Characterization of Fe sites in Fe-zeolites by FTIR spectroscopy of adsorbed NO: are the spectra obtained in static vacuum and dynamic flow set-ups comparable?
The present paper shows a direct comparison of IR spectra of adsorbed NO on two catalyst systems (Fe-silicalite and Fe-ZSM-5), recorded in a flow-through cell (in operando, where NO is carried by an excess of inert gas) and static cell (in situ, where a given pure NO equilibrium pressure is dosed)....
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Published in | Physical chemistry chemical physics : PCCP Vol. 12; no. 2; pp. 358 - 364 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
01.01.2010
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Subjects | |
Online Access | Get full text |
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Summary: | The present paper shows a direct comparison of IR spectra of adsorbed NO on two catalyst systems (Fe-silicalite and Fe-ZSM-5), recorded in a flow-through cell (in operando, where NO is carried by an excess of inert gas) and static cell (in situ, where a given pure NO equilibrium pressure is dosed). A progressive NO poly-adsorption is observed in the static cell upon increasing the NO equilibrium pressure (from Fe(2+)...(NO)(2) to Fe(2+)...(NO)(3)), while predominantly Fe(2+)...NO adducts are observed in the flow-through cell. By comparing literature spectra, it is shown that these spectral differences are intrinsically inherent to the two different experimental approaches. The two experimental set-ups are able to observe preferentially only a part of the total Fe species present on Fe-zeolites. Water contamination experiments employing different experimental conditions (order of dosage, co-dosage, different NO/H(2)O ratios) did not reproduce in the static environment the IR spectra collected with the dynamic set-up. The spectral differences could have a thermodynamic origin and be related to different adsorption enthalpies of mono- and di-nitrosyl complexes of the two Fe(2+) families and to the different NO partial pressure adopted in the two experimental configurations. These considerations have important consequences for the conclusions reached by different research groups on the structure of active Fe sites. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/b917646m |