ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress

  • Austin M. Evans
    Austin M. Evans
    Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  • Matthew R. Ryder
    Matthew R. Ryder
    Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  • Nathan C. Flanders
    Nathan C. Flanders
    Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  • Edon Vitaku
    Edon Vitaku
    Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
    More by Edon Vitaku
  • Lin X. Chen
    Lin X. Chen
    Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
    More by Lin X. Chen
  • , and 
  • William R. Dichtel*
    William R. Dichtel
    Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
    *E-mail: [email protected]
Cite this: Ind. Eng. Chem. Res. 2019, 58, 23, 9883–9887
Publication Date (Web):May 22, 2019
https://doi.org/10.1021/acs.iecr.9b01288
Copyright © 2019 American Chemical Society

    Article Views

    1886

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    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. 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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.9b01288.

    • Detailed information regarding monomer and materials synthesis, materials characterization, and computational results (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 29 publications.

    1. LanPui ChingResearcher, Ph.D.MaShengqianProfessor and Welch Chair in ChemistryAidan F. Greene, Graduate Student, The Ohio State University in the Department of Chemistry and Biochemistry.. Covalent Organic Frameworks. 2023https://doi.org/10.1021/acsinfocus.7e7028
    2. Dongyang Zhu, Qianqian Yan, Yifan Zhu, Xinbo Tong, Alec Ajnsztajn, Muhammad M. Rahman, Pulickel M. Ajayan, Rafael Verduzco. Solvent-Induced Incremental Pore Collapse in Two-Dimensional Covalent Organic Frameworks. ACS Materials Letters 2022, 4 (11) , 2368-2374. https://doi.org/10.1021/acsmaterialslett.2c00672
    3. Jeong-Min Seo, Hyuk-Jun Noh, Jong-Pil Jeon, Hyeongjun Kim, Gao-Feng Han, Sang Kyu Kwak, Hu Young Jeong, Lianli Wang, Feng Li, Jong-Beom Baek. Conductive and Ultrastable Covalent Organic Framework/Carbon Hybrid as an Ideal Electrocatalytic Platform. Journal of the American Chemical Society 2022, 144 (43) , 19973-19980. https://doi.org/10.1021/jacs.2c08344
    4. Austin M. Evans, Michael J. Strauss, Amanda R. Corcos, Zoheb Hirani, Woojung Ji, Leslie S. Hamachi, Xavier Aguilar-Enriquez, Anton D. Chavez, Brian J. Smith, William R. Dichtel. Two-Dimensional Polymers and Polymerizations. Chemical Reviews 2022, 122 (1) , 442-564. https://doi.org/10.1021/acs.chemrev.0c01184
    5. Sebastian T. Emmerling, Robin Schuldt, Sebastian Bette, Liang Yao, Robert E. Dinnebier, Johannes Kästner, Bettina V. Lotsch. Interlayer Interactions as Design Tool for Large-Pore COFs. Journal of the American Chemical Society 2021, 143 (38) , 15711-15722. https://doi.org/10.1021/jacs.1c06518
    6. Steve R. Lustig, Jan W. Andzelm, Eric D. Wetzel. Highly Thermostable Dynamic Structures of Polyaramid Two-Dimensional Polymers. Macromolecules 2021, 54 (3) , 1291-1303. https://doi.org/10.1021/acs.macromol.0c01931
    7. Samik Jhulki, Cameron H. Feriante, Roman Mysyk, Austin M. Evans, Alexandre Magasinski, Ashwin Sankara Raman, Kostiantyn Turcheniuk, Stephen Barlow, William R. Dichtel, Gleb Yushin, Seth R. Marder. A Naphthalene Diimide Covalent Organic Framework: Comparison of Cathode Performance in Lithium-Ion Batteries with Amorphous Cross-linked and Linear Analogues, and Its Use in Aqueous Lithium-Ion Batteries. ACS Applied Energy Materials 2021, 4 (1) , 350-356. https://doi.org/10.1021/acsaem.0c02281
    8. Keyu Geng, Ting He, Ruoyang Liu, Sasanka Dalapati, Ke Tian Tan, Zhongping Li, Shanshan Tao, Yifan Gong, Qiuhong Jiang, Donglin Jiang. Covalent Organic Frameworks: Design, Synthesis, and Functions. Chemical Reviews 2020, 120 (16) , 8814-8933. https://doi.org/10.1021/acs.chemrev.9b00550
    9. Martin Ratsch, Chen Ye, Yizhou Yang, Airui Zhang, Austin M. Evans, Karl Börjesson. All-Carbon-Linked Continuous Three-Dimensional Porous Aromatic Framework Films with Nanometer-Precise Controllable Thickness. Journal of the American Chemical Society 2020, 142 (14) , 6548-6553. https://doi.org/10.1021/jacs.9b10884
    10. Samik Jhulki, Austin M. Evans, Xue-Li Hao, Matthew W. Cooper, Cameron H. Feriante, Johannes Leisen, Hong Li, David Lam, Mark C. Hersam, Stephen Barlow, Jean-Luc Brédas, William R. Dichtel, Seth R. Marder. Humidity Sensing through Reversible Isomerization of a Covalent Organic Framework. Journal of the American Chemical Society 2020, 142 (2) , 783-791. https://doi.org/10.1021/jacs.9b08628
    11. Edon Vitaku, Cara N. Gannett, Keith L. Carpenter, Luxi Shen, Héctor D. Abruña, William R. Dichtel. Phenazine-Based Covalent Organic Framework Cathode Materials with High Energy and Power Densities. Journal of the American Chemical Society 2020, 142 (1) , 16-20. https://doi.org/10.1021/jacs.9b08147
    12. Austin M. Evans, Ioannina Castano, Alexandra Brumberg, Lucas R. Parent, Amanda R. Corcos, Rebecca L. Li, Nathan C. Flanders, David J. Gosztola, Nathan C. Gianneschi, Richard D. Schaller, William R. Dichtel. Emissive Single-Crystalline Boroxine-Linked Colloidal Covalent Organic Frameworks. Journal of the American Chemical Society 2019, 141 (50) , 19728-19735. https://doi.org/10.1021/jacs.9b08815
    13. Liliana P.L. Gonçalves, Javier Garcia Ben, Karol Strutyński, Laura Rodriguez-Lorenzo, Joana Araújo, A.Sofia G.G. Santos, O. Salomé G.P. Soares, M. Fernando R. Pereira, Yury V. Kolen'ko, Manuel Melle-Franco, Laura M. Salonen. Covalent organic frameworks as catalyst support: A case study of thermal, hydrothermal, and mechanical pressure stability of β-ketoenamine-linked TpBD-Me2. Microporous and Mesoporous Materials 2024, 366 , 112916. https://doi.org/10.1016/j.micromeso.2023.112916
    14. Bing Wang, Penghua Ying, Jin Zhang. The thermoelastic properties of monolayer covalent organic frameworks studied by machine-learning molecular dynamics. Nanoscale 2023, 16 (1) , 237-248. https://doi.org/10.1039/D3NR04509A
    15. Shiyuan Zhou, Qi Lin, Zhongfei Ren, Congsheng Zhou, Yuhua Shan, Ping Liu. Synthesis of phenyl-based hyper-crosslinked porous organic polymers via Friedel-Crafts reaction for efficient organic dye adsorption. Microporous and Mesoporous Materials 2023, 362 , 112765. https://doi.org/10.1016/j.micromeso.2023.112765
    16. Nathan P. Bradshaw, Zoheb Hirani, Lidia Kuo, Siyang Li, Nicholas X. Williams, Vinod K. Sangwan, Lindsay E. Chaney, Austin M. Evans, William R. Dichtel, Mark C. Hersam. Aerosol‐Jet‐Printable Covalent Organic Framework Colloidal Inks and Temperature‐Sensitive Nanocomposite Films. Advanced Materials 2023, 35 (38) https://doi.org/10.1002/adma.202303673
    17. Mobina Ahmadi, Ahmad Asadinezhad. Synthesis and characterization of azodianiline covalent organic frameworks intended for energy storage. Journal of Molecular Structure 2023, 1286 , 135647. https://doi.org/10.1016/j.molstruc.2023.135647
    18. Mingchao Shao, Yunqi Liu, Yunlong Guo. Customizable 2D Covalent Organic Frameworks for Optoelectronic Applications. Chinese Journal of Chemistry 2023, 41 (10) , 1260-1285. https://doi.org/10.1002/cjoc.202200664
    19. Jinfang Kou, Jian Fang, Jianfeng Li, Huacheng Zhao, Mengmeng Gao, Gong Zeng, Wei David Wang, Fengwei Zhang, Jiantai Ma, Zhengping Dong. Electron-rich platinum single sites anchored on sulfur-doped covalent organic frameworks for boosting anti-Markovnikov hydrosilylation of alkenes. Chemical Engineering Journal 2023, 463 , 142255. https://doi.org/10.1016/j.cej.2023.142255
    20. Indranil Roy, Austin M. Evans, Partha Jyoti Das, Mohamed Ateia, Matthew R. Ryder, Leighton O. Jones, Masoud Kazem-Rostami, Subhadip Goswami, Yassine Beldjoudi, Dengke Shen, George C. Schatz, Joseph T. Hupp, William R. Dichtel, J. Fraser Stoddart. Cyclophane-based two-dimensional polymer formed by an interfacial click reaction. Cell Reports Physical Science 2022, 3 (4) , 100806. https://doi.org/10.1016/j.xcrp.2022.100806
    21. Yuting Tang, Junwei Che, Guangzhao Qin. On the microscopic view of the low thermal conductivity of buckling two-dimensional materials from molecular dynamics. Chemical Physics Letters 2021, 780 , 138954. https://doi.org/10.1016/j.cplett.2021.138954
    22. Austin M. Evans, Ashutosh Giri, Vinod K. Sangwan, Sangni Xun, Matthew Bartnof, Carlos G. Torres-Castanedo, Halleh B. Balch, Matthew S. Rahn, Nathan P. Bradshaw, Edon Vitaku, David W. Burke, Hong Li, Michael J. Bedzyk, Feng Wang, Jean-Luc Brédas, Jonathan A. Malen, Alan J. H. McGaughey, Mark C. Hersam, William R. Dichtel, Patrick E. Hopkins. Thermally conductive ultra-low-k dielectric layers based on two-dimensional covalent organic frameworks. Nature Materials 2021, 20 (8) , 1142-1148. https://doi.org/10.1038/s41563-021-00934-3
    23. Jelle Wieme, Veronique Van Speybroeck. Unravelling thermal stress due to thermal expansion mismatch in metal–organic frameworks for methane storage. Journal of Materials Chemistry A 2021, 9 (8) , 4898-4906. https://doi.org/10.1039/D0TA09462E
    24. Austin M. Evans, Matthew R. Ryder, Woojung Ji, Michael J. Strauss, Amanda R. Corcos, Edon Vitaku, Nathan C. Flanders, Ryan P. Bisbey, William R. Dichtel. Trends in the thermal stability of two-dimensional covalent organic frameworks. Faraday Discussions 2021, 225 , 226-240. https://doi.org/10.1039/D0FD00054J
    25. Austin M. Evans, Nathan P. Bradshaw, Brian Litchfield, Michael J. Strauss, Bethany Seckman, Matthew R. Ryder, Ioannina Castano, Christopher Gilmore, Nathan C. Gianneschi, Catherine R. Mulzer, Mark C. Hersam, William R. Dichtel. High‐Sensitivity Acoustic Molecular Sensors Based on Large‐Area, Spray‐Coated 2D Covalent Organic Frameworks. Advanced Materials 2020, 32 (42) https://doi.org/10.1002/adma.202004205
    26. Keyu Geng, Vasanthakumar Arumugam, Huanjun Xu, Yanan Gao, Donglin Jiang. Covalent organic frameworks: Polymer chemistry and functional design. Progress in Polymer Science 2020, 108 , 101288. https://doi.org/10.1016/j.progpolymsci.2020.101288
    27. David W. Burke, Chao Sun, Ioannina Castano, Nathan C. Flanders, Austin M. Evans, Edon Vitaku, David C. McLeod, Robert H. Lambeth, Lin X. Chen, Nathan C. Gianneschi, William R. Dichtel. Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films. Angewandte Chemie 2020, 132 (13) , 5203-5209. https://doi.org/10.1002/ange.201913975
    28. David W. Burke, Chao Sun, Ioannina Castano, Nathan C. Flanders, Austin M. Evans, Edon Vitaku, David C. McLeod, Robert H. Lambeth, Lin X. Chen, Nathan C. Gianneschi, William R. Dichtel. Acid Exfoliation of Imine‐linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films. Angewandte Chemie International Edition 2020, 59 (13) , 5165-5171. https://doi.org/10.1002/anie.201913975
    29. Cameron H. Feriante, Samik Jhulki, Austin M. Evans, Raghunath R. Dasari, Kaitlin Slicker, William R. Dichtel, Seth R. Marder. Rapid Synthesis of High Surface Area Imine‐Linked 2D Covalent Organic Frameworks by Avoiding Pore Collapse During Isolation. Advanced Materials 2020, 32 (2) https://doi.org/10.1002/adma.201905776

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect