Tuning of Microenvironment in Covalent Organic Framework via Fluorination Strategy promotes Selective CO2 Capture.

Abstract

Herein, we have designed and synthesized two heteroatom (N, O) rich covalent organic frameworks (COF), PD-COF and TF-COF, respectively, to demonstrate their relative effect on CO2adsorption capacity and also CO2/N2 selectivity. Compared to the non-fluorinated PD-COF (BET surface area 805 m2g-1, total pore volume 0.3647 ccg-1), a decrease in BET surface area and also pore volume have been observed for fluorinated TF-COF due to the incorporation of fluorine to the porous framework (BET surface area 451 m2g-1, total pore volume 0.2978 ccg-1). This fact leads to an enormous decrease in the CO2adsorption capacity and CO2/N2 selectivity of TF-COF, though it shows stronger affinity towards CO2 with a Qst of 37.76 KJ/mol. The more CO2 adsorption capacity by PD-COF can be attributed to the large specific surface area with considerable amount of micropore volume compared to the TF-COF. Further, PD-COF exhibited CO2/N2 selectivity of 16.8, higher than that of TF-COF (CO2/N2 selectivity 13.4).