Ambient mechanosynthesis of flexible two-dimensional covalent organic frameworks

Nailwal, Yogendra; Baker, Bryson; Alsudairy, Ziad; El Hariri El Nokab, Mustapha; Zhang, Qingsong; Wang, Tuo; Cai, Songliang; Liu, Yi; Li, Xinle

doi:10.1039/d5gc01728a

Ambient mechanosynthesis of flexible two-dimensional covalent organic frameworks

Journal Article · Sun Jun 22 20:00:00 EDT 2025 · Green Chemistry

DOI:https://doi.org/10.1039/d5gc01728a· OSTI ID:3008735

^[1]; Baker, Bryson ^[2]; ^[3]; ^[4]; Zhang, Qingsong ^[5]; ^[4]; ^[6]; ^[5]; ^[1]

Clark Atlanta University, Atlanta, GA (United States)
Howard University, Washington, DC (United States)
Clark Atlanta University, Atlanta, GA (United States); Qassim University, Buraidah (Saudi Arabia)
Michigan State University, East Lansing, MI (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
South China Normal University (SCNU), Guangzhou (China)

Flexible two-dimensional covalent organic frameworks (2D COFs) constructed from nonplanar building blocks represent an emerging paradigm in COF design. Nevertheless, the prevailing solvothermal synthesis suffers from low time efficiency, environmental unfriendliness, and cumbersome protocols. Here, in this study, we address these challenges by developing the first ambient mechanosynthesis of a diverse library of flexible 2D COFs. Sixteen distinct triazine-cored Schiff-base COFs, including five as-yet-unreported ones, were rapidly synthesized via ball milling using 2,4,6-tris(4-aminophenoxy)-1,3,5-triazine (TPT-NH2) and 2,4,6-tris(4-formylphenoxy)-1,3,5-triazine (TPT-CHO) as building blocks. Notably, the representative COF, MC-flexible-COF-1, was synthesized in as little as one hour under mechanosynthesis conditions, whereas it remained unattainable via the traditional solvothermal method, despite prolonged heating and extensive solvent screening. The highly dynamic nature of the imine linkage was unequivocally demonstrated through mechanochemical “scrambling” experiments using molecular model compounds. Furthermore, MC-flexible-COF-1 exhibited a high iodine uptake capacity of ∼4.30 g g⁻¹ from aqueous solutions and 5.97 g g⁻¹ from the vapor phase. This work underscores the immense potential of mechanochemistry as a powerful and sustainable tool for the rapid synthesis of advanced 2D COFs, including those inaccessible via conventional solution-based methods.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: SC0022000; AC02-05CH11231

OSTI ID:: 3008735

Journal Information:: Green Chemistry, Journal Name: Green Chemistry Journal Issue: 29 Vol. 27; ISSN 1463-9270; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Ambient mechanosynthesis of flexible two-dimensional covalent organic frameworks

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Ambient mechanosynthesis of flexible two-dimensional covalent organic frameworks

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