Tunable Water and CO2 Sorption Properties in Isostructural Azine-Based Covalent Organic Frameworks through Polarity Engineering

Abstract

The use of covalent organic frameworks (COFs) in environmental settings such as atmospheric water capture or CO2 separation under realistic pre- and post-combustion conditions is largely unexplored to date. Herein, we present two isostructural azine-linked COFs based on 1,3,5-triformyl benzene (AB-COF) and 1,3,5-triformylphloroglucinol (ATFG-COF) and hydrazine building units, respectively, whose sorption characteristics are precisely tunable by the rational design of the chemical nature of the pore walls. This effect is particularly pronounced for atmospheric water harvesting, which is explored for the first time using COFs as adsorbents. We demonstrate that the less polar AB-COF acts as a reversible water capture and release reservoir, featuring among the highest water vapor uptake capacity at low pressures reported to date (28 wt % at <0.3 p p0−1). Furthermore, we show tailored CO2 sorption characteristics of the COFs through polarity engineering, demonstrating high CO2 uptake at low pressures ( <1 bar)...