Low Evaporation Enthalpy Ionic Covalent Organic Frameworks for Efficient Atmospheric Water Harvesting at Low Humidity

Abstract Herein, we introduce a series of ionic covalent organic frameworks (iCOFs) with a focus on addressing the challenge of water collection at low relative humidity levels below 25 %. These iCOFs are characterized by numerous hydrophilic sites and high water stability, enabling efficient water vapor adsorption even at relatively low humidity levels. Through the use of various hygroscopic salt cations and precise control of ion concentration within the pores, the water state within the iCOFs pores can be effectively managed. Among the iCOFs, TB‐COF‐Li stands out with an impressive adsorption capacity of 0.24 g g −1 from 0 to 22 % RH. Notably, due to its ionic porous structure, TB‐COF‐Li exhibits a significantly lower enthalpy of evaporation, measured at 967.04 J g −1 , compared to bulk water with an enthalpy of 2387.40 J g −1 . Moreover, under simulated conditions of 1.5 solar intensity at 60 °C, the majority of the adsorbed water can be rapidly desorbed without the need for additional energy input. This efficient desorption process contributes to a high water collection rate of 0.092 g g −1 h −1 in the final atmospheric water harvesting device. The development of these iCOFs offers a promising and cost‐effective solution for obtaining fresh water in arid regions.