Covalent organic framework crystallization using a continuous flow packed-bed reactor

• Published in: CrystEngComm 2023-12, Vol.26 (1), p.27-31
• Main Authors: Bhagwandin, Dayanni D, Dunlap, John H, Tran, Ly D, Reidell, Alexander, Austin, Drake, Putnam-Neeb, Amelia A, Loveday, Morgan, Rao, Rahul, Baldwin, Luke A, Glavin, Nicholas R
• Format: Article
• Language: English
• Subjects: Continuous flow; Crystallization; Organic materials; Surface analysis (chemical)
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/d3ce01030a

Flow systems enable in-line synthesis and processing of organic materials in a continuous reaction pathway, which is advantageous for high-throughput and scale-up. In this work, a highly crystalline TAPB-OHPDA covalent organic framework (COF) was directly crystallized under continuous flow conditions in as little as 30 minutes. Brunauer-Emmett-Teller (BET) surface analysis reveals high surface areas greater than 1700 m 2 g −1 can be afforded in 2 hours, resulting in a 36× faster processing time compared to a majority of other reported solvothermal methods. Additionally, the crystalline COF material was also washed with solvent in flow to reduce the required post-processing burden typically performed iteratively during purification and activation. The results presented herein provide foundational knowledge for COF syntheses under packed-bed flow conditions and reveal an opportunity to accelerate the formation and processing of highly crystalline COF materials. Covalent organic frameworks were crystallized directly in flow, resulting in a substantial decrease in required synthesis and processing time for a diverse class of nanomaterials.