Incorporation of Multiple Binding Sites into an Adaptive MOF for Sieving Butane Isomers

Abstract Efficient separation of liner alkanes from branched alkanes is of prime importance in the petrochemical industry. Herein an adaptive metal‐organic framework FJI‐H38 is reported with 1D channel which can vary delicately ≈4.0 Å. The activated FJI‐H38 displays extremely large butane ( n‐ C 4 H 10 ) capacity, especially at low pressure (44.15 cm 3 g −1 at 298 K and 0.1 bar), but barely adsorbs isobutane ( i so‐C 4 H 10 ). Remarkably, FJI‐H38 possesses a high n‐ C 4 H 10 / iso‐ C 4 H 10 selectivity of 246.75. Gas‐loaded single crystal X‐ray analysis and modeling calculation reveal that the synergetic effect of pore confinement and surfaces decorated with uncoordinated carboxyl group plays a critical role in the capture of the relatively smaller n‐ C 4 H 10 while the exclusion of the larger iso‐ C 4 H 10 . In addition, dynamic breakthrough tests explicitly prove FJI‐H38 displays prominent separation performance for n / iso‐ C 4 H 10 under various conditions with ultra‐high productivity of high‐purity n‐ C 4 H 10 (42.48 L/kg, ≥99.0%) and iso‐ C 4 H 10 (42.35 L/kg, ≥99.95%).