Abstract
We designed and synthesized a perfluorinated covalent triazine-based framework (FCTF-1) for selective CO2 capture. The incorporation of fluorine (F) groups played multiple roles in improving the framework's CO2 adsorption and separation capabilities. Thermodynamically, the strongly polar C-F bonds promoted CO2 adsorption via electrostatic interactions, especially at low pressures. FCTF-1's CO2 uptake was 1.76 mmol g(-1) at 273 K and 0.1 bar through equilibrium adsorption, exceeding the CO(2)w adsorption capacity of any reported porous organic polymers to date. In addition, incorporating F groups produced a significant amount of ultra-micropores (<0.5 nm), which offered not only high gas adsorption potential but also kinetic selectivity for CO2-N-2 separation. In mixed-gas breakthrough experiments, FCTF-1 exhibited an exceptional CO2-N-2 selectivity of 77 under kinetic flow conditions, much higher than the selectivity (31) predicted from single-gas equilibrium adsorption data. Moreover, FCTF-1 proved to be tolerant to water and its CO2 capture performance remained excellent when there was moisture in the gas mixture, due to the hydrophobic nature of the C-F bonds. In addition, the moderate adsorbate-adsorbent interaction allowed it to be fully regenerated by pressure swing adsorption processes. These attributes make FCTF-1 a promising sorbent for CO2 capture from flue gas.