Alexander Lauerer

The role of crystal diversity in understanding mass transfer in nanoporous materials

Nanoporous materials find widespread applications in our society: from drug delivery to environmentally friendly catalysis and separation technologies. The efficient design of these processes depends crucially on understanding the mass transfer mechanism. This is conventionally determined by uptake or release experiments, carried out with assemblages of nanoporous crystals, assuming all crystals to be identical. Using micro-imaging techniques, we now show that even apparently identical crystals (that is, crystals of similar size and shape) from the same batch may exhibit very different uptake rates. The relative contribution of the surface resistance to the overall transport resistance varied with both the crystal and the guest molecule. As a consequence of this crystal diversity, the conventional approach may not distinguish correctly between the different mass transfer mechanisms. Detection of this diversity adds an important new piece of evidence in the search for the origin of the surface barrier phenomenon. Our investigations were carried out with the zeolite SAPO-34, a key material in the methanol-to-olefins (MTO) process, propane-propene separation and adsorptive heat transformation.

Scale-dependent diffusion anisotropy in nanoporous silicon

Nanoporous silicon produced by electrochemical etching of highly B-doped p-type silicon wafers can be prepared with tubular pores imbedded in a silicon matrix. Such materials have found many technological applications and provide a useful model system for studying phase transitions under confinement. This paper reports a joint experimental and simulation study of diffusion in such materials, covering displacements from molecular dimensions up to tens of micrometers with carefully selected probe molecules. In addition to mass transfer through the channels, diffusion (at much smaller rates) is also found to occur in directions perpendicular to the channels, thus providing clear evidence of connectivity. With increasing displacements, propagation in both axial and transversal directions is progressively retarded, suggesting a scale-dependent, hierarchical distribution of transport resistances (“constrictions” in the channels) and of shortcuts (connecting “bridges”) between adjacent channels. The experimental evidence from these studies is confirmed by molecular dynamics (MD) simulation in the range of atomistic displacements and rationalized with a simple model of statistically distributed “constrictions” and “bridges” for displacements in the micrometer range via dynamic Monte Carlo (DMC) simulation. Both ranges are demonstrated to be mutually transferrable by DMC simulations based on the pore space topology determined by electron tomography.