Vanadium oxide monolayer catalysts. 3. A Raman spectroscopic and temperature-programmed reduction study of monolayer and crystal-type vanadia on various supports Roozeboom, F.; Mittelmeijer-Hazeleger, M.C.; Moulijn, J.A.; Medema, J.; de Beer, V.H.J.; Gellings, P.J. Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.
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Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Vanadium(V) oxide supported on 7-A1203, GO2, Cr2O3, Si02, Ti02, and Zr02 was studied by X-ray fluorescence, by X-ray diffraction, and especially by the combination of Raman spectroscopy and temperature-programmed reduction (TPR) for qualitative and quantitative structural analysis, respectively. Catalysts were prepared via ion-exchange and wet-impregnation methods. The V contents ranged from -1 to 40 wt % V. At low surface concentrations only surface vanadate phases of two-dimensional character are observed for all carriers. According to Raman and TPR data the structure of these surface vanadate species is independent of the preparation technique. At medium and high surface concentrations, the webimpregnated samples already contain crystalline V20b At equal surface concentrations the ion-exchanged catalysts contain no V205 crystallites. An exception is Si02 on which also crystalline V206 is formed in both preparation techniques. Monolayer stability toward thermal treatment decreases in the order AZO3 > Ti02 > Ce02, whereas on heating ion-exchanged V/Si02 the crystalline V206 spreads out over the silica surface. The reducibilities of the ion-exchanged catalyats, as measured by TPR, can be used as a measure for the contact interaction between vanadia and the carrier oxides. At temperatures of 500-800 K, this interaction ranges fr...
A lack of temperature information makes it impossible to judge this point.Two theoretical studies8,9 provide no HOC1 absorption bands for /nm > 300. It is questionable how accurate such predictions are, especially in cases where elements of the third period with unoccupied 3d orbitals such as Cl or S atoms participate. The stratospheric HOC1 photodissociation rate calculated on the basis of our cross sections is about 25% smaller than the photolysis rate derived from Molina's data, corresponding to an equally enlarged HOC1 lifetime.
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