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Direct Synthesis of Amide-Linked COFs via Ester-Amine Exchange Reaction
Rui-Zhi Li1,2, Song-Chen Yu3, Wei Jiang4
1CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Science (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
None:
Achieving both crystallinity and stability is challenging for covalent organic frameworks (COFs) as the reversible reaction required for enhancing crystallinity compromises stability. Amide linkages, a type of chemically stable bond for COF construction, are predominantly synthesized via postmodifications. This work presents a direct and convenient method for synthesizing highly crystalline amide-linked COFs via the ester-amine exchange reaction. The reaction is irreversible, as demonstrated by the investigation of model reactions and COFTAPT-TTPF polymerization process. The water absorption capacity of COFTAPT-TTPF was 0.56 g/g at 25 °C and 94% relative humidity. Meanwhile, via direct synthesis, we grew COFTAPT-TTPF on anodized aluminum oxide membranes to form COF@AAO composite membranes. The composite membrane achieved an output power density of 7.70 W/m2 under a 50-fold salinity gradient in osmotic energy conversion. This direct polymerization protocol improves the convenience and accessibility of amide-linked COFs.
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