Miguel I. Gonzalez, Douglas A. Reed, Matthew T. Kapelewski, Jonathan E. Bachman, Jeffrey R. Long
The metal–organic frameworks M2(m-dobdc) (M = Mn, Fe, Co, Ni; m-dobdc4– = 4,6-dioxido-1,3-benzenedicarboxylate) were evaluated as adsorbents for separating olefins from paraffins. Using single-component and multicomponent equilibrium gas adsorption measurements, we show that the coordinatively unsaturated M2+ sites in these materials lead to superior performance for the physisorptive separation of ethylene from ethane and propylene from propane relative to any known adsorbent, including para-functionalized structural isomers of the type M2(p-dobdc) (p-dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate). Notably, the M2(m-dobdc) frameworks all exhibit an increased affinity for olefins over paraffins relative to their corresponding structural isomers, with the Fe, Co, and Ni variants showing more than double the selectivity. Among these frameworks, Fe2(m-dobdc) displays the highest ethylene/ethane (>25) and propylene/propane (>55) selectivity under relevant conditions, together with olefin capacities exceeding 7 mmol/g. Differential enthalpy calculations in conjunction with structural characterization of ethylene binding in Co2(m-dobdc) and Co2(p-dobdc) via in situ single-crystal X-ray diffraction reveal that the vast improvement in selectivity arises from enhanced metal–olefin interactions induced by increased charge density at the metal site. Moderate olefin binding enthalpies, below 55 and 70 kJ/mol for ethylene and propylene, respectively, indicate that these adsorbents maintain sufficient reversibility under mild regeneration conditions. Additionally, transient adsorption experiments show fast kinetics, with more than 90% of ethylene adsorption occurring within 30 s after dosing. Breakthrough measurements further indicate that Co2(m-dobdc) can produce high purity olefins without a temperature swing, an important test of process applicability. The excellent olefin/paraffin selectivity, high olefin capacity, rapid adsorption kinetics, and low raw materials cost make the M2(m-dobdc) frameworks the materials of choice for adsorptive olefin/paraffin separations.