Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Burke, David W.; Sun, Chao; Castano, Ioannina; Flanders, Nathan C.; Evans, Austin M.; Vitaku, Edon; McLeod, David C.; Lambeth, Robert H.; Chen, Lin X.; Gianneschi, Nathan C.; Dichtel, William R.

doi:10.1002/ange.201913975

Title: Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

Journal Article · 22 December 2019 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201913975 · OSTI ID:1760292

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Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Max Planck Institute for Brain Research Frankfurt (Germany)
US Army Research Laboratory, Aberdeen Proving Grounds, MD (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge-storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large-scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two-dimensional imine-linked COF powders by temporarily protonating their linkages. In this work, the resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 μm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: Dow Chemical Company; E.I. DuPont de Nemours & Co.; International Institute for Nanotechnology (IIN); Keck Foundation; National Science Foundation (NSF); Northwestern University Materials Research Science and Engineering Center (NU-MRSEC); Ryan Fellowship; State of Illinois; US Army Research Laboratory (USARL); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1760292

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 13 Vol. 132; ISSN 0044-8249

Publisher:: German Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films

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