Pore Chemistry and Architecture Control in Anionic Functional Ultramicroporous Materials for Record Dense Packing of Xenon

Adsorptive separation of Xe and Kr is an industrially promising but challenging process because of their identical shape and similar physicochemical properties. Herein, we demonstrate a strategy through rationally designing the linkers of anionic functional ultramicroporous materials (FUMs) to finely regulate the pore chemistry and architecture, which creates unique stepped channels incorporating dense polar nanotraps to generate a larger effective pore space and enables dense packing of Xe. A new hydrolytically stable FUM (ZUL-530) was prepared, which for the first time achieves a Xe packing density exceeding the liquid Xe density at atmospheric conditions in metal−organic frameworks (MOFs) (based on experimental data), resulting in both excellent Xe uptake (2.55 mmol g–1 at 0.2 bar) and high IAST selectivity (20.5). GCMC and DFT-D calculations reveal the essential role of the stepped traps in the dense packing of Xe. Breakthrough experiments demonstrate remarkable productivities of both high-purity Kr (6.70 mmol g–1) and Xe (1.78 mmol g–1) for the Xe/Kr (20:80) mixture. In a model nuclear industry exhaust gas, ZUL-530 exhibits a top-class Xe dynamic capacity (28.8 mmol kg–1) for trace Xe, which proves it is one of the best candidates for Xe/Kr separation.