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  • 1
    ISSN: 1572-879X
    Keywords: Carbon supported Fe ; Fe-Mn ; K-Fe-Mn catalysts ; mixed metal carboxyl clusters ; chemisorption ; kinetic measurements ; calorimetric measurements ; infrared spectroscopy ; Mössbauer spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Carbon-supported Fe, Fe-Mn, and K-Fe-Mn catalysts derived from stoichiometric mixed-metal carbonyl clusters were pretreated at either 473 K or 673 K in hydrogen. Chemisorption and kinetic measurements were conducted following these pretreatments. The iron remained highly dispersed at all times except after high temperature reductions when potassium was present. The single promotion by either Mn or K increases the olefin/paraffin ratio, while the doubly promoted catalyst gave very high selectivities for light olefins. Isothermal, integral heats of adsorption of CO were determined at 300 K, and they increased from 15 kcal/mole for Fe3/C to nearly 17 kcal/mole for both the singly promoted Fe2Mn/C and KFe3/C catalysts to 21 kcal/mole for the doubly promoted KFe2Mn/C sample. A model of the decomposition of these carbonyl clusters is proposed based on calorimetric, Mössbauer effect spectroscopic and diffuse reflectance Fourier transform infrared spectroscopic studies. The state of the MnOx and K phases on the iron surface, as well as the Fe crystallite size, appears to play a dominant role in determining the catalytic behavior.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Topics in catalysis 8 (1999), S. 211-222 
    ISSN: 1572-9028
    Keywords: reforming ; methane ; carbon dioxide ; Rh/SiO2 ; vanadia-promoted Rh/SiO2 ; FTIR spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reforming of methane with carbon dioxide over rhodium dispersed on silica, Rh/SiO2, and vanadia-promoted silica, Rh/VOx/SiO2, was studied by kinetic test reactions under differential conditions in a temperature range from 723 to 773 K. Transmission infrared spectroscopy was applied to observe the interaction of CO2 with the catalysts and the formation of surface intermediates during the CO2–CH4 reforming reaction. To analyze carbon deposition XP spectroscopy and TPO was carried out. It has been shown that the promotion of Rh/SiO2 catalysts with vanadium oxide enhances the catalytic activity for CO2 reforming of methane and decreases the deactivation by carbon deposition. This is attributed to the formation of a partial VOx overlayer on the Rh surface, which reduces the size of accessible ensembles of Rh atoms required for coke formation and creates new sites at the Rh–VOx interfacial region that are considered to be active sites for the activation/dissociation of carbon dioxide.
    Type of Medium: Electronic Resource
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