The nature of surface barriers on nanoporous solids explored by microimaging of transient guest distributions.

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).

Assessing molecular transport properties of nanoporous materials by interference microscopy: remarkable effects of composition and microstructure on diffusion in the silicoaluminophosphate zeotype STA-7.

The influence of the chemical composition and of the storage and activation protocol on the diffusion of methanol into strongly chemically zoned crystals of the silicoaluminophosphate zeotype STA-7 has been investigated by interference microscopy. Analysis of the evolution of transient intracrystalline concentration profiles reveals that just-calcined SAPO STA-7 crystals with lower Si content (Si/(Si + P) = 0.18) exhibit higher surface permeability and bulk diffusivity than those with higher Si content (S/(Si + P) = 0.

Ensemble measurement of diffusion: novel beauty and evidence.

Recording the evolution of concentration profiles in nanoporous materials opens a new field of diffusion research with particle ensembles. The technique is based on the complementary application of interference microscopy and IR micro-imaging. Combining the virtues of diffusion measurements with solids and fluids, it provides information of unprecedented wealth and visual power on transport phenomena in molecular ensembles.

Assessing surface permeabilities from transient guest profiles in nanoporous host materials.

Easy come, easy go? Transport resistances on particle surfaces are important for mass transfer in nanoporous materials and bulk diffusion in crystals. Interference microscopy and IR micro-imaging are shown to be excellent tools for determining such transport resistances. By studying short-chain-length alkane guest molecules in crystals of the metal-organic framework compound Zn(tbip) a data collection of surface permeabilities is established.

Assessing guest diffusivities in porous hosts from transient concentration profiles.

Using the short-chain-length alkanes from ethane to n-butane as guest molecules, transient concentration profiles during uptake or release (via interference microscopy) and tracer exchange (via IR microimaging) in Zn(tbip), a particularly stable representative of a novel family of nanoporous materials (the metal organic frameworks), were recorded. Analyzing the spatiotemporal dependence of the profiles provides immediate access to the transport diffusivities and self-diffusivities, yielding a data basis of unprecedented reliability for mass transfer in nanoporous materials. As a particular feature of the system, self- and transport diffusivities may be combined to estimate the rate of mutual passages of the guest molecules in the chains of pore segments, thus quantifying departure from a genuine single-file system.