EPR and ESEEM study of silver clusters in ZK-4 molecular sieves

Silver clusters generated by g-irradiation in ZK-4 zeolites – isostructural with Linde type A (LTA) zeolite, have been studied by electron paramagnetic resonance (EPR) spectroscopy. It was shown that even a small decrease of cation capacity resulting from a lower Si/Al ratio in the framework affects distinctly silver agglomeration. In dehydrated ZK-4 with Si/Al = 1.2 and 2.4 only silver dimers are stabilized, whereas in Linde 4A silver hexamers were trapped. In ZK-4 exposed to H2O and CH3OH, silver tetramers Ag43+ efficiently are formed. The results of electron spin echo envelope modulation (ESEEM) showed that the adsorbate molecules are in close vicinity to the clusters. It was postulated that in zeolites with low cation capacity the adsorbate molecules make difficult Ag0 migration promoting the reactions with Ag+ cations located in the same sodalite cage.