Interplay of Tri- And Bidentate Linkers to Evolve Micropore Environment in a Family of Quasi-3D and 3D Porous Coordination Polymers for Highly Selective CO₂ Capture

In the design and construction of porous materials, these with exceptional structure and composition are often highly expected, as they may offer unique nanopore space for desired applications. Here, a new family of quasi-3D and a 3D porous coordination polymers (PCPs) (termed NTU-43 to NTU-50) were constructed via an evolution strategy from a layered structure (termed NTU-42). Single gas adsorption isotherms of CO₂, N₂, and CH₄ display the dependency of gas capacity on optimized effects of pore size, functionality, and charged framework of these quasi-3D PCPs, where NTU-45 and NTU-46, the two with NH₂-BDC and OH-BDC bidentate linkers (NH₂-BDC = 2-aminoterephthalic acid and OH-BDC = 2-hydroxyterephthalic acid) have demonstrated outstanding ability for selective CO₂ uptake. To the best of our knowledge, this is the first time to well explore the synergistic effects toward gas adsorption on a platform of quasi-3D frameworks. More importantly, the efficient CO₂ capture from CO₂/CH₄ and CO₂/N₂ mixtures has been also validated by breakthrough experiments under continuous and dynamic conditions at 298 K.