Adenine-based metal–organic framework with 1 D narrow channel for molecular-sieving separation of n-butane and isobutane

Molecular-sieving separation of isomeric C4 paraffins, n-butane (n-C4H10) and isobutane (iso-C4H10), is highly desired but challenging because of their very close molecular sizes and physical properties. However, most of the MOF adsorbents often undergo framework flexibility or ligand rotation or swing, leading to the variation of pore size and the loss of the molecular-sieving effect. In this work, an adenine-based MOF with a suitable window size and rigid narrow 1D channel, namely IPM-101, was selected for n-C4H10/iso-C4H10 separation. Adsorption experiments demonstrate that IPM-101 can sensitively adsorb n-C4H10 in the low-pressure region (0–0.05 bar) and reach a saturation state at 0.1 bar while iso-C4H10 is excluded by the size-exclusion effect. Owing to the high porosity, IPM-101 exhibits a high n-C4H10 adsorption capacity (51.6 cm3 g−1) at 1 bar and 298 K. Density functional theory (DFT) calculations clearly reveal the molecular-sieving mechanism that n-C4H10 molecule can diffuse into the pore channel of IPM-101 easily but the diffusion of iso-C4H10 in IPM-101 is kinetically forbidden for its high diffusion energy barrier. The breakthrough experiments show that n-C4H10 and iso-C4H10 can be efficiently separated and iso-C4H10 with a purity of up to 99.9 % can be directly collected. The regeneration experiments show that IPM-101 has good cycling stability for n-C4H10 adsorption and n-C4H10/iso-C4H10 separation. Therefore, the high separation efficiency, excellent regeneration ability, and low cost indicate that IPM-101 has great application potential for practical n-C4H10/ iso-C4H10 separation in industry.