Efficient Xe/Kr separation on two Metal-Organic frameworks with distinct pore shapes

Adsorptive separation of xenon (Xe) from krypton (Kr) is challenging owing to their low concentrations and similar physical properties. Herein, we report two metal–organic frameworks (MOFs) assembled from the same aliphatic ligand ( trans -1, 4-cyclohexanedicarboxylic acid, H 2 CDC), but showing distinct pore shapes. The rhombus pores on Al-CDC show a narrower pore aperture of 4.5 Å × 6.0 Å, contracting to the pseudo-square pores (5.8 Å × 6.8 Å) on Cu-CDC. As a result, Al-CDC exhibits a high Xe adsorption capacity (2.45 mmol g −1 ) and Xe/Kr selectivity (10.7) at 298 K and 1.0 bar. The confined pore space and abundant saturated C-H groups provide stronger van der Waals interactions toward Xe, which is disclosed by the Grand Canonical Monte Carlo (GCMC) and Density Functional Theory (DFT) calculations. Dynamic breakthrough experiments further confirm their industrial application potential and stable reusability.