Integrating Self-Partitioned Pore Space and Amine Functionality into an Aromatic-Rich Coordination Framework with Ph...

A great demand for high-purity C₂ hydrocarbons calls for the development of chemically stable porous materials for the effective isolation of C₂ hydrocarbons from CH₄ and CO₂. However, such separations are challenged by their similar physiochemical parameters and have not been systematically studied to date. In this work, we reported a cadmium-based rod-packing coordination framework compound ZJNU-140 of a new 5,6,7-c topology built up from a custom-designed tricarboxylate ligand. The metal-organic framework (MOF) features an aromatic-abundant pore surface, uncoordinated amine functionality, and self-partitioned pore space of suitable size. These structural characteristics act synergistically to provide the MOF with both selective recognition ability and the confinement effect toward C₂ hydrocarbons. As a result, the MOF displays promising potential for adsorptive separation of C₂-CH₄ and C₂-CO₂ mixtures. The IAST-predicted C₂/CH₄ and C₂/CO₂ adsorption selectivities, respectively, fall in the ranges of 7.3-10.2 and 2.1-2.9 at 298 K and 109 kPa. The real separation performance was also confirmed by dynamic breakthrough experiments. In addition, the MOF can maintain skeleton intactness in aqueous solutions with a wide pH range of 3-11, as confirmed by powder X-ray diffraction (PXRD) and isotherm measurements, showing no loss of framework integrity and porosity. The excellent hydrostability, considerable uptake capacity, impressive adsorption selectivity, and mild regeneration make ZJNU-140 a promising adsorbent material applied for the separation and purification of C₂ hydrocarbons.