Hydrocarbon Sorption in Flexible MOFs—Part III: Modulation of Gas Separation Mechanisms

Single gas sorption experiments with the C4-hydrocarbons n -butane, iso -butane, 1-butene and iso -butene on the flexible MOFs Cu-IHMe-pw and Cu-IHEt-pw were carried out with both thermodynamic equilibrium and overall sorption kinetics. Subsequent static binary gas mixture experiments of n -butane and iso -butane unveil a complex dependence of the overall selectivity on sorption enthalpy, rate of structural transition as well as steric effects. A thermodynamic separation favoring iso -butane as well as kinetic separation favoring n -butane are possible within Cu-IHMe-pw while complete size exclusion of iso -butane is achieved in Cu-IHEt-pw. This proof-of-concept study shows that the structural flexibility offers additional levers for the precise modulation of the separation mechanisms for complex mixtures with similar chemical and physical properties with real selectivities of >10.