Reversed CO2/C2H2 separation with ultrahigh carbon dioxide adsorption capacity in Zn-based pillared metal-organic frameworks

The removal of CO2 impurities from CO2/C2H2 gas mixtures to obtain high-purity acetylene used for manufacturing of various commodity chemicals, is very important for the chemical purifying of acetylene. However, CO2 and C2H2 exhibit analogous physical properties as well as molecular sizes causing their separation to become an industrially challenging process, and developing energy-efficient CO2-selective adsorbents is a class of materials of vast value. In this work, a pillared-layer ultramicroporous metal-organic framework (MOF) constructed from zinc (II) and triazolium planar layers with oxalic acid, which has been termed as CALF-20, can preferentially absorb CO2 from C2H2. Unique pore environment and electrostatic effects enable this material foremost capture CO2. CALF-20 shows higher affinities towards CO2 than C2H2 based on heats of adsorption computed from single-component adsorption isotherms. Grand Canonical Monte Carlo simulations confirm the affinity interactions and multiple host-guest interactions between CO2 and CALF-20. Sorption experiments revealed that CALF-20 has excellent trapping volume with extremely high CO2 uptake capacity (140.2 cm(3) cm(-3)).