Abstract

The rates of uptake and release of guest molecules in nanoporous solids are often strongly influenced or even controlled by transport resistances at the external surface (“surface barriers”) rather than by intraparticle diffusion, which was assumed to be rate controlling in many of the earlier kinetic studies.

By correlating the surface resistance with the intracrystalline diffusivity, we develop here a microkinetic model which closely reproduces the experimentally observed results for short-chain alkanes in Zn(tbip), a member of the novel metal-organic framework family of nanoporous materials. It seems likely that this mechanism, which is shown to provide a rational explanation of the commonly observed discrepancies between “macro” and “micro” measurements of intracrystalline diffusion, may be fairly general.