Cation Control of Molecular Sieving by Flexible Li-Containing Zeolite Rho

Abstract

The adsorption of CO2 on zeolite Li-Rho (unit cell composition Li9.8Al9.8Si38.2O96) has been investigated by the measurement of adsorption isotherms (273–300 K), breakthrough curves with a CO2/CH4/He mixture (308 K), and in situ synchrotron X-ray powder diffraction in CO2 (298 K). The Rho framework distorts when in the Li-form to give a shape selective adsorbent for CO2 over CH4, although breakthrough curves reveal diffusional limitations. In situ synchrotron powder XRD follows the expansion of the Li-Rho unit cell upon adsorption, which remains single phase to a CO2 pressure of ca. 0.6 bar. Partial cation exchange of Li-Rho by Na+ or Cs+ gives two series of M,Li-Rho zeolites (M = Na, Cs). Where the occupancy of window sites (8R, D8R) between lta cages is less than 50%, hysteresis is not observed in CO2 isotherms at 298 K. For Cs1.8Li8-Rho, which has a larger unit cell and a wider window than zeolite Li-Rho due to the presence of large Cs+ cations in double 8-ring sites, breakthrough curves indicate faste...