Covalent organic
frameworks (COFs) have emerged as functional materials
for various potential applications. However, the availability of three-dimensional
(3D) COFs is still limited, and nearly all of them exhibit neutral
porous skeletons. Here we report a general strategy to design porous
positively charged 3D ionic COFs by incorporation of cationic monomers
in the framework. The obtained 3D COFs are built of 3-fold interpenetrated
diamond net and show impressive surface area and CO2 uptakes.
The ion-exchange ability of 3D ionic COFs has been highlighted by
reversible removal of nuclear waste model ions and excellent size-selective
capture for anionic pollutants. This research thereby provides a new
perspective to explore 3D COFs as a versatile type of ion-exchange
materials.