Nickel exsolution driven phase transformation from an n=2 to an n=1 Ruddlesden Popper manganite for methane steam reforming reaction in SOFC conditions

This is the peer reviewed version of the following article: S. Vecino-Mantilla, P. Gauthier-Maradei, M. Huvé, J. M. Serra, P. Roussel, G. H. Gauthier, ChemCatChem 2019, 11, 4631, which has been published in final form at https://doi.org/10.1002/cctc.201901002. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] An original way to perform the exsolution of Ni nanoparticles on a ceramic support was explored for the development of methane steam reforming catalyst in SOFC anode conditions. The n=2 Ruddlesden-Popper (RP) phase La1.5Sr1.5Mn1.5Ni0.5O7 +/-delta has been synthesized by the Pechini method and subsequently reduced with an H-2-N-2 mixture at different temperatures and reducing times to induce the formation of two phases: LaSrMnO4 (n=1 RP) decorated with metallic Ni nanoparticles. Preliminary measurements of catalytic behavior for the steam reforming have been carried out in a reduction-reaction process with a mixture of 82 mol %CH4, 18 mol %N-2 and low steam to carbon ratio (S/C=0.15). The catalyst exhibits a selectivity for CO production (0.97), 14.60 mol % CH4 conversion and around 24.19 mol % H-2 production. Such catalytic behavior was maintained for more than 4 h, with a constant rate of hydrogen production and CH4 conversion rate.The authors acknowledge the financial support of the Colombian Administrative Department of Science, Technology and Innovation COLCIENCIAS (Project #110265842833 "Symmetrical high temperature Fuel Cell operating with Colombian natural gas" (contract #038-2015) and S. Vecino-Mantilla's Ph.D. scholarship (call #647)) and of the Spanish National Research Council CSIC (Project #COOPA20112). The authors are also grateful to UIS' X-Ray Laboratory (Parque Tecnologico Guatiguara) for XRD measurements, UPV's Electronic Microscopy Laboratory for the FESEM analysis, and finally to Margarita Vecino-Mantilla, Carolina Cardenas-Velandia, Santiago Paez-Duque, Ivan Suarez-Acelas (UIS), Maria Fabuel (UPV) and Olivier Gardoll (UCCS) for their contribution to materials synthesis and characterization. As well as Santiago Palencia, Monica Sandoval (UIS) and Caroline Pirovano (UCCS) are warmly acknowledged for useful discussions.Vecino-Mantilla, S.; Gauthier-Maradei, P.; Huvé, M.; Serra Alfaro, JM.; Roussel, P.; Gauthier, GH. (2019). Nickel exsolution driven phase transformation from an n=2 to an n=1 Ruddlesden Popper manganite for methane steam reforming reaction in SOFC conditions. ChemCatChem. 11(18):4631-4641. https://doi.org/10.1002/cctc.201901002S463146411118Ghezel-Ayagh, H., & Borglum, B. P. (2017). Review of Progress in Solid Oxide Fuel Cells at FuelCell Energy. 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Study of the oxygen reduction reaction on pure and Zr-doped YMnO3+δ SOFC electrode

The effect of Zr-doping on the novel SOFC cathode YMnO3 and its O2-Reduction Reaction (ORR) was studied using electrochemical impedance spectroscopy (EIS) as a function of temperature (500 < T < 800 °C) and the oxygen partial pressure (10−4 < pO2 < 1 atm). EIS technique allows identifying three processes controlling the ORR for each electrode, differentiated by their characteristic frequency, activation energies and pO2 dependence. High frequency contribution, only observed at 600°C for both electrodes, was attributed to oxygen ion transfer trough the electrode/electrolyte interface. In both electrodes, the Intermediate frequency contribution was described by a Gerischer impedance, related to a co-limiting process between oxygen ion diffusion and a surface process. However, whereas the EIS characteristics for YMnO3 can be explained by a surface process controlled by the electron transfer from oxide to O-adsorbed, it seems related for Y0.9Zr0.1MnO3 to the probability of finding a second free-surface site near to a diatomic intermediated for the O2 dissociation. These differences are in agreement with the improvement of the electrical properties when YMnO3 is doped with Zr. The low frequency contribution became important as pO2 decreased and temperature increased, and its characteristics would indicate a secondary surface process, co-limited with O2 gas diffusion for Y0.9Zr0.1MnO3 porous electrode.Fil: Moreno Botello, Zulma L.. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Universidad Industrial Santander; ColombiaFil: Montenegro Hernández, Alejandra. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; ArgentinaFil: Mogni, Liliana Verónica. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche | Comision Nacional de Energia Atomica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia. Unidad Ejecutora Instituto de Nanociencia y Nanotecnologia - Nodo Bariloche.; ArgentinaFil: Gauthier, Gilles H.. Universidad Industrial Santander; Colombi

Synthesis and Characterization of High Temperature Properties of YBa2Cu3O6+δ Superconductor as Potential Cathode for Intermediate Temperature Solid Oxide Fuel Cells

YBa2Cu3O6+δ (YBC) oxygen deficient perovskite was synthesized by an auto-combustion method and was studied as potential cathode for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC). Synchrotron X-ray thermodiffraction in air shows a phase transition from orthorhombic Pmmm to tetragonal P4/mmm space groups at ~ 425 °C. The chemical compatibility with Ce0.9Gd0.1O1.95 (GDC) electrolyte was investigated in air where certain reactivity wasobserved above 800 °C. However, the main phase is Ba(Ce1-xYx)O3, a good ionic conductor. The catalytic performance in air was obtained by electrochemical impedance spectroscopy (EIS) measurements on YBC/GDC/YBC symmetrical cells. The area specific resistance (ASR) values change from 13.66 to 0.14 Ω cm2 between 500 and 800 °C, with activation energy (Ea) of 0.41 eV. The results suggest potential applications of YBC as IT-SOFC cathode.Fil: Grassi, Joaquín. Universidad de la República. Facultad de Química; UruguayFil: Macías, Mario A.. Universidad de los Andes; ColombiaFil: Basbus, Juan Felipe. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; ArgentinaFil: Castiglioni, Jorge. Universidad de la República. Facultad de Química; UruguayFil: Gauthier, Gilles H.. Universidad Industrial Santander; ColombiaFil: Serquis, Adriana Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; ArgentinaFil: Suescun, Leopoldo. Universidad de la República. Facultad de Química; Urugua

Des géographes à l'œuvre: 50 ans de géographie à l’Université du Québec à Chicoutimi 1969-2019 Recueil de textes

L’idée de souligner les 50 ans d’existence des programmes de géographie à l’Université du Québec à Chicoutimi (UQAC) a germé en 2017; dès qu’ont surgi les premières réflexions sur la manière de rappeler l’évènement au sein de l’Institution. Il nous semblait important, nous géographes, de faire une pause, de regarder en arrière (et aussi en avant). En fait, de faire plus qu’une revue et plus qu’un bilan; en passant non seulement par les différentes activités qui se sont déroulées au cours de la période, mais aussi de faire part de nos préoccupations actuelles. Somme toute, de là l’importance de poser une pierre, de laisser une marque, de franchir un jalon. Pourquoi ne pas montrer comment les professeurs et les diplômés-es de l’UQAC ont occupé une place, disons enviable, à différentes échelles (régionale, nationale et internationale) par leur enseignement, par leur recherche, par leur implication dans l’aménagement du territoire, en matière de développement régional et auprès de la population? La publication d’un recueil de textes semblait une façon parfaite de regrouper dans un même élan des textes relatant ce que les géographes ont réalisé et ce qui les fait encore vibrer. Nous nous sommes limités aux professeurs de géographie actuels et retraités de même qu’aux étudiants diplômés des différents baccalauréats en géographie et des certificats qui leur étaient associés. Évidemment, ce qui a été rassemblé ne peut être qu’un échantillon de ce qu’ont effectué les géographes qui sont passés par l’UQAC. En effet, l’invitation à participer à ce volume, même si nous avons fouillé largement notre mémoire et nos réseaux, n’a pu rejoindre que les personnes dont les coordonnées nous étaient connues soit par les cercles d’amis et les réseaux sociaux ainsi que ceux ayant leur dossier à jour au sein de l’Association des diplômés-es de l’UQAC

Reversible inhibition of cathepsin L-like proteases by 4-mer pseudopeptides

AbstractA library of 121 pseudopeptides was designed to develop reversible inhibitors of trypanosomal enzymes (cruzain from Trypanosoma cruzi and congopain from Trypanosoma congolense). The peptides share the framework: Cha-X1-X2-Pro (Cha=cyclohexyl-alanine, X1 and X2 were phenylalanyl analogs), based on a previous report [Lecaille, F., Authié, E., Moreau, T., Serveau, C., Gauthier, F. and Lalmanach, G. (2001) Eur. J. Biochem. 268, 2733–2741]. Five peptides containing a nitro-substituted aromatic residue (Tyr/Phe) and one a 4-chloro-phenylalanine at the X1 position, and 3-(2-naphthyl)-alanine, homocyclohexylalanine or 3-nitro-tyrosine (3-NO2-Tyr) at the X2 position, were selected. They inhibited congopain more effectively than cruzain, except Cha-4-NO2-Phe-3-NO2-Tyr-Pro which bound the two parasitic enzymes similarly. Among this series, Cha-3-NO2-Tyr-HoCha-Pro and Cha-4-NO2-Phe-3-NO2-Tyr-Pro are the most selective for congopain relative to host cathepsins. No hydrolysis occurred upon prolonged incubation time with purified enzymes. In addition introduction of non-proteogenic residues in the peptidyl backbone greatly enhanced resistance to proteolysis by mammalian sera

Density‑dependent winter survival of immatures in an irruptive raptor with pulsed breeding

Highly mobile predators can show strong numerical responses to pulsed resources, sometimes resulting in irruptions where large numbers of young invade landscapes at a continental scale. High production of young in irruption years may have a strong influence on the population dynamics unless immature survival is reduced compared to non-irruption years. This could occur if subordinate individuals (mainly immatures) are forced into suboptimal habitats due to density-dependent effects in irruption years. To test whether irruptive individuals had lower survival than non-irruptive ones, we combined necropsy results (N = 365) with telemetry (N = 185) from more than 20 years to record timing and causes of mortality in snowy owls (Bubo scandiacus), which irrupt into eastern North America during winter following high breeding output caused by lemming peaks in the Arctic. Mortality was more than four times higher in irruption years than non-irruption years, but only for immatures, and occurred disproportionately in early winter for immatures, but not adults. Mortality was also higher in eastern North America, where owl abundance fluctuates considerably between years, compared to core winter regions of the Arctic and Prairies where populations are more stable. Most mortality was not due to starvation, but rather associated with human activity, especially vehicle collisions. We conclude that immature snowy owls that irrupt into eastern North America are limited by density-dependent factors, such as increased competition forcing individuals to occupy risky human-altered habitats. For highly mobile, irruptive animals, resource pulses may have a limited impact on population dynamics due to low subsequent survival of breeding output during the nonbreeding season.publishedVersio

Search for squarks and gluinos in events with isolated leptons, jets and missing transverse momentum at s√=8 TeV with the ATLAS detector

The results of a search for supersymmetry in final states containing at least one isolated lepton (electron or muon), jets and large missing transverse momentum with the ATLAS detector at the Large Hadron Collider are reported. The search is based on proton-proton collision data at a centre-of-mass energy s√=8 TeV collected in 2012, corresponding to an integrated luminosity of 20 fb−1. No significant excess above the Standard Model expectation is observed. Limits are set on supersymmetric particle masses for various supersymmetric models. Depending on the model, the search excludes gluino masses up to 1.32 TeV and squark masses up to 840 GeV. Limits are also set on the parameters of a minimal universal extra dimension model, excluding a compactification radius of 1/R c = 950 GeV for a cut-off scale times radius (ΛR c) of approximately 30

Measurements of fiducial and differential cross sections for Higgs boson production in the diphoton decay channel at s√=8 TeV with ATLAS

Measurements of fiducial and differential cross sections are presented for Higgs boson production in proton-proton collisions at a centre-of-mass energy of s√=8 TeV. The analysis is performed in the H → γγ decay channel using 20.3 fb−1 of data recorded by the ATLAS experiment at the CERN Large Hadron Collider. The signal is extracted using a fit to the diphoton invariant mass spectrum assuming that the width of the resonance is much smaller than the experimental resolution. The signal yields are corrected for the effects of detector inefficiency and resolution. The pp → H → γγ fiducial cross section is measured to be 43.2 ±9.4(stat.) − 2.9 + 3.2 (syst.) ±1.2(lumi)fb for a Higgs boson of mass 125.4GeV decaying to two isolated photons that have transverse momentum greater than 35% and 25% of the diphoton invariant mass and each with absolute pseudorapidity less than 2.37. Four additional fiducial cross sections and two cross-section limits are presented in phase space regions that test the theoretical modelling of different Higgs boson production mechanisms, or are sensitive to physics beyond the Standard Model. Differential cross sections are also presented, as a function of variables related to the diphoton kinematics and the jet activity produced in the Higgs boson events. The observed spectra are statistically limited but broadly in line with the theoretical expectations