Self‐assembled Metal−Organic Framework Microspheres for Thermodynamic−Kinetic Synergistic Separation of Propylene and Propane^†

Comprehensive Summary Separating propylene (C 3 H 6 ) from propane (C 3 H 8 ) is a complex procedure in the petrochemical sector due to the comparable characteristics of the two gases. Herein, we reported the self‐assembly phenomenon of NbOFFIVE‐1‐Ni (KAUST‐7) crystals under different synthetic routes. The material features a decreased framework strain energy compared to original KAUST‐7 and exhibits completely different adsorption performance, achieving the efficient separation of C 3 H 6 /C 3 H 8 by synergetic effect of equilibrium and kinetics. The C 3 H 6 adsorption capacity was as high as 46.2 cm 3 ·g −1 (298 K, 1 bar), increasing by 53% compared to the original material. The diffusion rates of C 3 H 6 were faster than C 3 H 8 as confirmed by time dependent kinetic adsorption profiles. It concurrently combines an excellent C 3 H 6 /C 3 H 8 uptake ratio of 3.1 and kinetic selectivity (96.5) for C 3 H 6 /C 3 H 8 separation with an equilibrium‐kinetic combined selectivity of 42.5. Meanwhile, it can be regenerated easily due to moderate isosteric heat of adsorption (28.7 kJ·mol −1 ). Breakthrough experiment for C 3 H 6 /C 3 H 8 gas mixture was conducted and confirmed the high‐purity recovery of C 3 H 6 over C 3 H 8 . Moreover, it exhibited excellent water and moisture stability and can be easily synthesized through stirring at room temperature, which confers them with great potential for industrial application.