Understanding the role of open metal sites in MOFs for the efficient separation of benzene/cyclohexane mixtures

Separating C6 cyclic hydrocarbons, specifically benzene and cyclohexane, presents a significant industrial challenge due to their similar physicochemical properties. We conducted Monte Carlo simulations in the Grand-Canonical ensemble to acquire adsorption properties and separation performance data for benzene and cyclohexane in three metal–organic frameworks featuring coordinatively unsaturated metal sites (Ni-MOF-74, Ni-ClBBTA, and Ni-ClBTDD). The separation performance of these MOFs was analyzed and compared with literature data for adsorbents of different natures, demonstrating superior performance. Additionally, we explored the molecular origins of this effective separation, examining the pore-filling mechanism, interaction of guest molecules with metal centers, and mutual interactions of each adsorbate. Our results highlight that the selected adsorbents, with remarkable loading capacity, can efficiently separate both compounds in a mixture with exceptional effectiveness.