Coordination Environment of Copper Sites in Cu-CHA Zeolite Investigated by Electron Paramagnetic Resonance

Anita Godiksen, Frederick N. Stappen, Peter N. R. Vennestrøm, Filippo Giordanino, Søren Birk Rasmussen, Lars F. Lundegaard, Susanne Mossin

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Abstract

Cu-CHA combines high activity for the selective catalytic reduction (SCR) reaction with better hydrothermal stability and selectivity compared to other copper-substituted zeolites. At the same time Cu-CHA offers an opportunity for unraveling the coordination environment of the copper centers since the zeolite framework is very simple with only one crystallographically independent tetrahedral site (T-site). In this study the results of an X-band electron paramagnetic resonance (EPR) investigation of ion-exchanged Cu-CHA zeolite with a Si/Al ratio of 14 ± 1 is presented. Different dehydration treatments and rehydration experiments are performed in situ while monitoring with EPR. The results are compared with recent literature evidence from temperature-programmed reduction, X-ray methods, IR spectroscopic methods, and UV–visible spectroscopy. On the basis of these findings quantitative information is obtained for the different copper positions in dehydrated Cu-CHA. The well-defined copper sites in the six-membered ring of the CHA structure are found to be EPR active, to give two distinct sets of signals in an approximate 1:1 ratio, and to add up to 19 ± 2% of the total copper in the material. The long-standing question of the EPR silent monomeric Cu2+ in copper-substituted zeolites is suggested to be copper species with an approximate trigonal coordination sphere appearing during the dehydration. After complete dehydration at 250 °C the majority of the EPR silent Cu2+ is suggested to exist as Cu2+–OH– coordinated to two framework oxygen atoms located in the microenvironment of an isolated Al T-site.
Original languageEnglish
JournalJournal of Physical Chemistry C
Volume118
Issue number40
Pages (from-to)23126–23138
ISSN1932-7447
DOIs
Publication statusPublished - 2014

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