Breaking the trade-off between selectivity and adsorption capacity for gas separation

The trade-off between selectivity and adsorption capacity with porous materials is a major roadblock to reducing the energy footprint of gas separation technologies. To address this matter, we report herein a systematic crystal engineering study of C₂H₂ removal from CO₂ in a family of hybrid ultramicroporous materials (HUMs). The HUMs are composed of the same organic linker ligand, 4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, pypz, three inorganic pillar ligands, and two metal cations, thereby affording six isostructural pcu topology HUMs. All six HUMs exhibited strong binding sites for C₂H₂ and weaker affinity for CO₂. The tuning of pore size and chemistry enabled by crystal engineering resulted in benchmark C₂H₂/CO₂ separation performance. Fixed-bed dynamic column breakthrough experiments for an equimolar (v/v = 1:1) C₂H₂/CO₂ binary gas mixture revealed that one sorbent, SIFSIX-21-Ni, was the first C₂H₂ selective sorbent that combines exceptional separation selectivity (27.7) with high adsorption capacity (4 mmol·g^-1).