Optimized Pore Nanospace through the Construction of a Cagelike Metal-Organic Framework for CO₂/N₂ Separation

The development of metal-organic framework (MOF) adsorbents with a potential molecule sieving effect for CO₂ capture and separation from flue gas is of critical importance for reducing the CO₂ emissions to the atmosphere yet challenging. Herein, a cagelike MOF with a suitable cage window size falling between CO₂ and N₂ and the cavity has been constructed to evaluate its CO₂/N₂ separation performance. It is noteworthy that the introduction of coordinated dimethylamine (DMA) and N,N'-dimethylformamide (DMF) molecules not only significantly reduces the cage window size but also enhances the framework-CO₂ interaction via C-H···O hydrogen bonds, as proven by molecular modeling, thus leading to an improved CO₂ separation performance. Moreover, transient breakthrough experiments corroborate the efficient CO₂/N₂ separation, revealing that the introduction of DMA and DMF molecules plays a vital role in the separation of a CO₂/N₂ gas mixture.