Controlled gas adsorption properties of various pillared clays

Abstract

Microporous pillared clays (PILC) were prepared by the intercalation of montmorillonite with particles of titania (Ti-PILC), zirconia (Zr-PILC), alumina (Al-PILC), iron oxide (Fe-PILC) and mixed lanthania/alumina (LaAl-PILC). Nitrogen adsorption isotherms (77 K) and XRD data provided information on the porosity, surface area, micropore volume and interlayer distance of these samples. The surface area varied between 198 and 266 m2/g for Ti- and Fe-PILC, respectively. The titania pillared clay had also the highest micropore volume (0.142 cc/g) and interlayer spacing (16–20 A), compared to the Zr-PILC, which had the smallest spacing between the layers (max, 4 A). Despite this fact, Zr-PILC always showed a high adsorption capacity for gases such as N2, O2, Ar or CO2, due to its high adsorption field in the very small micropores. From gas adsorption experiments on these various PILCs, it became clear that their adsorption properties depend on the pillars in three ways: (i) the pillar height, (ii) the distribution of the pillars between the clay layers and (iii) the nature of the pillaring species. The incorporation of other elements in the pillars leads to specific adsorption sites in the pores. This was demonstrated by the preparation of mixed Fe/Cr and Fe/Zr pillared clays. Compared to the parent Fe-PILC, the incorporation of chromium and zirconium in the iron oxide pillars had a positive influence on the adsorption capacity. Also the modification of a PILC with cations increases both capacity and selectivity for gases. This was confirmed by the increased adsorption of N2, O2 and CO2 at 273 K on a Sr2+ exchanged Al-PILC.