A scalable microporous metal–organic framework with symmetric amino clamp sites for efficient Xe/Kr separation

Efficient Xe/Kr separation remains a formidable challenge because of their striking molecular similarity, despite its importance for high‐purity Xe production and nuclear off‐gas treatment. Here we report a scalable microporous metal–organic framework, Zn(MA)(TDC) 2 , that undergoes activation‐triggered pore‐surface reconstruction through inward reorientation of coordinated melamine ligands, thereby generating a more nitrogen‐rich confined binding environment for Xe recognition. Single‐crystal X‐ray diffraction reveals that this reconfigured pore hosts a symmetry‐defined dual‐Xe adsorption motif with a local constriction well matched to Xe, resulting in a high Xe uptake of 103.7 cm 3 g −1 and a Xe/Kr uptake ratio of 4.1 at 298 K and 1 bar, while breakthrough measurements confirm effective Xe capture from both air‐relevant and nuclear off‐gas‐mimicking streams at trace partial pressures. Combined with its moderate Xe adsorption enthalpy, facile regeneration, and robust cycling stability, this work highlights pore‐surface reconfiguration as an effective strategy for energy‐efficient noble‐gas separations.