Decorating the Node of a Zirconium-Based Metal–Organic Framework to Tune Adsorption Behavior and Surface Permeation

Surface barriers are commonly observed in nanoporous materials. Although researchers have explored methods to repair defects or create flawless crystals to mitigate surface barriers, these approaches may not always be practical or readily achievable in targeted metal–organic frameworks (MOFs). In our study, we propose an alternative approach focusing on the introduction of diverse ligands onto a MOF-808 node to finely adjust its adsorption and mass transport characteristics. Significantly, our findings indicate that while adsorption curves can be inferred based on the MOF’s chemical composition and the probing molecule, surface permeabilities exhibit variations dependent on the specific probe utilized and the incorporated ligand. Our investigation, considering van der Waals forces exclusively between the adsorbate (e.g., n -hexane, propane, and benzene) and the adsorbent, revealed that augmenting these interactions can indeed improve surface permeation to a certain extent. Conversely, strong adsorption resulting from hydrogen bonding interactions, particularly with water in modified MOFs, led to compromised permeation within the MOF crystals. These outcomes provide valuable insights for the porous materials community and offer guidance in the development of adsorbents with enhanced affinity and superior mass transport properties for gases and vapors.