Highly stable nanoporous covalent triazine-based frameworks with an adamantane core for carbon dioxide sorption and separation

Abstract

Adamantane substituted with two to four 4-cyanophenyl groups was used for preparation of a new series of robust Porous Covalent Triazine-based Framework (PCTF) materials. Novel adamantane PCTFs were synthesized in good yields (>80%) by the trimerization reaction of 1,3-bis-, 1,3,5-tris- and 1,3,5,7-tetrakis(4-cyanophenyl)adamantane, respectively, in the presence of ZnCl2 (Lewis acid condition) and CF3SO3H (strong Bronsted acid condition). From N2 adsorption isotherms, the Lewis acid condition gives higher surface areas than the strong Bronsted acid condition. The amorphous nano- to microporous frameworks (>50% micropore fraction) exhibit excellent thermal stabilities (>450 °C) with BET surface areas up to 1180 m2 g−1. A very similar ultramicropore size distribution between 4 and 10 A was derived from CO2 adsorption isotherms with a “CO2 on carbon based slit-pore model”. At 1 bar the gases H2 (at 77 K), CO2 (at 273 and 293 K) and CH4 (at 273 K) are adsorbed up to 1.24 wt%, 58 cm3 g−1 and 20 cm3 g−1, respectively. Gas uptake increases with BET surface area and micropore volume which in turn increase with the number of cyano groups in the monomer. From single component adsorption isotherms, IAST-derived ideal CO2:N2, CO2:CH4 and CH4:N2 selectivity values of up to 41 : 1, 7 : 1 and 6 : 1, respectively, are calculated for p → 0 at 273 K. The adamantane PCTFs have isosteric heats of adsorption for CO2 of 25–28 kJ mol−1 at zero loading and most of them also >25 kJ mol−1 over the entire adsorption range which is well above the heat of liquefaction of bulk CO2 or the isosteric enthalpy of adsorption for CO2 on activated carbons.