Separation Of Xenon And Krypton In The Metal-Organic Frameworks M-2(M-Dobdc) (M=Co, Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal-organic frameworks M-2(m-dobdc) (M=Co, Ni; m-dobdc(4-)=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M2+ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M2+ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M-2(m-dobdc) materials in the adsorptive separation of Xe and Kr.