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Ultra-fast supercritically solvothermal polymerization for large single-crystalline covalent organic frameworks

Nature Protocols volume 19, pages 340–373 (2024)Cite this article

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Abstract

Crystalline polymer materials, e.g., hyper-crosslinked polystyrene, conjugate microporous polymers and covalent organic frameworks, are used as catalyst carriers, organic electronic devices and molecular sieves. Their properties and applications are highly dependent on their crystallinity. An efficient polymerization strategy for the rapid preparation of highly or single-crystalline materials is beneficial not only to structure–property studies but also to practical applications. However, polymerization usually leads to the formation of amorphous or poorly crystalline products with small grain sizes. It has been a challenging task to efficiently and precisely assemble organic molecules into a single crystal through polymerization. To address this issue, we developed a supercritically solvothermal method that uses supercritical carbon dioxide (sc-CO2) as the reaction medium for polymerization. Sc-CO2 accelerates crystal growth due to its high diffusivity and low viscosity compared with traditional organic solvents. Six covalent organic frameworks with different topologies, linkages and crystal structures are synthesized by this method. The as-synthesized products feature polarized photoluminescence and second-harmonic generation, indicating their high-quality single-crystal nature. This method holds advantages such as rapid growth rate, high productivity, easy accessibility, industrial compatibility and environmental friendliness. In this protocol, we provide a step-by-step procedure including preparation of monomer dispersion, polymerization in sc-CO2, purification and characterization of the single crystals. By following this protocol, it takes 1–5 min to grow sub-mm-sized single crystals by polymerization. The procedure takes ~4 h from preparation of monomer dispersion and polymerization in sc-CO2 to purification and drying of the product.

Key points

  • While covalent organic frameworks are interesting materials with useful properties, their application has been limited, because most processes used to prepare two- and three-dimensional crystals are either slow or unreliable.

  • Replacing traditional solvents with supercritical CO2 has profound effects on the reaction kinetics and it is possible to produce large, high-quality crystalline covalent organic frameworks in a short time.

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Fig. 1: Schematic illustration of the crystal growth process.
Fig. 2: Single-crystal polymerization mechanism of COFs in sc-CO2.
Fig. 3: Workflow of the preparation of monomer dispersion.
Fig. 4: Workflow of polymerization in sc-CO2.
Fig. 5: Workflow of purifying and drying the product.
Fig. 6: The polymerization reactions for producing COFs in sc-CO2.
Fig. 7: Ultra-fast crystal growth of sc-COFs.
Fig. 8: Equipment setup for supercritically solvothermal synthesis.
Fig. 9: Stainless steel reactor.
Fig. 10: Workflow of optical microscope characterization.
Fig. 11: Morphologies of the as-synthesized sc-COFs.
Fig. 12: PXRD characterization of sc-COFs and os-COFs.
Fig. 13: HR-TEM images and SAED patterns of 2D sc-COFs.
Fig. 14: HR-TEM images and SAED patterns of 3D sc-COFs.
Fig. 15: Characterization of the sc-COFTP–Py single crystals.
Fig. 16: Polarized PL and SHG results of sc-COFs.

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Data availability

The data supporting the findings of this study are available within the article, its Supplementary Information and the supporting primary research papers15,16.

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Acknowledgements

We thank L. Zhao and D. Hu for their support on this protocol. This work was supported by the National Key R&D Program of China (2018YFA0703200), the National Natural Science Foundation of China (61890940), the Chongqing Bayu Scholar Program (DP2020036), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB30000000), Program of Shanghai Academic Research Leaders (23XD1420200), State Key Laboratory of Molecular Engineering of Polymers and Fudan University.

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Authors and Affiliations

  1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China

    Jiang Sun, Xuejun Wang, Qiankun Wang, Lan Peng & Dacheng Wei

  2. Laboratory of Molecular Materials and Devices, Fudan University, Shanghai, China

    Jiang Sun, Xuejun Wang, Qiankun Wang, Lan Peng, Yunqi Liu & Dacheng Wei

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  1. Jiang Sun
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Contributions

D.W. conceived, designed and originally developed the protocol. L.P. and J.S. performed the experiments and analyzed the data. J.S., X.W., Q.W. and D.W. wrote the manuscript. J.S., X.W., Q.W., Y.L. and D.W. edited the manuscript. D.W. supervised the research. All authors read, commented on and accepted the final manuscript. J.S., X.W. and Q.W. contributed equally to this protocol.

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Correspondence to Dacheng Wei.

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Nature Protocols thanks Rahul Banerjee, Zhi Xu, and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Related links

Key references using this protocol:

Peng, L. et al. Nat. Commun. 12, 5077 (2021): https://doi.org/10.1038/s41467-021-24842-x

Peng, L. et al. Chem. Mater. 34, 2886−2895 (2022): https://doi.org/10.1021/acs.chemmater.1c02382

Extended data

Extended Data Fig. 1 Growth of sc-COFTP-Py in sc-CO2 with different concentrations of n-BuOH.

a, PXRD patterns of the as-synthesized sc-COFTP-Py. b-e, SEM images of sc-COFTP-Py. The samples are grown for 1 hour in sc-CO2 with 0.25% to 25% (vol.) n-BuOH. Scale bars: b, 5 μm; c–e, 2 μm. Figure adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/).

Extended Data Fig. 2 Morphologies of the as-synthesized os-COFs.

a-c, OM, SEM, and TEM images of os-COFTP-Py. d-f, OM, SEM, and TEM images of os-COF300. Scale bars: a,d, 30 μm; b,e, 2 μm; f, 1 μm; c, 200 nm. Panels a–c adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/). Panels d–f adapted with permission from ref. 16, American Chemical Society.

Extended Data Fig. 3 FT-IR spectra of the samples.

a, sc-COFTP-Py and os-COFTP-Py. b, sc-COF300 and os-COF300. c, sc-COF320 and os-COF320. d, sc-COFTPE and os-COFTPE. Panel a adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/). Panels b–d adapted with permission from ref. 16, American Chemical Society.

Extended Data Fig. 4 N2 adsorption isotherms of the samples.

a, sc-COFTP-Py after purification in sc-CO2. b, os-COFTP-Py after purification in THF. This result clearly shows a type IV isotherm. Figure adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/).

Extended Data Fig. 5 13C solid-state NMR spectra.

os-COF300 (red curve) and sc-COF300 (black curve). Figure adapted with permission from ref. 16, American Chemical Society.

Extended Data Fig. 6 PXRD characterization of sc-COFs and os-COFs.

a,b, PXRD and the simulated patterns of COFTB-BA and COF5. Sc-COFs are grown for 5 min, and os-COFs are grown for 30 min or 3 days. b, PXRD and simulated patterns of COF320 and COFTPE. Sc-COFs are grown for 1 min, and os-COFs are grown for 30 min or 3 days. Panels a and b adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/). Panel c adapted with permission from ref. 16, American Chemical Society.

Extended Data Fig. 7 TEM images of sc-COFTB-BA.

a, TEM image of sc-COFTB-BA. b, Cross-section TEM image of sc-COFTB-BA. The inset is the FFT pattern obtained from the dashed square. Scale bars: a, 200 nm; b, 20 nm. Figure adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/).

Extended Data Fig. 8 TEM images of a sc-COFTP-Py single crystal.

a, TEM image and b, enlarged image collected from the dashed area in a. c-l, HR-TEM images collected from the dashed areas in b. Scale bars: a, 10 μm; b, 5 μm; c–l, 50 nm. Figure adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/).

Extended Data Fig. 9 OM images and cross-polarized OM images of sc-COFs.

a, OM image of sc-COF300 crystals on Si/SiO2. b−d, Cross-polarized OM images of sc-COF300 when the wafer is rotated by angles of 0°, 45°, and 90°. e, OM image of sc-COF320 crystals on Si/SiO2. f−h, Cross-polarized OM images of sc-COF320 when the wafer is rotated by angles of 0°, 45°, and 90°. i, OM image of sc-COFTPE crystals on Si/SiO2. j−l, Cross-polarized OM images of sc-COFTPE when the wafer is rotated by angles of 0°, 45°, and 90°. Uniform polarized light extinction is observed over the entire length of the rods, indicating the single-crystalline nature of the samples. Scale bars, 10 μm. Figure adapted with permission from ref. 16, American Chemical Society.

Extended Data Fig. 10 Comparison with different polymerization methods.

a, Schematic of the COFTP-Py synthesis by supercritically solvothermal method and solvothermal method. b, Crystal size and growth rate in this protocol (sc-COFs and os-COFs) compared with the reported results. The red star indicates the best result in sc-CO2. Figure adapted from ref. 15, CC BY 4.0 (http://creativecommons.org/licenses/by/4.0/).

Supplementary Information

Reporting Summary

Supplementary Video 1

Procedures to add the monomer dispersion into the reactor and to install the pressure transmitter and the thermocouple.

Supplementary Video 2

Procedures to open the reactor and take out the product from the reactor.

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Sun, J., Wang, X., Wang, Q. et al. Ultra-fast supercritically solvothermal polymerization for large single-crystalline covalent organic frameworks. Nat Protoc 19, 340–373 (2024). https://doi.org/10.1038/s41596-023-00915-7

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