Fabrication of Pillar‐Cage Fluorinated Anion Pillared Metal–Organic Frameworks via a Pillar Embedding Strategy and Efficient Separation of SO2 through Multi‐Site Trapping

Flue gas desulfurization is crucial for both human health and ecological environments. However, developing efficient SO2 adsorbents that can break the trade‐off between adsorption capacity and selectivity is still challenging. In this work, a new type of fluorinated anion‐pillared metal–organic frameworks (APMOFs) with a pillar‐cage structure is fabricated through pillar‐embedding into a highly porous and robust framework. This type of APMOFs comprises smaller tetrahedral cages and larger icosahedral cages interconnected by embedded [NbOF5]2− and [TaOF5]2− anions acting as pillars. The APMOFs exhibits high porosity and density of fluorinated anions, ensuring exceptional SO2 adsorption capacity and ultrahigh selectivity for SO2/CO2 and SO2/N2 gas mixtures. Furthermore, these two structures demonstrate excellent stability towards water, acid/alkali, and SO2 adsorption. Cycle dynamic breakthrough experiments confirm the excellent separation performance of SO2/CO2 gas mixtures and their cyclic stability. SO2‐loaded single‐crystal X‐ray diffraction, Grand canonical Monte Carlo (GCMC) simulations combined with density functional theory (DFT) calculations reveal the preferred adsorption domains for SO2 molecules. The multiple‐site host–guest and guest‐guest interactions facilitate selective recognition and dense packing of SO2 in this hybrid porous material. This work will be instructive for designing porous materials for flue gas desulfurization and other gas‐purification processes. Pillar‐cage fluorinated metal‐organic frameworks were fabricated via a pillar embedding strategy and applied in the efficient separation of SO2 through multi‐site trapping.