Ce0.8Gd0.2O2‐δ / La0.6Sr0.4CoO3 Heterostructures prepared by pulsed laser deposition

Oxide interfaces have received greater attention due to the possibility to obtain properties that are very different from bulk materials. Due to the wide variety of electronic and ionic phenomena than can be detected at the interfaces, such materials have many technological applications [1]. Attention is being drawn to oxide heterostructures, a new family of artificial materials where electronic and ionic properties can be modulated at the interfaces by varying the characteristics of the layers [2, 3]. Slight variations in the near anionic-cationic order might take place if there exists strained interfaces. The interest in multilayared heterostructures derives from the mobility deffects and the space-charge-zone effects at the interfaces. In addition, a new degree of freedom related to the capacitive and resistive contributions is provided as a consequence of the size effects of these artificial structures. In the present work, for the first time, we investigate the structure, microstructure and electrical properties of a new family of heterostructured materials with alternated thin layers of La0.6Sr0.4CoO3 (LSC) and Ce0.8Gd0.2O2-δ (CGO) deposited by pulsed laser deposition on (110) NdGaO3 (NGO) single crystal substrates. In order to evaluate the interfacial contribution to ionic-electronic conductivity and know what is actually happens at the interface of MIECs, different heterostructures were prepared by varying both the number of bilayers (N) and the total thickness of the samples (N = 2 and 5; and the thickness were 50, 100 and 300 nm).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Novel microstructural strategies to enhance the electrochemical performance of La0.8Sr0.2MnO3-δ cathodes

Solid oxide fuel cells (SOFCs) are one of the most efficient technologies for direct conversion of fuels to electricity. La0.8Sr0.2MnO3-δ (LSM) is the cathode material most widely used in SOFCs [1], however, LSM exhibits high activation energy for oxygen reduction reaction (ORR) and low ionic conductivity, which limits its application at reduced temperatures. In this material the electrochemically active reaction sites are restricted to the triple-phase boundary (TPB) near the electrolyte/electrode interface, where the electrolyte, air and electrode meet. Different strategies have been investigated to enlarge the TPB area of LSM, such as the production of nanocrystalline powders by precursor routes, preparation of composites by infiltration methods and thin films [2-4]. Here we present and compare innovative procedures to extend the TPB of LSM in contact with yttria-stabilized zirconia electrolyte: i) nanocrystalline LSM films deposited by spray-pyrolysis on polished YSZ electrolyte; ii) the addition of polymethyl methacrylate microspheres as pore formers during the spray-pyrolysis deposition to further increase the porosity of these films and (iii) the deposition of LSM by spray-pyrolysis on porous backbones of Zr0.84Y0.16O1.92 (YSZ), Ce0.9Gd0.1O1.95 (CGO) and Bi1.5Y0.5O3- (BYO) electrolytes previously fixed onto the YSZ electrolyte. The most remarkable peculiarity of this novel preparation method, compared to the traditional impregnation, is the formation of LSM thick film of 500 nm on the electrode surface (Fig. 1), which improves the electrical conductivity of the composite cathode. Thus, the optimization of this novel method would be an alternative to the classical infiltration with several advantages for the industry of planar SOFCs allowing the deposition of a wide variety of ceramic films over large areas with more uniform distribution of the catalyst, lower cost and only one deposition step is required to form the electrode. The morphology and electrochemical performance of the electrode have been investigated by scanning electron microscopy and impedance spectroscopy. Very low values of area specific resistance were obtained ranging from 1.4 cm2 for LSM deposited on polished YSZ to 0.06 cm2 for LSM deposited onto BYO backbone at a measured temperature of 650 ºC. This electrodes exhibit high performance even after annealing at 950 ºC making them interesting for applications at intermediate temperatures.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Influence of lanthanum doping on the structure and transport properties of CeO2

LaxCe1-xO2-x/2 materials are oxide and/or proton conductors depending on the La-content and they are of interest for numerous electrochemical applications at high temperatures, including membranes for hydrogen separation and fuel cell electrolytes. Samples with low La-content exhibit (x0.4) crystallize with cubic fluorite type structure; while for x>0.4 the structure is still unclear. The crystal structure of these materials is still unknown, some authors reported that the materials exhibit fluorite type structure in the whole compositional range. However, another authors reported a pyrochlore type structure for x0.5. The stabilization of the fluorite or pyrochlore type structure depends mainly on the oxygen sublattice and the vacancy ordering1. In this contribution, LaxCe1-xO2-δ (0<x0.7) materials are prepared by the freeze-drying precursor method and the sintering conditions have been optimized to obtain dense ceramic samples. A complete structural characterization has been carried out by X-ray powder diffraction and scanning electron microscopy. The average structure determined by conventional XRD indicates that the materials are single fluorite compounds for x0.6. However, the local structure determined by combined electron diffraction and HRTEM is more complex. The SAED patterns reveal diffuse scatterings for x0.5 that have been associated with O-vacancy ordering, leading to a superstructure relative to a single fluorite . This finding is further confirmed by the HRTEM images in the same zone axis. Thermogravimetric and Raman analysis confirmed an increase of oxygen vacancy concentration with La-doping. The overall conductivity was determined by complex impedance spectroscopy in different atmospheres. The samples with high La-content exhibit an important proton contribution at low temperature. In addition, all samples are mixed ion-electronic conductors in hydrogen containing atmosphereUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Nanocrystalline cathodes for PC-SOFCs based on BCZY

Perovskites based on BaCeO3-δ exhibit the highest proton conductivity among this class of materials, however, they are susceptible to hydration and carbonation in presence of water vapor and CO2 [1]. In contrast, the chemical stability of BaZrO3-based protonic conductors is better, but they require sintering temperatures as high as 1700 ºC and suffer from high intrinsic grain boundary resistance, limiting the final performance. Partial substitution of Zr for Ce in Ba(Ce0.9-xZrx)Y0.2O3-δ allows obtaining electrolytes with both high proton conductivity and good chemical stability. The performance of a PC-SOFC at low temperatures depends significantly on the ohmic resistance of the electrolyte, although it can be lowered by reducing the electrolyte thickness. Another important limiting factor is the increase of the cathode polarization resistance due to the thermally activated nature of the oxygen reduction reaction. For this reason, it is essential to obtain high efficiency cathodes operating at reduced temperatures. In this work, BaCe0.6Zr0.2Y0.2O3-δ (BCZY) powders were prepared by freeze-drying precursor method. These powders were mixed with a Zn-containing solution as sintering additive in order to obtain dense pellets with submicrometric grain size at only 1200 ºC. After that, La0.6Sr0.4Co0.8Fe0.2O3 nanocrystalline electrodes were deposited symmetrically onto dense pellets BCZY by conventional spray-pyrolysis [3]. The structure, microstructure and electrochemical properties of these electrodes have been examined by XRD, FE-SEM and impedance spectroscopy. The stability of these electrodes at intermediate temperatures was evaluated as a function of time. These nanocrystalline cathodes exhibit a substantial improvement of the electrode polarization resistance with respect to the same materials prepared by screen-printing method at high sintering temperatures, e.g. 0.7 and 3.2 cm2 at 600 ºC for LSCF cathodes prepared by spray-pyrolysis and screen-printing method respectively (Figure). An anode supported cell with composition LSCF/BCZY/NiO-BCZY was also prepared to test the electrochemical performance.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Solid Oxide Fuel Cells based on Lanthanum Tungstates Electrolytes

Lanthanum tungstate with composition La27W4NbO55- (LWNO) has been tested as proton conductor electrolyte for Solid Oxide Fuel Cells (SOFCs). For this purpose, different electrodes and composite electrodes are considered, including: La0.8Sr0.2MnO3-, La0.6Sr0.4Co1-xFexO3-, La0.5Sr0.5Cr0.5Mn0.5O3-, SrFe0.75Nb0.25O3- and NiO. Chemical compatibility between the cell components is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) of the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis do not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of a SOFC (600-900 ºC). However, minor interdiffusion of elements at the electrolyte/electrode interface affects both the ohmic losses and electrode polarization of the cells. ASR values are significantly improved by using a buffer layer of Ce0.8Gd0.2O1.9, between the electrolyte and electrode materials, to prevent reactivity. A single cell with 350 µm thick electrolyte, NiO-Ce0.8Gd0.2O1.9 anode and La0.6Sr0.4Co0.8Fe0.2O3- cathode, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 ºC, respectively.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Compatibility and performance of SOFCs based on lanthanum tungstates

Rare-earth tungstates with general composition “Ln6WO12” have attracted great attention in last few years due to their relatively high mixed proton-electron conductivity [1, 2]. One of the main ad-vantages of these electrolytes, compared to the traditional perovskites based on BaCeO3, is that they exhibit high tolerance towards CO2 and H2S environments. Therefore, this material is a potential electrolyte for proton conducting solid oxide fuel cells (PC-SOFC). In this work, the lanthanum tungstate with com-position La27W4NbO55-δ (LWNO) has been tested as proton conductor electrolyte [3]. For this purpose, different electrodes and composite electrodes have been considered, including: La0.8Sr0.2MnO3-δ, La0.6Sr0.4Co1-xFexO3-δ, La0.5Sr0.5Cr0.5Mn0.5O3-δ, SrFe0.75Nb0.25O3-δ and NiO. Chemical compatibility between the cell compo-nents is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) of the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis do not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of a SOFC (600-900 ºC). However, minor interdiffusion of elements at the electrolyte/electrode interface affects both the ohmic losses and electrode polarization of the symmetric cells. ASR values are significantly improved by using a buffer layer of Ce0.8Gd0.2O1.9, between the electrolyte and electrode materials, to prevent reactivity. A single cell with 350 µm thick electrolyte, NiO-Ce0.8Gd0.2O1.9 anode and La0.6Sr0.4Co0.8Fe0.2O3-δ cathode, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 ºC, respectively. Hence, lanthanum tungstates could be competitive proton conductors for PC-SOFCs with similar performance to those based on BaZrO3 if thin film electrolytes are used.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Solvent-free ring opening of e-caprolactone with amines assisted by microwave irradiation

The 11th International Electronic Conference on Synthetic Organic Chemistry session Symposium on Microwave Assisted SynthesisIrradiation of e-caprolactone with microwaves in the presence of secondary or primary amines lead to e-hydroxyamides in good yieldsXUNTA DE GALICIA for financial support: PGIDIT05PXIB26201PR, PR405 A 098/59-0. USC for a predoctoral fellowship to JC

Tolerance towards difference: Adaptation and psychometric properties of the Spanish version of a new measure of tolerance and sex-moderated relations with prejudice

Abstract The present research aims at adapting to the Spanish context and language a measure of tolerance toward diversity recently developed, at analyzing its psychometric properties, and at examining the moderating effect of participants' sex on the relations between tolerance and prejudice. We conducted two studies considering two Spanish samples taken from the general population. In Study 1 (N = 586; 70.5 % females; Mage = 37.77, SD = 12.34) we confirmed the three-factorial structure of the questionnaire (i.e., acceptance of diversity, respect for diversity and appreciation of diversity) and their invariance across sex groups. In Study 2 (N = 333; 60.4 % females; Mage = 36.20, SD = 13.36) evidence of validity based on the relations of tolerance with prejudice (modern racism, hostile sexism, and benevolent sexism) are presented. Additional findings reveal the role of the appreciation of diversity dimension to reduce prejudice, as well as differences between men and women in this relation: when participants express low appreciation of diversity, men show more hostile sexism and modern racism than women. Such differences did not emerge for those who highly appreciate diversity. The implications of using this multidimensional questionnaire to measure tolerance are discussed

Biomarkers in ocular chronic graft versus host disease: tear cytokine- and chemokine-based predictive model.

Producción CientíficaPurpose: To develop a tear molecule level-based predictive model based on a panel of tear cytokines and their correlation with clinical features in ocular chronic graft versus host disease (cGVHD). Methods: Twenty-two ocular cGVHD patients and 21 healthy subjects were evaluated in a controlled environmental research laboratory (CERLab). Clinical parameters were recorded, and tears were collected. Levels of 15 molecules (epidermal growth factor [EGF], IL receptor antagonist [IL-1Ra], IL-1β, IL-2, IL-6, IL-8/CXCL8, IL-10, IL-12p70, IL-17A, interferon inducible protein [IP]-10/CXCL10, IFN-γ, VEGF, TNF-α, eotaxin 1, and regulated on activation normal T cell expressed and secreted [RANTES]) were measured by multiplex-bead assay and correlated with clinical parameters. Logistic regression was used to develop a predictive model. Leave-one-out cross-validation was applied. Classification capacity was evaluated in a cohort of individuals with dry eye (DE) of other etiologies different from GVHD. Results: Epidermal growth factor and IP-10/CXCL10 levels were significantly decreased in ocular cGVHD, positively correlating with tear production and stability and negatively correlating with symptoms, hyperemia, and vital staining. Interleukin-1Ra, IL-8/CXCL8, and IL-10 were significantly increased in ocular cGVHD, and the first two correlated positively with symptoms, hyperemia, and ocular surface integrity while negatively correlating with tear production and stability. Predictive models were generated, and the best panel was based on IL-8/CXCL8 and IP-10/CXCL10 tear levels along with age and sex, with an area under the receiving operating curve of 0.9004, sensitivity of 86.36%, and specificity of 95.24%. Conclusions: A predictive model based on tear levels of IL-8/CXCL8 and IP-10/CXCL10 resulted in optimal sensitivity and specificity. These results add further knowledge to the search for potential biomarkers in this devastating ocular inflammatory disease.Ministry of Economy and Competitiveness, Madrid, Spain, SAF-2010 15631 (AES)

Durability and performance of CGO barriers and LSCF cathode deposited by spray-pyrolysis

Ce0.9Gd0.1O1.95 (CGO) protective layers are prepared by two different methods to prevent the reaction between the Zr0.84Y0.16O1.92 (YSZ) electrolyte and the La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode. In the first method, the CGO layers are deposited by an airbrushing technique from an ink containing CGO particles without and with cobalt as sintering aids. The second strategy consists in preparing both a dense CGO barrier layer and a porous LSCF cathode by spray-pyrolysis deposition, in order to further reduce the fabrication temperature and minimize the reaction between the cell components. The samples prepared by spray-pyrolysis exhibit better performance and durability than those obtained by conventional sintering methods. The results suggest that the interfacial reactivity between YSZ and LSCF as well as the Sr-enrichment at the cathode surface can be avoided by using low-temperature fabrication methods and by operating at temperatures lower than 650 °C.Ministerio de Ciencia e Innovación, EC2014-53906-R y MAT2016-77648-