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 (C3H6) and propane (C3H8) in a phosphate anion‐functionalized metal–organic framework (MOF) ZnAtzPO4 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 C3H6 under moderate isosteric heat of adsorption (27.5 kJ mol−1) while obstruct the diffusion of C3H8. It simultaneously combines excellent thermodynamic selectivity (uptake ratio of 1.71) and kinetic selectivity (~31) for C3H6/C3H8 separation, meanwhile can be easily regenerated. Breakthrough experiment for C3H6/C3H8 gas mixture was conducted and confirmed the outstanding separation capability of ZnAtzPO4. The equilibrium and kinetics cooperative C3H6/C3H8 adsorption separation was for the first time found in anion‐functionalized MOFs, and further confirmed by computational studies.