Lawrence Berkeley National Laboratory

Covalent organic frameworks (COFs) are functional porous crystalline “molecular Legos” entirely composed of light elements and held together by covalent bonds. Their synthesis typically relies on the formation of reversible covalent bonds linking multivalent monomers. While the reversibility in linkage formation imparts error correction and defect healing that dictate crystallinity, the thermodynamic characteristics intrinsically limit the chemical stability of COFs and constrain their further applications. To overcome chemical stability issues, considerable research efforts have been devoted to developing robust COFs by strengthening covalent linkages, tailoring noncovalent interactions, and manipulating inherent properties of linkers. In this review, we first summarize the state-of-the-art development of chemically robust COFs, then scrutinize the intriguing applications of chemically robust COFs in heterogeneous catalysis, environmental remediation, chiral separation, corrosive gas sensing, and lithium-ion batteries. We further present the major challenges and opportunities in future research directions and perspectives of chemically robust COFs.