The pore size of adsorbents plays a vital role in determining the overall separation performance of gas separation and purification by adsorption. In this work, the pore apertures of the coordination pillared layer (CPL) was systematically controlled by adjusting the length of pillared ligands. We used pyrazine, 4,4′-bipyridine, and 1,2-di(4-pyridyl)-ethylene with increased length to synthesize CPL-1 (L = pyrazine), CPL-2 (L = 4,4′-bipyridine), and CPL-5 [L = 1,2-di(4-pyridyl)-ethylene], respectively. The aperture size of these CPLs varies from 4 to 11 Å: CPL-1 (4 × 6 Å 2 ), CPL-2 (9 × 6 Å 2 ), and CPL-5 (11 × 6 Å 2 ). Among the three frameworks, CPL-2 exhibits the highest C 2 H 2 uptake at ambient conditions as it has moderate pore size and porosity. However, CPL-1 has the best separation performance in the breakthrough experiments with binary gas mixture of C 2 H 2 /C 2 H 4 , thanks to the optimal pore size nearly excluding C 2 H 4 , which is only observed in the state-of-the-art UTSA-300a so far. The DFT calculations were carried out to elucidate the specific adsorption sites for both acetylene and ethylene among these frameworks. The modeling results suggest that binding strength is highly related to aperture size and that CPL-1 shows the highest adsorption selectivity owing to the optimal pore size. This work demonstrates that engineering pore size enables us to fabricate the highly efficient metal−organic framework (MOF)-based adsorbents for specific gas separation on the basis of the isoreticular chemistry.
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