Unique adsorption properties and potential energy profiles of microporous pillared clays

The adsorption isotherms of O₂, N₂, CH₄, CO₂, SO₂, and NO on five pillared clays (Zr, Al, Cr, Fe, and Ti‐PILCs) are measured. The equilibrium selectivity of CH₄/N₂ on Al‐PILC is greater than 5.0, which exceeds all known sorbents by a large margin. In addition, high SO₂/CO₂ equilibrium selectivities are observed on these pillared clays. The sorption characteristics of these pillared clays (PILCs) exhibit characteristic trends that are better understood with the aid of the potential energy profiles. A new semi‐empirical approach is presented for the calculations of the potential energy profiles of PILCs. This approach requires the adsorption isotherms and an isotherm equation that accounts for the structural heterogeneity of the adsorbents. A comparison of the energy profiles obtained using the semi‐empirical approach with the corresponding results obtained via the Kirkwood‐Muller formalism, where only dispersion forces are taken into account, provides a measure of the importance of the electrostatic forces in the sorption characteristics of these PILCs. Sizable differences are observed for the potential energy profiles, indicating that the electrostatic forces are not negligible, and can significantly enhance the adsorption potential, resulting in large increases in the amounts adsorbed on these PILCs.