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  • 1
    ISSN: 1572-879X
    Keywords: cerium oxides ; SO2 ; desulfurization ; copper ; X‐ray absorption spectroscopy ; photoemission and XPS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract CeO2 and Cu/CeO2 are effective catalysts/sorbents for the removal or destruction of SO2. Synchrotron‐based high‐resolution photoemission, X‐ray absorption near‐edge spectroscopy (XANES), and temperature‐programmed desorption (TPD) have been employed to study the reaction of SO2 with pure and reduced CeO2 powders, ceria films (CeO2, CeO2−x, Ce2O3+x) and model Cu/CeO2 catalysts. The results of XANES and photoemission provide evidence that SO4 was formed upon the adsorption of SO2 on pure powders or films of CeO2 at 300 K. The sulfate decomposed in the 390–670 K temperature range with mainly SO2 and some SO3 evolving into gas phase. At 670 K, there was still a significant amount of SO4 present on the CeO2 substrates. The introduction of O vacancies in the CeO2 powders or films favored the formation of SO3 instead of SO4. Ceria was able to fully dissociate SO2 to atomic S only if Ce atoms with a low oxidation state were available in the system. When Cu atoms were added to CeO2 new active sites for the destruction of SO2 were created improving the catalytic activity of the system. The surface chemistry of SO2 on the Cu‐promoted CeO2 was much richer than on pure CeO2. The behavior of ceria in several catalytic processes (oxidation of SO2 by O2, reduction of SO2 by CO, automobile exhaust converters) is discussed in light of these results.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: nickel molybdate ; HDS catalysts ; sulfur poisoning ; X-ray absorption spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This study aims at characterizing the properties of pure and sulfided NiMoO4 catalysts using synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) and temperature-programmed reduction (TPR). Mo LII-edge and MIII-edge NEXAFS spectra indicate that on reaction with H2S, the Mo component of NiMoO4 gets partially reduced with the formation of MoS2 type species. For the β-phase of NiMoO4, the sulfidation of Mo is more extensive than for the α-phase, making the former a better precursor for catalysts of hydrodesulfurization (HDS) reactions. The Ni LII-edge features are relatively insensitive to the changes accompanying the partial sulfidation of NiMoO4. The sulfidation of the Ni component is confirmed by analysis of the Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra which show the formation of Ni–S bonds (bond length ∼2.48 Å) and a NiMoSx phase. The S K-edge NEXAFS spectra show the presence of at least two types of sulfur species, one associated with a formal oxidation state of 2- and another associated with a formal oxidation state of 6+. We attribute the former to the presence of metal–sulfur bonds (MoSx and NiSy). The latter is associated with the formation of S–O bonds (SO 4 2- ). The formation of sulfates is also supported by the O K-edge NEXAFS spectra. The partially sulfided NiMoO4 catalysts (both α- and β-isomorphs) have a much lower thermal stability in a reducing environment than pure NiMoO4 and MoS2. The sulfided molybdates react with H2 in TPR producing H2O and H2S at temperatures above 400 K.
    Type of Medium: Electronic Resource
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