Heterogeneous Diffusion of Alkanes in the Hierarchical Metal-Organic Framework NU-1000

The metal-organic framework (MOF) NU-1000 is a hierarchical material that comprises both micropores and mesopores in its crystalline structure. Because the pore structure is perfectly defined, NU-1000 is an interesting material for improving our understanding of diffusion in hierarchically structured materials. Here, we present molecular dynamics simulations aimed at probing the transport properties of n-alkanes in NU-1000 and introduce methods from the microrheology literature for analyzing the mean-squared displacements and their spatial heterogeneity. Adsorption occurs initially in the smaller channels, and diffusion at low loading is limited by interaction between adsorbate and framework atoms. The larger channels provide a region of low density where molecules are able to diffuse at higher rates predominantly along the channel axes. The disparate size of the channels gives rise to heterogeneity in the diffusivity of the guest molecules, whereas the asymmetry of the channels leads to anisotropic diffusion. Together, the channels form a network of "highways" and "side streets" that provide enhanced diffusion in one dimension.