Simulating Enhanced Methane Deliverable Capacity of Guest Responsive Pores in Intrinsically Flexible MOFs

A novel computational procedure, based on the principles of flat-histogram Monte Carlo, is developed for facile prediction of the adsorption thermodynamics of intrinsically flexible adsorbents. We then demonstrate how an accurate prediction of methane deliverable capacity in a metal–organic framework (MOF) with significant intrinsic flexibility requires use of such a method. Dynamic side chains in the framework respond to methane adsorbates and reorganize to exhibit a more conducive pore space at high adsorbate densities while simultaneously providing a less conducive pore space at low adsorbate densities. This “responsive pore” MOF achieves ∼20% higher deliverable capacity than if the framework were rigid and elucidates a strategy for designing high deliverable capacity MOFs in the future.