Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal–Organic Frameworks toward CO2/N2Separation

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal–organic frameworks (Co-MOFs), namely, {[Co3(NTB)2(bib)]·(DMA)2·(H2O)4}n(DZU-211) and {[Co3(NTB)2(bmip)]·(DMA)2}n(DZU-212) (H3NTB = 4,4′,4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane) to realize efficient CO2/N2separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure. The two MOFs both possess large coordination spaces and small open pore sizes, via the bib ligand insertion and framework interpenetration, respectively. Comparatively, DZU-211 reveals superior selective CO2uptake properties due to its more suitable pore characteristics. Gas sorption experiments show that DZU-211 has a CO2uptake of 52.6 cm3g–1with a high simulated CO2/N2selectivity of 101.7 (298 K, 1 atm) and a moderate initial adsorption heat of 38.1 kJ mol–1. Moreover, dynamic breakthrough experiments confirm the potential application of DZU-211 as a CO2separation material from postcombustion flue gases.