Crystallographic Study on Zeolite 4A Reacted with Rubidium Vapor

루비듐 증기와 반응한 제올라이트 4A에 대한 결정학적 연구

Three fully dehydrated fully Rb+-exchanged zeolite A single crystals have been prepared by the reduction of all Na+ ions in dehydrated Na12-A by rubidium vapor at various experimental conditions (220 $\leq$ T $\leq$ 33$0^{\circ}C$, 2 $\leq$ t $\leq$24 hours, and 0.1 $\leq$ PRb $\leq$ 1.1 Torr). Their structures were determined by single-crystal X-ray diffraction methods in the space group {{{{ RHO }}m3m (a=12.245(3) A) at 22(1)$^{\circ}C$. In these structures 12.6(2) to 13.5(2) Rb species are found per unit cell, more than the 12 Rb+ ions needed to balance the anionic charge of the zeolite framework, indication that the sorption of Rb0 has occurred. In each structure, three Rb+ ions per unit cell are located at the centers of 8-rings. Beyond that, the fractional occupancies observed are simply explained by two unit cell arrangments. In one, two Rb+ ions are in the sodalite unit near opposite 6-rings, six are in the large cavity near 6-ring, and one is in the large cavity near a 4-ring. In the other, three Rb species in the sodalite cavity (forming a triangle 3.7 A on an edge) each bond (3.4 A) through a 6-ring to an Rb species in the large cavity to give an (Rb6)4+ cluster of symmetry 3m (C3V). Five additional Rb+ ions fill the remaining large-cavity 6-ring sites.