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

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 informatiion is obtained for the different copper positions in dehydrated Cu-CHA. The wel-defined copper sites in the six membered ring of the CHA structure are found to be EPR active to give two distinct sets of signal 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 degrees 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.