کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
10244425 | 47684 | 2005 | 12 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Dimeric Cu(I) species in Cu-ZSM-5 catalysts: the active sites for the NO decomposition
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موضوعات مرتبط
مهندسی و علوم پایه
مهندسی شیمی
کاتالیزور
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
In this study data are presented which support the view that a special configuration of dimeric Cu(I) species in Cu-ZSM-5 catalysts may be the active site for NO decomposition. Such dimeric Cu(I) species, produced by self-reduction of Cu(II) during the thermal activation of Cu-ZSM-5 catalysts in He or under vacuum, are the sites where N2 is generated from two adsorbed NO molecules, and from which O2 desorbs from the catalyst at the steady state. It was found that these dimeric Cu(I) species adsorb N2 irreversibly at low temperature (273-325 K). DFT calculations for cluster models obtained from the crystallographic structure of orthorhombic ZSM-5 suggested that Cu(I)-N2-Cu(I) species may be IR-silent or have a very low extinction coefficient, as suggested by previous diffuse reflectance FT results. The isosteric heat of adsorption of N2 on Cu-ZSM-5, obtained with the Clausius-Clapeyron equation from adsorption isotherms in the temperature range of 273-325 K, is 10.3 kcalâmolâ1 at a coverage of 0.4 mol N2/mol Cu. This value is much larger than the heat of condensation of N2 at 77 K (1.33 kcalâmolâ1) and significantly higher than the heat of adsorption of N2 on Li-ZSM-5 (8.68 kcalâmolâ1 at zero coverage) obtained with the Clausius-Clapeyron equation from adsorption isotherms in the temperature range of 196-273 K. The turnover frequency (TOF) for the NO decomposition, calculated assuming that the active sites are those titrated by the irreversible adsorbed N2 at 273 K, is independent of the copper loading and of the ZSM-5 Si/Al atomic ratio. The present model is also supported by the evidence that Cu-Y, Cu-S-1, and Cu-[Al]-MCM-41 catalysts, containing Cu(I) species that do not adsorb irreversibly N2 at 273-325 K, were found to be inactive or scarcely active (Cu-Y) for the NO decomposition reaction under the same experimental conditions as employed for Cu-ZSM-5.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Catalysis - Volume 232, Issue 2, 10 June 2005, Pages 476-487
Journal: Journal of Catalysis - Volume 232, Issue 2, 10 June 2005, Pages 476-487
نویسندگان
Giuliano Moretti, Giovanni Ferraris, Giuseppe Fierro, Mariano Lo Jacono, Simone Morpurgo, Marco Faticanti,