Structural study of Zn-exchanged natural clinoptilolite using powder XRD and positron annihilation data

Abstract

AbstractZn-exchanged natural clinoptilolite was studied by powder X-ray diffraction and positron annihilation lifetime spectroscopy. The original clinoptilolite tuff was subjected to size fractionation by sedimentation and dissolution of cristobalite (opal-C). After Zn2+-exchange the purified clinoptilolite sample contained 2.2 Zn2+ ions per unit cell. Structural details obtained by Rietveld refinement showed that the Zn2+ cations are located in three sites (Zn1, Zn2 and Zn3) in the channels of the clinoptilolite. Site Zn1 is located in the centre of channel-A (Mg2+-M4 site). Site Zn2 is in channel-B, next to the calcium M2 position. A new Zn3 site is located in channel-A, in imminent proximity to Zn1. Positron Annihilation Lifetime Spectroscopy (PALS) was employed to assess the Zn exchange. As the cation content influences the free volume of the channels, the ionexchange process can be monitored by PALS. The results suggest the existence of two sizes of cavities, in accordance with the structural refinement.