Covalent Triazine-Based Frameworks with Ultramicropores and High Nitrogen Contents for Highly Selective CO2 Capture.

Porous organic frameworks (POFs) are a class of porous materials composed of organic precursors linked by covalent bonds. The objective of this work is to develop POFs with both ultramicropores and high nitrogen contents for CO2 capture. Specifically, two covalent triazine-based frameworks (CTFs) with ultramicropores (pores of width <7 Å) based on short (fumaronitrile, FUM) and wide monomers (1,4-dicyanonaphthalene, DCN) were synthesized. The obtained CTF-FUM and CTF-DCN possess excellent chemical and thermal stability with ultramicropores of 5.2 and 5.4 Å, respectively. In addition, they exhibit excellent ability to selectively capture CO2 due to ultramicroporous nature. Especially, CTF-FUM-350 has the highest nitrogen content (27.64%) and thus the highest CO2 adsorption capacity (57.2 cc/g at 298 K) and selectivities for CO2 over N2 and CH4 (102.4 and 20.5 at 298 K, respectively) among all CTF-FUM and CTF-DCN. More impressively, as far as we know, the CO2/CH4 selectivity is larger than that of all reported CTFs and ranks in top 10 among all reported POFs. Dynamic breakthrough curves indicate that both CTFs could indeed separate gas mixtures of CO2/N2 and CO2/CH4 completely.