Separation of propylene and propane with a microporous metal–organic framework via equilibrium‐kinetic synergetic effect

Abstract Adsorption separation of olefin and paraffin can greatly lower the energy consumption associated with the currently utilized distillation technique but remains a great challenge. Herein, we report the efficient separation of propylene (C 3 H 6 ) and propane (C 3 H 8 ) in a phosphate anion‐functionalized metal–organic framework (MOF) ZnAtzPO 4 by synergetic effect of equilibrium and kinetics. The material features periodically expanded and contracted apertures decorated with electronegative groups, offering eligible pore shape and pore chemistry to effectively trap C 3 H 6 under moderate isosteric heat of adsorption (27.5 kJ mol −1 ) while obstruct the diffusion of C 3 H 8 . It simultaneously combines excellent thermodynamic selectivity (uptake ratio of 1.71) and kinetic selectivity (~31) for C 3 H 6 /C 3 H 8 separation, meanwhile can be easily regenerated. Breakthrough experiment for C 3 H 6 /C 3 H 8 gas mixture was conducted and confirmed the outstanding separation capability of ZnAtzPO 4 . The equilibrium and kinetics cooperative C 3 H 6 /C 3 H 8 adsorption separation was for the first time found in anion‐functionalized MOFs, and further confirmed by computational studies.