Ultramicroporous Metal–Organic Framework Featuring Multiple Polar Sites for Efficient Xenon Capture and Xe/Kr Separation

Efficient adsorption separation of xenon/krypton (Xe/Kr) mixtures is an important technological challenge due to their similar sizes and shapes. Herein, we report an ultramicroporous metal-organic framework (MOF), ZJU-Bao-302a, with pore sizes close to the kinetic diameter of Xe and pore surfaces lined with a high density of polar sites, including methyl groups, amines, and uncoordinated oxygen atoms. The synergistic effect of these polar sites enables ZJU-Bao-302a to exhibit a high Xe uptake of 2.77 mmol g^-1 and a balanced Xe/Kr selectivity of 14.6 under ambient conditions. Dynamic breakthrough experiments demonstrate the material's capability to efficiently separate Xe/Kr mixtures (20/80) as well as capture Xe at ultralow concentrations (400 ppmv) from nuclear reprocessing exhausts, achieving a superior dynamic Xe capacity of 24.2 mmol kg^-1. Density functional theory calculations reveal that the localized polar groups/atoms in ZJU-Bao-302a provide more effective recognition sites for Xe than Kr, enhancing the thermodynamic selectivity. This study highlights the importance of integrating tailored pore sizes and dense polar sites in metal-organic frameworks for developing high-performance Xe/Kr separation adsorbents.