Synergic Effect of Metal and Fluorine Doping on the Structural and Electrical Properties of La5.4MoO11.1-Based Materials.

Cationic and anionic frameworks of La5.4MoO11.1 proton conductors have been modified by means of metal (Ti4+, Zr4+, and Nb5+) and fluorine (F-) doping. This synergic effect leads to the stabilization of high-symmetry and single-phase polymorphs. The materials have been fully characterized by structural techniques, such as X-ray and neutron powder diffraction and transmission electron microscopy. The fluorine content was determined by ion chromatography. Impedance spectroscopy analysis under different atmospheres (dry and wet N2 and O2 and wet 5% H2-Ar) showed an improvement in the electronic conductivity under reducing conditions, making these materials potential candidates for hydrogen separation membranes.

Metal-Doping of La5.4MoO11.1 Proton Conductors: Impact on the Structure and Electrical Properties.

La5.4MoO11.1 proton conductors with different metal doping (Ca2+, Sr2+, Ba2+, Ti4+, Zr4+, and Nb5+) have been prepared and structurally and electrically characterized. Different polymorphs are stabilized depending on the doping and cooling rate used during the synthesis process. The most interesting results are obtained for Nb-doping, La5.4Mo1- xNb xO11.1- x/2, where single compounds are obtained in the compositional range 0 ≤ x ≤ 0.2. These materials are fully characterized by structural techniques such as X-ray and neutron powder diffraction and transmission electron microscopy, which independently confirm the changes of polymorphism. Scanning electron microscopy and impedance spectroscopy measurements in dry/wet gases (N2, O2, and 5% H2-Ar) showed an enhancement of the sinterability and electrical properties of the materials after Nb-doping. Conductivity measurements under very reducing conditions revealed that these materials are mixed ionic-electronic conductors, making them potential candidates for hydrogen separation membranes.

Enhancing the Electrochemical Performance in Symmetrical Solid Oxide Cells through Nanoengineered Redox-Stable Electrodes with Exsolved Nanoparticles.

Symmetrical solid oxide cells (SSOCs) have recently gained significant attention for their potential in energy conversion due to their simplified cell configuration, cost-effectiveness, and excellent reversibility. However, previous research efforts have mainly focused on improving the electrode performance of perovskite-type electrodes through different doping strategies, neglecting microstructural optimization. This work presents novel approaches for the nanostructural tailoring of (La0.8Sr0.2)0.95Fe1-xTixO3-δ (LSFTx, x = 0.2 and 0.4) electrodes using a single-step spray-pyrolysis deposition process. By incorporating these electrodes into a Ce0.9Gd0.1O1.95 (CGO) porous backbone or employing a nanocomposite architecture with nanoscale particle size, we achieved significant improvements in the polarization resistance (Rp) compared with traditional screen-printed electrodes. To further boost the fuel oxidation performance, a Ni-doping strategy, coupled with meticulous microstructural optimization, was implemented. The exsolution of Ni nanoparticles under reducing conditions resulted in remarkable Rp values as low as 0.34 and 0.11 Ω cm2 in air and wet H2 at 700 °C, respectively. Moreover, an electrolyte-supported cell with symmetrical electrodes demonstrated a stable maximum power density of 617 mW cm-2 at 800 °C. These findings highlight the importance of combining electrode composition optimization with advanced morphology control in the design of highly efficient and durable SSOCs.

Transparent, plasticized cellulose-glycerol bioplastics for food packaging applications.

Free-standing films have been obtained by drop-casting cellulose-glycerol mixtures (up to 50 wt% glycerol) dissolved in trifluoroacetic acid and trifluoroacetic anhydride (TFA:TFAA, 2:1, v:v). A comprehensive examination of the optical, structural, mechanical, thermal, hydrodynamic, barrier, migration, greaseproof, and biodegradation characteristics of the films was conducted. The resulting cellulose-glycerol blends exhibited an amorphous molecular structure and a reinforced H-bond network, as evidenced by X-ray diffraction analysis and infrared spectroscopy, respectively. The inclusion of glycerol exerted a plasticizing influence on the mechanical properties of the films, while keeping their transparency. Hydrodynamic and barrier properties were assessed through water uptake and water vapor/oxygen transmission rates, respectively, and obtained values were consistent with those of other cellulose-based materials. Furthermore, overall migration levels were below European regulation limits, as stated by using Tenax® as a dry food simulant. In addition, these bioplastics demonstrated good greaseproof performance, particularly at high glycerol content, and potential as packaging materials for bakery products. Biodegradability assessments were carried out by measuring the biological oxygen demand in seawater and high biodegradation rates induced by glycerol were observed.

Unraveling the Influence of the Electrolyte on the Polarization Resistance of Nanostructured La0.6Sr0.4Co0.2Fe0.8O3-δ Cathodes.

Large variations in the polarization resistance of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathodes are reported in the literature, which are usually related to different preparation methods, sintering temperatures, and resulting microstructures. However, the influence of the electrolyte on the electrochemical activity and the rate-limiting steps of LSCF remains unclear. In this work, LSCF nanostructured electrodes with identical microstructure are prepared by spray-pyrolysis deposition onto different electrolytes: Zr0.84Y0.16O1.92 (YSZ), Ce0.9Gd0.1O1.95 (CGO), La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM), and Bi1.5Y0.5O3-δ (BYO). The ionic conductivity of the electrolyte has a great influence on the electrochemical performance of LSCF due to the improved oxide ion transport at the electrode/electrolyte interface, as well as the extended ionic conduction paths for the electrochemical reactions on the electrode surface. In this way, the polarization resistance of LSCF decreases as the ionic conductivity of the electrolyte increases in the following order: YSZ > LSGM > CGO > BYO, with values ranging from 0.21 Ω cm2 for YSZ to 0.058 Ω cm2 for BYO at 700 °C. In addition, we demonstrate by distribution of relaxation times and equivalent circuit models that the same rate-limiting steps for the ORR occur regardless of the electrolyte. Furthermore, the influence of the current collector material on the electrochemical performance of LSCF electrodes is also analyzed.

LaCrO3-CeO2-Based Nanocomposite Electrodes for Efficient Symmetrical Solid Oxide Fuel Cells.

La0.98Cr0.75Mn0.25O3-δ-Ce0.9Gd0.1O1.95 (LCM-CGO) nanocomposite layers with different LCM contents, between 40 and 60 wt %, are prepared in a single step by a spray-pyrolysis deposition method and evaluated as both air and fuel electrodes for solid oxide fuel cells (SOFCs). The formation of fluorite (CGO) and perovskite (LCM) phases in the nanocomposite electrode is confirmed by different structural and microstructural techniques. The intimate mixture of LCM and CGO phases inhibits the grain growth, retaining the nanoscale microstructure even after annealing at 1000 °C with a grain size lower than 50 nm for LCM-CGO compared to 200 nm for pure LCM. The synergetic effect of nanosized LCM and CGO by combining their high electronic and ionic conductivity, respectively, leads to efficient and durable symmetrical electrodes. The best electrochemical properties are found for 50 wt % LCM-CGO, showing polarization resistance values of 0.29 and 0.09 Ω cm2 at 750 °C in air and H2, respectively, compared to 2.05 and 1.9 Ω cm2 for a screen-printed electrode with the same composition. This outstanding performance is mainly ascribed to the nanoscale electrode microstructure formed directly on the electrolyte at a relatively low temperature. These results reveal that the combination of different immiscible phases with different crystal structures and electrochemical properties could be a promising strategy to design highly efficient and durable air and fuel electrodes for SOFCs.

Transparent, UV-blocking, and high barrier cellulose-based bioplastics with naringin as active food packaging materials.

Free-standing, robust, and transparent bioplastics were obtained by blending cellulose and naringin at different proportions. Optical, thermal, mechanical, antioxidant, and antimicrobial properties were systematically investigated. In general, the incorporation of naringin produced important UV blocking and plasticizer effects and good antioxidant and antibacterial properties. Moreover, the barrier properties were characterized by determination of their water and oxygen transmission rates, finding that both parameters decreased by increasing the naringin content and reaching values similar to other petroleum-based plastics and cellulose derivatives used for food packaging applications. Finally, the biodegradability of these films was determined by measurement of the biological oxygen demand (BOD) in seawater, demonstrating an excellent decomposition in such conditions.

Pectin-cellulose nanocrystal biocomposites: Tuning of physical properties and biodegradability.

The fabrication of pectin-cellulose nanocrystal (CNC) biocomposites has been systematically investigated by blending both polysaccharides at different relative concentrations. Circular free-standing films with a diameter of 9 cm were prepared by simple solution of these carbohydrates in water followed by drop-casting and solvent evaporation. The addition of pectin allows to finely tune the properties of the biocomposites. Textural characterization by AFM showed fibrous morphology and an increase in fiber diameter with pectin content. XRD analysis demonstrated that pectin incorporation also reduced the degree of crystallinity though no specific interaction between both polysaccharides was detected, by ATR-FTIR spectroscopy. The optical properties of these biocomposites were characterized for the first time and it was found that pectin in the blend reduced the reflectance of visible light and increased UV absorbance. Thermal stability, analyzed by TGA, was improved with the incorporation of pectin. Finally, pectin-cellulose nanocrystal biocomposites showed a good biodegradability in seawater, comparable to other common bioplastics such as cellulose and low-molecular weight polylactide, among others.

Nanostructured BaCo0.4Fe0.4Zr0.1Y0.1O3-δ Cathodes with Different Microstructural Architectures.

Lowering the operating temperature of solid oxide fuel cells (SOFCs) is crucial to make this technology commercially viable. In this context, the electrode efficiency at low temperatures could be greatly enhanced by microstructural design at the nanoscale. This work describes alternative microstructural approaches to improve the electrochemical efficiency of the BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) cathode. Different electrodes architectures are prepared in a single step by a cost-effective and scalable spray-pyrolysis deposition method. The microstructure and electrochemical efficiency are compared with those fabricated from ceramic powders and screen-printing technique. A complete structural, morphological and electrochemical characterization of the electrodes is carried out. Reduced values of area specific resistance are achieved for the nanostructured cathodes, i.e., 0.067 Ω·cm2 at 600 °C, compared to 0.520 Ω·cm2 for the same cathode obtained by screen-printing. An anode supported cell with nanostructured BCFZY cathode generates a peak power density of 1 W·cm-2 at 600 °C.

Investigation into the effect of Si doping on the performance of Sr(1-y)Ca(y)MnO(3-δ) SOFC cathode materials.

In this paper we report the successful incorporation of silicon into Sr1-yCayMnO3-δ perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a (29)Si enriched Sr1-yCayMn1-xSixO3-δ perovskite system is confirmed by (29)Si MAS NMR measurements at low B0 field. The very large paramagnetic shift (~3000-3500 ppm) and anisotropy (span ~4000 ppm) suggests that the Si(4+) species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn(3+/4+) centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn(4+) to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr1-yCayMn1-xSixO3-δ perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr0.5Ca0.5Mn1-xSixO3-δ series; x = 0.075 for Sr0.7Ca0.3Mn1-xSixO3-δ; x = 0.10 for Sr0.8Ca0.2Mn1-xSixO3-δ; and x = 0.15 for SrMn1-xSixO3-δ. Composites with 50% Ce0.9Gd0.1O1.95 were examined on dense Ce0.9Gd0.1O1.95 pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.