40 research outputs found

    Exit the Way You Came

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    Contents: They overstay their visit; Arcadia, North Carolina; In the Cadaver Lab; Swan at Trout Lake; A fever ago; Skeleton; Build me a house; German immigrant; Build me a city; After surgery; Moving, Part I; When asked if your family was religious; Stay, static; I wanted you; The only picture of my parents I refuse to throw away; Lamentations; Moving, Part II; Registered organ donor; Father references fights with old addresses; Dear Sophie; The quieter one; Lessons on Marriage; Rocket; Elegy; Intention; She said I live in Arcadia; Whey I won’t buy this postcard with a heart on itBachelor of Art

    XANES study of rhenium oxide compounds at the L1 and L3 absorption edges

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    8 pagesInternational audienceWe report on the study of a set of rhenium oxide reference compounds (NH4ReO4, NaReO4, ReO3, ReO2, and Re2O7) using x-ray-absorption near-edge structure. The parallel use of Re L1 and L3 absorption edges permits a concomitant understanding of both the oxidation state and the local symmetry for these compounds. Experiments are compared with ab initio simulations. A good agreement is reached in most cases. The choice of the cluster size and the calculation method (full potential or not), which are mandatory ingredients allowing a satisfactory reproduction of the recorded spectra, is discussed in detail. In the meantime, these parameters give important pieces of information on the studied materials

    Préparation et caractérisation de catalyseurs bifonctionnels Re/SiO2 pour la conversion directe de méthanol en diméthoxyméthane

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    Les catalyseurs à base d oxyde de rhénium massique ou supporté sont connus pour présenter de bonnes performances dans la conversion directe du méthanol en diméthoxyméthane. Cette réaction élégante requiert un catalyseur bifonctionnel acide-redox et s inscrit dans la recherche de procédés courts mettant en œuvre des réactifs issues de la biomasse. La structure des phases actives oxorhénates supportées fait débat et semble conditionnée par (i) la désorption rapide des oxydes de rhénium et (ii) les propriétés physico-chimiques du support. Dans cette étude, nous avons, de manière incontestable, mis en évidence l existence d entités non équivalentes dont la structure est liée à la teneur en rhénium. Dans le cas de catalyseurs conventionnels, la désorption massive des oxydes de rhénium en conditions réactionnelles rend impossible l établissement d une corrélation structure-réactivité. Nous avons mis au point une voie de synthèse alternative et préparé un catalyseur ReOx/SiO2 dont les performances égalent les meilleurs catalyseurs actuels. Grâce à une première étude in situ basée sur les spectroscopies Raman et XAS en conditions operando, il a été possible de proposer, pour cette phase active, une structure originale de type adduit RexOy.nH2O. D autres particularités, comme la nano-texturation du catalyseur sont évoquées pour expliquer la limitation du phénomène de désorption de rhénium. Pendant la réaction, le couple redox ReVI/ReIV est responsable de l oxydation ménagée du méthanol en formaldéhyde, tandis que l espèce ReVII présente une acidité suffisante pour permettre la condensation rapide de deux molécules de méthanol avec le formaldéhyde adsorbé et former le diméthoxyméthane.Bulk or supported rhenium oxide based catalysts, are known to have good performances in terms of direct conversion of methanol to dimethoxymethane. This refined reaction needs a bifunctional acid-redox catalyst and, is in line with short process research dealing with biomass reagents. The supported oxorhenate active phase structure is still under debate, but seems to be highly dependent of (i) the rhenium oxide fast desorption rate (ii) and the support physical-chemical properties. In this study, we have, without any doubt, shown the presence of several entities which seem to be dependent of the rhenium loading. In the case of conformist catalysts, the massive rhenium oxide desorption during the reaction makes it very difficult to correlate structure and reactivity. So, we developed an alternate synthesis path and prepared a Re/SiO2 catalyst, which performances are among the best up to date. Thanks to an opening in situ study based on Raman spectroscopy and XAS in Operando conditions, it has been possible to suggest, for this active phase, a genuine structure looking like RexOy.nH2O. Other specificities, like the catalyst nano-structure are mentioned to explain the rhenium desorption restriction. During the reaction, the redox couple ReVI/ReIV is responsible of the mild methanol oxidation to formaldehyde, while the ReVII specie possesses enough acidity to rapidly condensate two methanol molecules with the absorbed formaldehyde to form dimethoxymethane.LILLE1-Bib. Electronique (590099901) / SudocSudocFranceF

    Operando Spectroscopic studies of methnol conversion over supported oxomolybdates catalysts

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    A study combining DFT calculations and complementary "in situ" and "operando" techniques is presented. The structure of oxomolybdate catalyst was found to be mandatory for the selected reaction. More precisely, our results converge to the same statement: isolated [MoO4] moieties are not active in methanol oxidation to formaldehyde
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