Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress
Abstract
Two-dimensional covalent organic frameworks (2D COFs) are periodic, permanently porous, and lightweight solids that are polymerized from topologically designed monomers. The predictable design and structural modularity of these materials make them promising candidates for applications including catalysis, environmental remediation, chemical separations, and organic electronics, many of which will require stability to mechanical and thermal stress. Based on their reinforced structures and high degradation temperatures, as determined by thermal gravimetric analysis (TGA), many reports have claimed that COFs have excellent thermal stability. However, their stability to heat and pressure has not been probed using methods that report on structural changes rather than the loss of volatile compounds. Here, we explore two structurally analogous 2D COFs with different polymerization chemistries using in operando X-ray diffraction (XRD), which demonstrates the loss of crystallinity at lower temperatures than the degradation temperatures measured by TGA. Density functional theory calculations suggest that an asymmetric buckling of the COF lattice is responsible for the observed loss of crystallinity. In addition to their thermal stability, XRD of the 2D COFs under gas pressures up to 100 bar showed no loss in crystallinity or structural changes, indicating that these materials are robust to mechanical stress by applied pressure. Inmore »
- Authors:
-
[1];
[2];
[1];
[1]
- Northwestern Univ., Evanston, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1526381
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Industrial and Engineering Chemistry Research
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 23; Journal ID: ISSN 0888-5885
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Evans, Austin M., Ryder, Matthew R., Flanders, Nathan C., Vitaku, Edon, Chen, Lin X., and Dichtel, William R. Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress. United States: N. p., 2019.
Web. doi:10.1021/acs.iecr.9b01288.
Evans, Austin M., Ryder, Matthew R., Flanders, Nathan C., Vitaku, Edon, Chen, Lin X., & Dichtel, William R. Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress. United States. https://doi.org/10.1021/acs.iecr.9b01288
Evans, Austin M., Ryder, Matthew R., Flanders, Nathan C., Vitaku, Edon, Chen, Lin X., and Dichtel, William R. Wed .
"Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress". United States. https://doi.org/10.1021/acs.iecr.9b01288. https://www.osti.gov/servlets/purl/1526381.
@article{osti_1526381,
title = {Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress},
author = {Evans, Austin M. and Ryder, Matthew R. and Flanders, Nathan C. and Vitaku, Edon and Chen, Lin X. and Dichtel, William R.},
abstractNote = {Two-dimensional covalent organic frameworks (2D COFs) are periodic, permanently porous, and lightweight solids that are polymerized from topologically designed monomers. The predictable design and structural modularity of these materials make them promising candidates for applications including catalysis, environmental remediation, chemical separations, and organic electronics, many of which will require stability to mechanical and thermal stress. Based on their reinforced structures and high degradation temperatures, as determined by thermal gravimetric analysis (TGA), many reports have claimed that COFs have excellent thermal stability. However, their stability to heat and pressure has not been probed using methods that report on structural changes rather than the loss of volatile compounds. Here, we explore two structurally analogous 2D COFs with different polymerization chemistries using in operando X-ray diffraction (XRD), which demonstrates the loss of crystallinity at lower temperatures than the degradation temperatures measured by TGA. Density functional theory calculations suggest that an asymmetric buckling of the COF lattice is responsible for the observed loss of crystallinity. In addition to their thermal stability, XRD of the 2D COFs under gas pressures up to 100 bar showed no loss in crystallinity or structural changes, indicating that these materials are robust to mechanical stress by applied pressure. In conclusion, we expect that these results will encourage further exploration of COF stability as a function of framework design and isolated form, which will guide the design of frameworks that withstand demanding application-relevant conditions.},
doi = {10.1021/acs.iecr.9b01288},
journal = {Industrial and Engineering Chemistry Research},
number = 23,
volume = 58,
place = {United States},
year = {Wed May 22 00:00:00 EDT 2019},
month = {Wed May 22 00:00:00 EDT 2019}
}
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Works referencing / citing this record:
Rapid Synthesis of High Surface Area Imine‐Linked 2D Covalent Organic Frameworks by Avoiding Pore Collapse During Isolation
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