Construction of a Fluorinated-Anion Pillared Metal-Organic Framework Exhibiting Dual-Pore Architecture for...

Physisorption-based separation processes represents a promising alternative to the conventional thermally driven methods, such as cryogenic separation. However, a significant challenge lies in balancing the trade-off between adsorption capacity and selectivity of adsorbents. In this study, we introduce a novel fluorinated-anion pillared metal-organic frameworks (APMOFs) featuring a dual-pore architecture, constructed using a pyridine-oxazole bifunctional ligand. The inherent low symmetry of the ligand leads to significant distortion of the fluorinated-anion pillars, resulting in a distinctive type of APMOFs characterized by dual-pore architecture. On pore structure with constrict pore width is enriched with a high density of anion fluorinated pillars, offering numerous active sites advantageous for enhancing separation selectivity. Concurrently, the other pore structure exhibits larger dimensions, facilitating increased gas molecule accommodation and thereby augmenting adsorption capacity. Gas sorption studies reveal a substantial C₂H₂ adsorption capacity and a high C₂H₂/CO₂ separation selectivity. Breakthrough experiments confirm its exceptional separation performance, while theoretical investigations elucidate a sequential adsorption process within these APMOFs, underscoring the efficacy of this strategy in overcoming trade-off limits in adsorbents.