Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films
Abstract
Abstract 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. 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.
- Authors:
-
[1];
[2];
[1];
[1];
[1];
[1];
[3];
[3];
[4];
[1];
[1]
- 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)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF); Northwestern University Materials Research Science and Engineering Center (NU-MRSEC); Ryan Fellowship; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; US Army Research Laboratory (USARL); State of Illinois; International Institute for Nanotechnology (IIN); Keck Foundation; E.I. DuPont de Nemours & Co.; Dow Chemical Company; USDOE
- OSTI Identifier:
- 1760292
- Alternate Identifier(s):
- OSTI ID: 1599241
- Grant/Contract Number:
- AC02-06CH11357; DGE-1842165; DGE-1324585
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Volume: 132; Journal Issue: 13; Journal ID: ISSN 0044-8249
- Publisher:
- German Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Kovalente organische; Gerüste; Exfoliation; Nanoschichten; Polymere; Lösungsverarbeitung
Citation Formats
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., and Dichtel, William R. Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films. United States: N. p., 2019.
Web. doi:10.1002/ange.201913975.
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. Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films. United States. https://doi.org/10.1002/ange.201913975
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., and Dichtel, William R. Mon .
"Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films". United States. https://doi.org/10.1002/ange.201913975. https://www.osti.gov/servlets/purl/1760292.
@article{osti_1760292,
title = {Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films},
author = {Burke, David W. and Sun, Chao and Castano, Ioannina and Flanders, Nathan C. and Evans, Austin M. and Vitaku, Edon and McLeod, David C. and Lambeth, Robert H. and Chen, Lin X. and Gianneschi, Nathan C. and Dichtel, William R.},
abstractNote = {Abstract 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. 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.},
doi = {10.1002/ange.201913975},
journal = {Angewandte Chemie},
number = 13,
volume = 132,
place = {United States},
year = {Mon Dec 23 00:00:00 EST 2019},
month = {Mon Dec 23 00:00:00 EST 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
A highly soluble, crystalline covalent organic framework compatible with device implementation
journal, January 2019
- Wang, Lingling; Zeng, Cheng; Xu, Hong
- Chemical Science, Vol. 10, Issue 4
High‐Lithium‐Affinity Chemically Exfoliated 2D Covalent Organic Frameworks
journal, May 2019
- Chen, Xiudong; Li, Yusen; Wang, Liang
- Advanced Materials, Vol. 31, Issue 29
Confined Synthesis of Two-Dimensional Covalent Organic Framework Thin Films within Superspreading Water Layer
journal, September 2018
- Hao, Qing; Zhao, Chuangqi; Sun, Bing
- Journal of the American Chemical Society, Vol. 140, Issue 38
A novel 3D covalent organic framework membrane grown on a porous α-Al 2 O 3 substrate under solvothermal conditions
journal, January 2015
- Lu, Hui; Wang, Chang; Chen, Juanjuan
- Chemical Communications, Vol. 51, Issue 85
Chemically Stable Multilayered Covalent Organic Nanosheets from Covalent Organic Frameworks via Mechanical Delamination
journal, November 2013
- Chandra, Suman; Kandambeth, Sharath; Biswal, Bishnu P.
- Journal of the American Chemical Society, Vol. 135, Issue 47
Covalent Organic Frameworks: Structures, Synthesis, and Applications
journal, July 2018
- Lohse, Maria S.; Bein, Thomas
- Advanced Functional Materials, Vol. 28, Issue 33
High aspect ratio nanotubes assembled from macrocyclic iminium salts
journal, August 2018
- Sun, Chao; Shen, Meng; Chavez, Anton D.
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 36
Covalent organic frameworks for membrane separation
journal, January 2019
- Yuan, Shushan; Li, Xin; Zhu, Junyong
- Chemical Society Reviews, Vol. 48, Issue 10
Designed Synthesis of 3D Covalent Organic Frameworks
journal, April 2007
- El-Kaderi, Hani M.; Hunt, Joseph R.; Mendoza-Cortes, Jose L.
- Science, Vol. 316, Issue 5822, p. 268-272
Switching on and off Interlayer Correlations and Porosity in 2D Covalent Organic Frameworks
journal, June 2019
- Sick, Torben; Rotter, Julian M.; Reuter, Stephan
- Journal of the American Chemical Society, Vol. 141, Issue 32
Exfoliation of Covalent Organic Frameworks into Few-Layer Redox-Active Nanosheets as Cathode Materials for Lithium-Ion Batteries
journal, March 2017
- Wang, Shan; Wang, Qianyou; Shao, Pengpeng
- Journal of the American Chemical Society, Vol. 139, Issue 12
Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress
journal, May 2019
- Evans, Austin M.; Ryder, Matthew R.; Flanders, Nathan C.
- Industrial & Engineering Chemistry Research, Vol. 58, Issue 23
Tuning delamination of layered covalent organic frameworks through structural design
journal, January 2012
- Berlanga, Isadora; Mas-Ballesté, Rubén; Zamora, Felix
- Chemical Communications, Vol. 48, Issue 64
Perylene-Based Covalent Organic Frameworks for Acid Vapor Sensing
journal, September 2019
- Ascherl, Laura; Evans, Emrys W.; Gorman, Jeffrey
- Journal of the American Chemical Society, Vol. 141, Issue 39
A Synthetic Route for Crystals of Woven Structures, Uniform Nanocrystals, and Thin Films of Imine Covalent Organic Frameworks
journal, September 2017
- Zhao, Yingbo; Guo, Lei; Gándara, Felipe
- Journal of the American Chemical Society, Vol. 139, Issue 37
Two-Dimensional Covalent Organic Framework (COF) Membranes Fabricated via the Assembly of Exfoliated COF Nanosheets
journal, March 2017
- Li, Gang; Zhang, Kai; Tsuru, Toshinori
- ACS Applied Materials & Interfaces, Vol. 9, Issue 10
Porous, Crystalline, Covalent Organic Frameworks
journal, November 2005
- Côté, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.
- Science, Vol. 310, Issue 5751, p. 1166-1170
Self-exfoliation of 2D covalent organic frameworks: morphology transformation induced by solvent polarity
journal, January 2018
- Zhang, Na; Wang, Taisheng; Wu, Xing
- RSC Advances, Vol. 8, Issue 7
Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films
journal, September 2017
- Dey, Kaushik; Pal, Manas; Rout, Kanhu Charan
- Journal of the American Chemical Society, Vol. 139, Issue 37
Reducing the Pore Size of Covalent Organic Frameworks in Thin-Film Composite Membranes Enhances Solute Rejection
journal, August 2019
- Corcos, Amanda R.; Levato, Gabrielle A.; Jiang, Zhiwei
- ACS Materials Letters, Vol. 1, Issue 4
Few layer covalent organic frameworks with graphene sheets as cathode materials for lithium-ion batteries
journal, January 2019
- Wang, Zhaolei; Li, Yongjun; Liu, Pengju
- Nanoscale, Vol. 11, Issue 12
Oriented Films of Conjugated 2D Covalent Organic Frameworks as Photocathodes for Water Splitting
journal, December 2017
- Sick, Torben; Hufnagel, Alexander G.; Kampmann, Jonathan
- Journal of the American Chemical Society, Vol. 140, Issue 6
Superior Charge Storage and Power Density of a Conducting Polymer-Modified Covalent Organic Framework
journal, August 2016
- Mulzer, Catherine R.; Shen, Luxi; Bisbey, Ryan P.
- ACS Central Science, Vol. 2, Issue 9
A two-dimensional cationic covalent organic framework membrane for selective molecular sieving
journal, January 2018
- Zhang, Wenxiang; Zhang, Liming; Zhao, Haifeng
- Journal of Materials Chemistry A, Vol. 6, Issue 27
Development and Performance Characterization of a Polyimine Covalent Organic Framework Thin-Film Composite Nanofiltration Membrane
journal, December 2017
- Valentino, Lauren; Matsumoto, Michio; Dichtel, William R.
- Environmental Science & Technology, Vol. 51, Issue 24
Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene
journal, April 2011
- Colson, J. W.; Woll, A. R.; Mukherjee, A.
- Science, Vol. 332, Issue 6026
In Situ Charge Exfoliated Soluble Covalent Organic Framework Directly Used for Zn–Air Flow Battery
journal, December 2018
- Peng, Peng; Shi, Lei; Huo, Feng
- ACS Nano, Vol. 13, Issue 1
Single-Step Solution-Phase Synthesis of Free-Standing Two-Dimensional Polymers and Their Evolution into Hollow Spheres
journal, September 2013
- Zhou, Tian-You; Lin, Feng; Li, Zhan-Ting
- Macromolecules, Vol. 46, Issue 19
Chemically Delaminated Free-Standing Ultrathin Covalent Organic Nanosheets
journal, November 2016
- Khayum, M. Abdul; Kandambeth, Sharath; Mitra, Shouvik
- Angewandte Chemie International Edition, Vol. 55, Issue 50
A bifunctional covalent organic framework as an efficient platform for cascade catalysis
journal, January 2017
- Sun, Qi; Aguila, Briana; Ma, Shengqian
- Materials Chemistry Frontiers, Vol. 1, Issue 7
The atom, the molecule, and the covalent organic framework
journal, March 2017
- Diercks, Christian S.; Yaghi, Omar M.
- Science, Vol. 355, Issue 6328
Boosting lithium storage in covalent organic framework via activation of 14-electron redox chemistry
journal, February 2018
- Lei, Zhendong; Yang, Qinsi; Xu, Yi
- Nature Communications, Vol. 9, Issue 1
Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications
journal, July 2009
- Furukawa, Hiroyasu; Yaghi, Omar M.
- Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8875-8883
Ultrathin Two-Dimensional Covalent Organic Framework Nanosheets: Preparation and Application in Highly Sensitive and Selective DNA Detection
journal, June 2017
- Peng, Yongwu; Huang, Ying; Zhu, Yihan
- Journal of the American Chemical Society, Vol. 139, Issue 25
Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films
journal, February 2015
- DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.
- ACS Nano, Vol. 9, Issue 3
Fast Desalination by Multilayered Covalent Organic Framework (COF) Nanosheets
journal, April 2019
- Zhou, Wei; Wei, Mingjie; Zhang, Xin
- ACS Applied Materials & Interfaces, Vol. 11, Issue 18
A Highly Ordered Nanoporous, Two-Dimensional Covalent Organic Framework with Modifiable Pores, and Its Application in Water Purification and Ion Sieving
journal, December 2018
- Kuehl, Valerie A.; Yin, Jiashi; Duong, Phuoc H. H.
- Journal of the American Chemical Society, Vol. 140, Issue 51
Oriented Thin Films of a Benzodithiophene Covalent Organic Framework
journal, March 2014
- Medina, Dana D.; Werner, Veronika; Auras, Florian
- ACS Nano, Vol. 8, Issue 4
Lewis-Acid-Catalyzed Interfacial Polymerization of Covalent Organic Framework Films
journal, February 2018
- Matsumoto, Michio; Valentino, Lauren; Stiehl, Gregory M.
- Chem, Vol. 4, Issue 2
Computational design of 2D functional covalent–organic framework membranes for water desalination
journal, January 2017
- Zhang, Kang; He, Zhongjin; Gupta, Krishna M.
- Environmental Science: Water Research & Technology, Vol. 3, Issue 4
Targeted Drug Delivery in Covalent Organic Nanosheets (CONs) via Sequential Postsynthetic Modification
journal, March 2017
- Mitra, Shouvik; Sasmal, Himadri Sekhar; Kundu, Tanay
- Journal of the American Chemical Society, Vol. 139, Issue 12
Chemically Delaminated Free-Standing Ultrathin Covalent Organic Nanosheets
journal, November 2016
- Khayum, M. Abdul; Kandambeth, Sharath; Mitra, Shouvik
- Angewandte Chemie, Vol. 128, Issue 50
Delamination of Layered Covalent Organic Frameworks
journal, April 2011
- Berlanga, Isadora; Ruiz-González, Maria Luisa; González-Calbet, José María
- Small, Vol. 7, Issue 9
Self-Exfoliated Guanidinium-Based Ionic Covalent Organic Nanosheets (iCONs)
journal, February 2016
- Mitra, Shouvik; Kandambeth, Sharath; Biswal, Bishnu P.
- Journal of the American Chemical Society, Vol. 138, Issue 8
Bulk Synthesis of Exfoliated Two-Dimensional Polymers Using Hydrazone-Linked Covalent Organic Frameworks
journal, September 2013
- Bunck, David N.; Dichtel, William R.
- Journal of the American Chemical Society, Vol. 135, Issue 40
Crystalline 2D Covalent Organic Framework Membranes for High-Flux Organic Solvent Nanofiltration
journal, October 2018
- Shinde, Digambar B.; Sheng, Guan; Li, Xiang
- Journal of the American Chemical Society, Vol. 140, Issue 43
Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts
journal, September 2015
- Xu, Hong; Gao, Jia; Jiang, Donglin
- Nature Chemistry, Vol. 7, Issue 11
Recent progress in covalent organic framework thin films: fabrications, applications and perspectives
journal, January 2019
- Wang, Han; Zeng, Zhuotong; Xu, Piao
- Chemical Society Reviews, Vol. 48, Issue 2