Exploring the effect of molecular size and framework functionalisation on transport in metal-organic frameworks using pulsed-field gradient nuclear magnetic resonance

Molecular transport is an important aspect in metal-organic frameworks (MOFs) as it affects many of their applications, such as adsorption/separation, drug delivery and catalysis. Yet probing the fundamental diffusion mechanisms in MOFs is challenging, and the interplay between the MOF's features (such as the pore structure and linker dynamics) and molecular transport remains mostly unexplored. Here, the pulsed-field gradient nuclear magnetic resonance (PFG NMR) technique is used to probe the diffusion of several probe molecules, i.e., water, xylenes and 1,3,5-triisopropylbenzene (TIPB), within the UiO-66 MOF and its derivatives (UiO-66NH2 and UiO-66Br). Exploiting differences in the size of probe molecules we were able to probe the diffusion rate selectively in the different pore environments of the MOFs. In particular, when relatively small molecules, such as water and small hydrocarbons, were used as probes, the PFG NMR log attenuation plots were non-linear with two distinctive diffusion regions, suggesting faster diffusion in the inter-crystalline space and slower diffusion within crystal aggregates, the latter occurring mostly inside the framework of the MOFs. Conversely, experiments with a larger probe molecule, i.e., TIPB, with a kinetic diameter of 0.95 nm, which makes it unable to access the framework windows of the MOF crystals, showed linear PFG NMR log attenuation plots, which indicates diffusion occurring in a single environment, most likely in the inter-crystalline space. Analysis of the apparent tortuosity values of the systems under investigation highlights the role of linker functionalisation in influencing the molecular diffusion of the probe molecules, which affects both intra-molecular interactions and pore accessibility within the MOF crystals. The findings of this work demonstrate that the diffusion behaviour of probe molecules within MOFs is influenced by the pore size, structure, functionalisation of the MOF linker and molecular interactions. Our study contributes to further advance the understanding of mass transport in MOFs by PFG NMR and provides insights that can inform the design and optimisation of MOF-based materials for various applications.