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Nanoporous solids are attractive materials for energetically efficient and environmentally friendly catalytic and adsorption separation processes. Although the performance of such materials is largely dependent on their molecular transport properties, our fundamental understanding of these phenomena is far from complete. This is particularly true for the mechanisms that control the penetration rate through the outer surface of these materials (commonly referred to as surface barriers). Recent detailed sorption rate measurements with Zn(tbip) crystals have greatly enhanced our basic understanding of such processes. Surface resistance in this material has been shown to arise from the complete blockage of most of the pore entrances on the outer surface, while the transport resistance of the remaining open pores is negligibly small. More generally, the revealed correlation between intracrystalline diffusion and surface permeation provides a new view of the nature of transport resistances in nanoporous materials acting in addition to the diffusion resistance of the regular pore network, leading to a rational explanation of the discrepancy which is often observed between microscopic and macroscopic diffusion measurements.

The effect of small amounts of water, in regard to inhibiting the adsorption of carbon dioxide (CO2), on several different cationic forms of zeolite X has been investigated using the zero length column (ZLC) technique, coupled with temperature-programmed desorption (TPD) measurements. This is shown to be a very effective way to study the effect of a strongly adsorbed species (water) on the adsorption of a less-strongly adsorbed species (CO2 or propane (C3H8)). It was observed that, for all systems studied, the Henry constant declines exponentially with the loading of water. As expected, this effect is stronger for CO2 than for C3H8.