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Colloidal Covalent Organic Frameworks.

Title: Colloidal Covalent Organic Frameworks.
Name(s): Smith, Brian J, author
Parent, Lucas R, author
Overholts, Anna C, author
Beaucage, Peter A, author
Bisbey, Ryan P, author
Chavez, Anton D, author
Hwang, Nicky, author
Park, Chiwoo, author
Evans, Austin M, author
Gianneschi, Nathan C, author
Dichtel, William R, author
Type of Resource: text
Genre: Journal Article
Date Issued: 2017-01-25
Physical Form: computer
online resource
Extent: 1 online resource
Language(s): English
Abstract/Description: Covalent organic frameworks (COFs) are two- or three-dimensional (2D or 3D) polymer networks with designed topology and chemical functionality, permanent porosity, and high surface areas. These features are potentially useful for a broad range of applications, including catalysis, optoelectronics, and energy storage devices. But current COF syntheses offer poor control over the material's morphology and final form, generally providing insoluble and unprocessable microcrystalline powder aggregates. COF polymerizations are often performed under conditions in which the monomers are only partially soluble in the reaction solvent, and this heterogeneity has hindered understanding of their polymerization or crystallization processes. Here we report homogeneous polymerization conditions for boronate ester-linked, 2D COFs that inhibit crystallite precipitation, resulting in stable colloidal suspensions of 2D COF nanoparticles. The hexagonal, layered structures of the colloids are confirmed by small-angle and wide-angle X-ray scattering, and kinetic characterization provides insight into the growth process. The colloid size is modulated by solvent conditions, and the technique is demonstrated for four 2D boronate ester-linked COFs. The diameter of individual COF nanoparticles in solution is monitored and quantified during COF growth and stabilization at elevated temperature using in situ variable-temperature liquid cell transmission electron microscopy imaging, a new characterization technique that complements conventional bulk scattering techniques. Solution casting of the colloids yields a free-standing transparent COF film with retained crystallinity and porosity, as well as preferential crystallite orientation. Collectively this structural control provides new opportunities for understanding COF formation and designing morphologies for device applications.
Identifier: FSU_pmch_28149954 (IID), 10.1021/acscentsci.6b00331 (DOI), PMC5269657 (PMCID), 28149954 (RID), 28149954 (EID)
Publication Note: This NIH-funded author manuscript originally appeared in PubMed Central at
Persistent Link to This Record:
Owner Institution: FSU
Is Part Of: ACS central science.
Issue: iss. 1, vol. 3

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Smith, B. J., Parent, L. R., Overholts, A. C., Beaucage, P. A., Bisbey, R. P., Chavez, A. D., … Dichtel, W. R. (2017). Colloidal Covalent Organic Frameworks. Acs Central Science. Retrieved from