Increasing demands in the field of sensing, especially for gas detection applications, require new approaches to chemical sensors. Metal–organic frameworks (MOFs) can play a decisive role owing to their outstanding performances regarding gas selectivity and sensitivity. The tetrathiafulvalene (TTF)-infiltrated MOF, Co-MOF-74, has been prepared following the host–guest concept and evaluated in resistive gas sensing. The Co-MOF-74-TTF crystal morphology has been characterized via X-ray diffraction and scanning electron microscopy, while the successful incorporation of TTF into the MOF has been validated via X-ray photoemission spectroscopy, thermogravimetric analysis, UV/vis, infrared (IR), and Raman investigations. We demonstrate a reduced yet ample uptake of CO2 in the pores of the new material by IR imaging and adsorption isotherms. The nanocomposite Co-MOF-74-TTF exhibits an increased electrical conductivity in comparison to Co-MOF-74 which can be influenced by gas adsorption from a surrounding atmosphere. This effect could be used for gas sensing.
Labeling in diffusion measurements by pulsed field gradient (PFG) NMR is based on the observation of the phase of nuclear spins acquired in a constant magnetic field with purposefully superimposed field gradients. This labeling does in no way affect microdynamics and provides information about the probability distribution of molecular displacements as a function of time. An introduction of the measuring principle is followed by a detailed description of the ranges of measurements and their limitation. Particular emphasis is given to an explanation of possible pitfalls in the measurements and the ways to circumvent them. Showcases presented for illustrating the wealth of information provided by PFG NMR include a survey on the various patterns of concentration dependence of intra-particle diffusion and examples of transport inhibition by additional transport resistances within the nanoporous particles and on their external surface. The latter information is attained by combination with the outcome of tracer exchange experiments, which are shown to become possible via a special formalism of PFG NMR data analysis. Further evidence provided by PFG NMR concerns diffusion enhancement in pore hierarchies, diffusion anisotropy and the impact of diffusion on chemical conversion in porous catalysts. A compilation of the specifics of PFG NMR and of the parallels with other measurement techniques concludes the paper.
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.
Through IR microimaging the spatially and temporally resolved development of the CO concentration in a ZIF-8@6FDA-DAM mixed matrix membrane (MMM) was visualized during transient adsorption. By recording the evolution of the CO concentration, it is observed that the CO molecules propagate from the ZIF-8 filler, which acts as a transport "highway", towards the surrounding polymer. A high-CO -concentration layer is formed at the MOF/polymer interface, which becomes more pronounced at higher CO gas pressures. A microscopic explanation of the origins of this phenomenon is suggested by means of molecular modeling. By applying a computational methodology combining quantum and force-field based calculations, the formation of microvoids at the MOF/polymer interface is predicted. Grand canonical Monte Carlo simulations further demonstrate that CO tends to preferentially reside in these microvoids, which is expected to facilitate CO accumulation at the interface.
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.
Measurement of molecular diffusion in nanoporous host materials, which are typically inhomogeneous and anisotropic, often involves an intricate web of factors and relations to be taken into account since the associated diffusivities are a function of the diffusion path of the guest molecules during a given observation time. Depending on the observation time, therefore, the result of the experimental measurement can point to completely different conclusions about the underlying diffusion phenomena. The risk of misinterpretation of the experimental data, by correlating them with irrelevant phenomena, may be reduced if there is an option to compare the data with the results of totally independent measurements. The present communication addresses this issue with reference to the particular potentials of pulsed field gradient NMR and microimaging by infrared microscopy as techniques of microscopic diffusion measurement.
The two-region (“Kärger”) model of diffusion in complex pore spaces is exploited for quantitating mass transfer in hierarchically organized nanoporous materials, consisting of a continuous microporous bulk phase permeated by a network of transport pores. With the implications that the diffusivity in the transport pores significantly exceeds the diffusivity in the micropores and that the relative population of the transport pores is far below that of the micropores, overall transport depends on only three independent parameters. Depending on their interrelation, enhancement of the overall mass transfer is found to be ensured by two fundamentally different mechanisms. They are referred to as the limiting cases of fast and slow exchange, with the respective time constants of molecular uptake being controlled by different parameters. Complemented with reaction terms, the two-region model may equally successfully be applied to the quantitation of the combined effect of diffusion and reaction in terms of the effectiveness factor. Generalization of the classical Thiele concept is shown to provide an excellent estimate of the effectiveness factor of a chemical reaction in hierarchically porous materials, solely based on the intrinsic reaction rate and the time constant of molecular uptake relevant to the given conditions.
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