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Mass transfer of toluene in a series of metal-organic frameworks: molecular clusters inside the nanopores cause slow and step-like release.

The mass transfer of the guest molecules in the pores is fundamental for the application of nanoporous materials like metal-organic frameworks, MOFs. In the present work, we explore the uptake and release of toluene in a series of Zr-based MOFs with different pore sizes. We find that intermolecular guest-guest interaction, sterically controlled by the pore size, has a substantial impact on the release kinetics. While the adsorption is rather fast, the desorption process is many orders of magnitude slower. Depending on the pore size, molecular clusters form, here (most likely) toluene dimers, which are rather stable and their break-up is rate-limiting during the desorption process. This results in a step-like desorption kinetics, deviating from the plain Fickian-diffusion-controlled release. Temperature-dependent experiments show that the minimum and maximum of the release rates are obtained at the same toluene loadings, independent of the temperature. Moreover, the activation energy for the release coincides with the binding energy of a toluene dimer. The work shows the importance of intermolecular guest-guest interaction, controlled by the MOF-nanoconfinement, for the uptake and release from nanoporous materials.