Crystallographic studies on the site selectivity of Ca2+, K+, and Rb+ ions within zeolite Y (Si/Al = 1.56)

Abstract

The single-crystals of Ca2+, K+-exchanged zeolite Y, and Ca2+, Rb+-exchanged zeolite Y were prepared by using flow method with mixed ion-exchange solution, whose Ca(NO3)2:KNO3 mole ratios were 1:1 (crystal 1) and 1:100 (crystal 2), and Ca(NO3)2:RbNO3 mole ratios were 1:1 (crystal 3) and 1:100 (crystal 4), respectively, with a total concentration of 0.05 M. They were fully dehydrated by vacuum dehydration at 723 K and 1 × 10−6 Torr for 2 days. Their crystals were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $$Fd \overline{3}$$ m, respectively, and were refined to the final error indices R 1/wR 2 = 0.057/0.196, 0.073/0.223, 0.055/0.188, and 0.049/0.175 for crystals 1, 2, 3, and 4, respectively. In the structure of crystal 1 (|Ca23K29|[Si117Al75O384]-FAU), 23 Ca2+ ions per unit cell occupy sites I, II′, and II; 29 K+ ions per unit cell are at sites II′, II, and III′. In the structure of crystal 2 (|Ca18.5K38|[Si117Al75O384]-FAU), 18.5 Ca2+ ions per unit cell occupy sites I, I′, and II; 38 K+ ions are at sites I′, II, and III′. In the structure of crystal 3 (|Ca27Rb21|[Si117Al75O384]-FAU), 27 Ca2+ ions per unit cell occupy sites I, II′, and II; 21 Rb+ ions per unit cell are at sites II′, II, and III. In the structure of crystal 4 (|Ca18Rb39|[Si117Al75O384]-FAU), 18 Ca2+ ions per unit cell occupy sites I and II; 39 Rb+ ions per unit cell are at sites I′, II′, II, III, and III′. In the four crystals, the Ca2+ ion which has much smaller size and higher charge than other cations such as K+ and Rb+ energetically preferred at site I and so the first to be filled on it. Unlike Ca2+ ion, no K+ and Rb+ ions are found at site I, which are clearly less favorable for K+ and Rb+ ions.