Hydrogen‐Bonded Metal–Nucleobase Frameworks for Efficient Separation of Xenon and Krypton

Xe/Kr separation is an industrially important but challenging process owing to their inert properties and low concentrations in the air. Energy-effective adsorption-based separation is a promising technology. Herein, two isostructural hydrogen-bonded metal-nucleobase frameworks (HOF-ZJU-201 and HOF-ZJU-202) are capable of separating Xe/Kr under ambient conditions and strike an excellent balance between capacity and selectivity. The Xe capacity of HOF-ZJU-201a reaches 3.01 mmol g^-1 at 298 K and 1.0 bar, while IAST selectivity and Henry's selectivity are 21.0 and 21.6, respectively. Direct breakthrough experiments confirmed the excellent separation performance, affording a Xe capacity of 25.8 mmol kg^-1 from a Xe/Kr mixed-gas at dilute concentrations. Density functional theory calculations revealed that the selective binding arises from the enhanced polarization in the confined electric field produced by the electron-rich anions and the electron-deficient purine heterocyclic rings.