Reversing Benzene/Cyclohexane Selectivity through Varying Supramolecular Interactions Using Aliphatic, Isoreticular MOFs

Effective solid-state adsorbent materials, such as metal organic frameworks (MOFs), rely upon tailored void spaces for selective adsorption of one component from a mixture. This is particularly crucial when separating challenging mixtures such as benzene (Bz) and cyclohexane (Cy) requiring a highly expensive and energy intensive process. Employing bulky "3D-linkers" to construct MOFs leads to materials with unique, contoured pore shapes which consequently allow for significant control over guest adsorption preferences. Investigation into these selectivity preferences is key to identifying suitable materials for industrial separations and is an area currently underexplored. Here, we provide an in-depth investigation exploring the selectivity path between planar and 3D-linkers and their preference to adsorb either Cy or Bz. To validate this principle, the adsorption selectivity of Cy and Bz in 3DL-MOF-1 ([Zn4O(pdc)3] (pdc = bicylo[1.1.1]pentane-1,3-dicarboxylate), CUB-5, and MOF-5 was explored. MOF-5 exhibits a selective preference for Cy adsorption at low pressures, contrary to popular belief, while CUB-5 and 3DL-MOF-1 are Bz selective. DFT-D3 calculations and breakthrough simulations explore this behavior and highlight CUB-5 and MOF-5 as strong candidates for future separation materials.