Customized H-bonding acceptor and aperture chemistry within a metal-organic framework for efficient C3H6/C3H8 separation

Efficient separation of propylene/propane (C 3 H 6 /C 3 H 8 ) is an imperative and extremely challenging process in the petrochemical industry due to their similar physicochemical characters. Known tactics mainly concentrate on unilateral thermodynamic or kinetic driven. Here, we report the efficient separation of C 3 H 6 /C 3 H 8 through cooperative equilibrium-kinetic synergetic effect in a nodes-engineered Zr-MOF scaffold (1to). The grafted -CF 3 motif with different isomers and resultant aperture chemistry awards 1to a late-model paradigm for efficient separation of C 3 H 6 /C 3 H 8 . Detailly, confined -CF 3 group having the role of H-bonding acceptor can result in improved adsorption enthalpy ( Q st ) of 38.1 kJ mol −1 , ideal adsorbed solution theory (IAST) selectivity of 80 and experimental selectivity of 25, respectively, indicating a marked thermodynamic driven for trapping C 3 H 6 . Besides, the contracted cross-sectional size and eligible pore shape of 1to could be judiciously adjusted through rationally engineering the pore microenvironment, yielding a topmost simulated diffusion selectivity of 408, which was 40.8 times higher than that of the pristine 1 example (10), effectively enabling the swift diffusion behavior of C 3 H 6 . Modeling simulations and breakthrough experiments confirmed the excellent C 3 H 6 /C 3 H 8 separation performance of 1to. This work successfully developed a novel nodes-engineered strategy for C 3 H 6 capture through equilibrium-kinetic synergetic effect, anticipating to set a new benchmark for gas separation and affording constructive guidance for tailoring delicate aperture chemistry.