کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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61713 | 47600 | 2010 | 13 صفحه PDF | دانلود رایگان |
The N2O decomposition over Fe-ferrierite, Fe-beta, and Fe-ZSM-5 has been recently studied [K. Jisa, J. Novakova, M. Schwarze, A. Vondrova, S. Sklenak, Z. Sobalik, J. Catal. 262 (2009) 27] and a superior activity of Fe-ferrierite with respect to Fe-beta and Fe-ZSM-5 has been shown. In this study, we investigated (1) plausible active sites for the N2O decomposition over Fe-ferrierite and (2) the origin of the distinct reactivity of Fe-ferrierite, Fe-ZSM-5 and Fe-beta employing a combined theoretical (periodic DFT) and experimental (UV–vis–NIR spectroscopy, IR spectroscopy, 29Si MAS NMR spectroscopy and catalytic batch experiments) approach. We evidenced that two Fe(II) cations accommodated in two adjacent six-membered rings in the eight-membered ring channel (β sites) of Fe-ferrierite (the calculated Fe–Fe distance is 7.4 Å) form the active site responsible for the superior activity of this catalyst in the N2O decomposition in the absence of NO. Similar structures can be formed in Fe-beta. However, the probability of their formation is very low. For Fe-ZSM-5, the geometrical arrangement of the cationic positions is far from that in Fe-ferrierite and it is not suitable for the N2O decomposition. Therefore, the predicted order of the activity of the Fe(II) exchanged zeolites agrees with our experimental findings and it is: Fe-ferrierite ≫ Fe-beta > Fe-ZSM-5. We further showed that the accommodation of divalent cations in rings forming cationic sites can lead to significant rearrangements of the local structures of the zeolite framework, and therefore, the precise structure of sites binding a divalent cation cannot be derived from results of X-ray diffraction experiments, but can be inferred from theoretical calculations.
Two Fe(II) cations accommodated in two adjacent β sites of Fe-ferrierite form the active site responsible for the superior activity of Fe-ferrierite in the N2O decomposition in the absence of NO.Figure optionsDownload high-quality image (88 K)Download as PowerPoint slide
Journal: Journal of Catalysis - Volume 272, Issue 2, 15 June 2010, Pages 262–274