As an omnipresent phenomenon in nature, diffusion is among the rate-determining processes in many technological processes. This is in particular true for catalytic conversion in nanoporous materials. We provide a critical review of the possibilities of exploring diffusion phenomena over microscopic dimensions in such media by direct experimental observation. By monitoring the probability distribution of molecular displacements as a function of time, the pulsed field gradient technique of NMR (PFG NMR) records the rate of molecular re-distribution. By varying the observation time, PFG NMR is thus able to trace even hierarchies of transport resistances as occurring, e.g., in catalyst particles in the form of binder-compacted assemblages of zeolite crystallites. Alternatively, and complementary to this information, interference microscopy (IFM) and IR microscopy (IRM) are able to follow the evolution of intracrystalline concentration profiles during uptake and release. This allows, in particular, an accurate quantification of the transport resistances on the surface of the individual crystallites and of the probability that reactant molecules from the gas phase, upon colliding with the external surface, are able to penetrate through such “surface barriers” into the crystal bulk phase. Being able to distinguish between different molecular species, IRM is able to record the evolution of intracrystalline concentration profiles even during multi-component adsorption and catalytic reactions (169 references).

Diffusion is known to be quantified by measuring the rate of molecular fluxes in the direction of falling concentration. In contrast with intuition, considering methanol diffusion in a novel type of nanoporous material (MOF ZIF-8), this rate has now been found to be enhanced rather than slowed down by an opposing flux of labeled molecules. In terms of the key quantities of random particle movement, this result means that the self-diffusivity exceeds the transport diffusivity. It is rationalized by considering the strong intermolecular interaction and the dominating role of intercage hopping in mass transfer in the systems under study.

The presence of mesopores in the interior of microporous particles may significantly improve their transport properties. Complementing previous macroscopic transient sorption experiments and pulsed field gradient NMR self-diffusion studies with such materials, the present study is dedicated to an in-depth study of molecular uptake and release on the individual particles of mesoporous zeolitic specimens, notably with samples of the narrow-pore structure types, CHA and LTA. The investigations are focused on determining the time constants and functional dependences of uptake and release. They include a systematic variation of the architecture of the mesopores and of the guest molecules under study as well as a comparison of transient uptake with blocked and un-blocked mesopores. In addition to accelerating intracrystalline mass transfer, transport enhancement by mesopores is found to be, possibly, also caused by a reduction of transport resistances on the particle surfaces.