Porous metal–organic frameworks have emerged to resolve important challenges of our modern society, such as CO₂ sequestration. Zeolitic imidazolate frameworks (ZIFs) can undergo a glass transition to form ZIF glasses; they combine the liquid handling of classical glasses with the tremendous potential for gas separation applications of ZIFs. Using millimetre-sized ZIF-62 single crystals and centimetre-sized ZIF-62 glass, we demonstrate the scalability and processability of our materials. Further, following the evolution of gas penetration into ZIF crystals and ZIF glasses by infrared microimaging techniques, we determine the diffusion coefficients and changes to the pore architecture on the ångström scale. The evolution of the material on melting and processing is observed in situ on different length scales by using a microscope-coupled heating stage and analysed microstructurally by transmission electron microscopy. Pore collapse during glass processing is further tracked by changes in the volume and density of the glasses. Mass spectrometry was utilized to investigate the crystal-to-glass transition and thermal-processing ability. The controllable tuning of the pore diameter in ZIF glass may enable liquid-processable ZIF glass membranes for challenging gas separations.

Mass transfer in hierarchically porous materials is a function of various parameters, notably including the diffusivities in the various pore spaces, their relative populations and the exchange rates. Their interplay is shown to be quantified in the two‐region model of diffusion which in magnetic resonance imaging is in common use under the name Kärger equations. After manifold applications in NMR diffusometry with compartmented systems, the underlying formalism is now demonstrated to offer an excellent tool for assessing mass transfer in hierarchically porous materials. The potentials include a comprehensive description of mass transfer, in parallel with the specification of the various limiting cases and their reflection by experimental measurement. Information provided by application of microscopic techniques of measurement such as microimaging and pulsed field gradient NMR is shown to notably exceed the message of, e.g., macroscopic uptake measurement of diffusion in hierarchically porous media. This includes, in particular, experimental insight into the dominating mechanisms of mass transfer, which is crucial for the development of optimal strategies of performance enhancement for the technological exploitation of such materials. Depending on the microstructural and microdynamic situation, elucidated in such studies, very different and even mutually opposing strategies for performance enhancement are shown to result.

Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e., by transient n-pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

Microimaging on the basis of, respectively, interference microscopy and IR microscopy permit the observation of the distribution of guest molecules in nanoporous solids and their variation with time. Thus attainable knowledge of both concentration gradients and diffusion fluxes provides direct access to the underlying diffusion phenomena. This includes, in particular, the measurement of transport diffusion under transient, i. e. under non-equilibrium conditions, and of self- or tracer diffusion on considering the rate of tracer exchange. Correlating the difference in guest concentration close to the external surface to its equilibrium value with the influx into the nanoporous solid, microimaging does as well allow the direct determination of surface resistances. Examples illustrating the variety of information thus attainable include the comparison of mass transfer under equilibrium and non-equilibrium conditions, single- and multicomponent diffusion and chemical reactions. They, finally, introduce into the potentials of microimaging for an in-depth study of mass transfer in mixed-matrix membranes. This tutorial review may serve as first introduction into the topic. Further references are linked for the interested reader.