conducting electrolytes that are potential candidates for fuel cells applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2178–2186, 2010     

Improved total conductivity of nanometric samaria-doped ceria powders sintered with molten LiNO3 additive

Nanometric 20% molar Sm-doped ceria (SDC20) powders were synthesized by co-precipitation in the presence of N, N, N′, N′ tetramethylethylendiamine (TMEDA). SDC20 powders were sintered using lithium nitrate salt in various concentrations (0.1, 1, 3, and 10 mol% with respect to the SDC20 total moles) as an additive to promote the liquid phase sintering and without additive for comparison. The addition of the Li salt allowed reducing significantly the sintering temperature of SDC. Electrochemical impedance spectroscopy (EIS) measurements were performed to estimate the contribution of grain boundary and bulk to the electrical conductivity in different sintering conditions. Liquid phase sintering allowed to produce dense samples with enhanced ionic conductivity especially at the grain boundary when compared to the samples sintered without additive. The additive liquid phase was evaporated in large part at the high temperatures throughout the sintering process. Residual extra phases were segregated at the grain boundary, generated probably by reaction of the Li salt with impurities, which were removed by a chemical etching.     

High performance anode-supported intermediate temperature solid oxide fuel cells (IT-SOFCs) with La0.8Sr0.2Ga0.8Mg0.2O3−δ electrolyte films prepared by electrophoretic deposition

Remarkable power density was obtained for anode-supported solid oxide fuel cells (SOFCs) based on La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte films, fabricated following an original procedure that allowed avoiding undesired reactions between LSGM and electrode materials, especially Ni. Electrophoretic deposition (EPD) was used for the fabrication of 30 μm-thick electrolyte films. Anode supports were made of La_0.4Ce_0.6O_2−x (LDC). The LSGM powder was deposited by EPD on an LDC green tape-cast membrane added with carbon powder, both as pore former and substrate conductivity booster. A subsequent co-firing step at 1490 °C produced dense electrolyte films on porous LDC skeletons. Then, a La_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (LSFC) cathode was applied by slurry-coating and calcined at 1100 °C. Finally, the porous LDC layer was impregnated with molten Ni nitrate to obtain, after calcination at 900 °C, a composite NiO–LDC anode. Maximum power densities of 780, 450, 275, 175, and 100 mW/cm² at 700, 650, 600, 550, and 500 °C, respectively, were obtained using H₂ as fuel and air as oxidant, demonstrating the success of the processing strategy. As a comparison, electrolyte-supported SOFCs made of the same materials were tested, showing a maximum power density of 150 mW/cm² at 700 °C, more than 5 times smaller than the anode-supported counterpart.     

Study of the thermal behaviour of hydroxide mixtures aimed at the preparation of Mg-Al spinels

The thermal behaviour of hydroxide mixtures aimed at Mg-Al spinel preparation is reported. The mixtures of hydroxides were prepared by precipitation reaction from Mg and Al nitrate solutions, stoichiometric to the spinel formation. Hydroxide mixtures with different phase distributions were investigated, prepared by varying the precipitation procedure. The results were related to the thermal behaviour of mechanical mixtures of separately precipitated hydroxides. The spinel formation was identified performing XRD analysis on powder samples heated at different temperatures. The coprecipitated mixtures are completely decomposed to spinel at 400C. The presence of the Mg-Al mixed hydroxide phase in the mixture is of primary concern to get spinel at low temperatures.

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Zusammenfassung Im Hinblick auf die PrÄparation von Mg-Al Spinell wird das thermische Verhalten von Hydroxid-Mischungen beschrieben. Letztere wurden durch FÄllung von Mg- und Al-Nitratlösungen im stöchiometrischen VerhÄltnis der Spinellbildung hergestellt. Durch Variation des FÄllungsvorgangs wurden Hydroxid-Mischungen unterschiedlicher Phasenzusammensetzung erzeugt. Die Resultate werden mit dem thermischen Verhalten von mechanischen Mischungen separat gefÄllter Hydroxide verglichen. Die Identifizierung der Spinellbildung erfolgte durch Röntgendiffraktion an pulverförmigen, auf verschiedene Temperaturen aufgeheizten Proben. Die durch simultane FÄllung erhaltenen Mischungen wurden bei 400C vollstÄndig zu Spinell zersetzt. Um bei tiefer Temperatur Spinell zu erhalten, kommt dem Vorhandensein der Mg-Al-Mischhydroxidphase in der Mischung vorrangige Bedeutung zu.

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This work was supported by the Italian National Research Council (C.N.R.), under the Targeted Project Special Materials for Advanced Technologies.     

Sol-Gel Preparation and Characterization of Ag-TiO2 Nanocomposite Thin Films

Ag-TiO₂ thin films were prepared with a sol-gel route, using titanium isopropoxide and silver nitrate as precursors, at 0.03 and 0.06 Ag/Ti nominal atomic ratios. After drying at 80°C, the films were fired at 300°C and 500°C for 30 min. The films were analysed by X-ray diffraction (XRD) with glancing angle, and X-ray photoelectron spectroscopy (XPS), with depth profiling of the concentration. XPS analysis showed the presence of C and N as impurities in the nanocomposite films. Their concentration decreased with increasing the firing temperature. Chemical state analysis showed that Ag was present in metallic state, except for the very outer layer where it was present as Ag⁺. For the films prepared with a Ag/Ti concentration of 0.06, depth profiling measurements of the film fired at 300°C showed a strong Ag enrichment at the outer surface, while composition remained almost constant within the rest of the film, at 0.019. For the films heated to 500°C, two layers were found, where the Ag/Ti ratios were 0.015 near the surface and 0.026 near the substrate.     

NMR conformational analysis of antide, a potent antagonist of the gonadotropin releasing hormone

Antide is a decapeptide [(N-Ac-D-Nal(1)-D-Cpa(2)-D-Pal(3)-Ser(4)-Lys(Nic)(5)-D-Lys(Nic)(6)-Leu(7)-Ilys(8)-Pro(9)-D-Ala(10)-NH(2)] that acts in vivo as an antagonist of GnRH (gonadotropin-releasing hormone). The conformational behavior of antide has been studied in water, TFE, DMF, and DMSO solutions by means of 2D-NMR spectroscopy and molecular dynamics calculations. Antide adopts in aqueous solution a delta-shaped backbone conformation, which is characterized by an irregular turn around residues D-Pal(3)-Ser(4) and by the close spatial proximity of the side chains belonging to D-Nal(1) and Ilys(8) (as many as 17 NOE peaks were detected between these side chains). The side-chain protons of Ilys(8) (especially the H(gamma) ones) present remarkably upfield shifted resonances, because of ring current effects induced by the naphthyl moiety. The upfield shifted resonances of the Ilys(8) H(gamma) hydrogen atoms are strictly characteristic of the water delta-shaped conformation and can be considered as structure markers. The observation of ring current shifted Ilys(8) H(gamma) resonances under different conditions (temperature, pH, solvent) indicates a remarkable stability of the water delta-shaped conformation. Such a conformation is at least partially disrupted in solvent mixtures containing high percentages of organic solvents. TFE can induce a well-defined conformation, which is characterized by an S-shaped backbone conformation. In DMF and DMSO solution, the molecule is basically endowed with a random coil conformation and high fluxionality. Antide fulfills the conformational requirements that are known to play a crucial role in receptor recognition, namely (i) the presence of a turn in the backbone and (ii) the all-trans nature of peptide bonds. In addition, the structural rigidity of antide likely adds a further contribution to the receptor binding affinity.