Reverse Hierarchy of Alkane Adsorption in Metal–Organic Frameworks (MOFs) Revealed by Immersion Calorimetry

Immersion calorimetry into liquids of different dimensions is a powerful tool to learn about the pore size and shape in nanoporous solids. In general, in the absence of specific interactions with the solid surface, the accessibility of the liquid probe molecule to the inner porosity and the associated enthalpy value decreases with an increase in its kinetic diameter (bulkier molecules have lower accessibility and packing density). Although this is true for the majority of solids (e.g., activated carbons and zeolites), this study anticipates that this is not straightforward in the specific case of metal–organic frameworks (MOFs). The evaluation of different hydrocarbons and their derivatives reveals the presence of reverse selectivity for C₆ isomers (2,2-dimethylbutane > 2-methylpentane > n-hexane) in UiO-66 and HKUST-1, whereas size exclusion effects take place in ZIF-8. The immersion calorimetric findings have been compared with vapor adsorption isotherms and computational studies. Monte Carlo simulations suggest that the reverse selectivity in UiO-66 is attributed to the strong confinement of the dibranched hydrocarbons in the small tetragonal cages, whereas the presence of strong interactions with the open metal sites accounts for the preferential adsorption in HKUST-1. These results open the gate toward the application of immersion calorimetry for the prescreening of MOFs to identify in an easy, fast and reliable way interesting characteristics and/or properties such as separation ability, reversed hierarchy, pore-window size, presence of unsaturated metal sites, molecular accessibility, and so on.