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Using sound to synthesize covalent organic frameworks in water

Nature Synthesis volume 1, pages 87–95 (2022)Cite this article

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Abstract

Covalent organic frameworks (COFs) are typically synthesized using solvothermal conditions (>120 °C, >72 hours) in harmful organic solvents. Here we report a strategy to rapidly (<60 minutes) synthesize imine-linked COFs in aqueous acetic acid using sonochemistry and thus avoid most of the disadvantages of solvothermal methods. Using the sonochemical method, we synthesized to our knowledge previously unreported COFs. The crystallinity and porosity of these COFs is comparable to or better than those of the same materials made by established solvothermal routes. The sonochemical method even works in sustainable solvents, such as food-grade vinegar. The generality of the method is shown in the preparation of a 2D COF with pendant functionalization and of a COF with 3D connectivity. Finally, a COF synthesized sonochemically acts as an excellent photocatalyst for the sacrificial hydrogen evolution from water, showing a more sustained catalytic performance compared with that of its solvothermal analogue. The speed, ease and generality of this sonochemical method together with improved material quality makes the use of sound an enabling methodology for the rapid discovery of functional COFs.

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Fig. 1: Apparatus and conditions used for sonochemical synthesis, the COFs studied and the monomers used to synthesize them.
Fig. 2: Systematic investigation of the effect of reaction time on the prototypical COF TAPB-DMTA formed by sonochemical synthesis (sonoCOF-1) in aqueous AcOH.
Fig. 3: The structures of sonoCOF-1–sonoCOF-9 confirmed by Pawley refinements based on the modelled crystal structures.
Fig. 4: Synthetic routes for COFs sonoCOF-8 and sonoCOF-9.
Fig. 5: Photocatalytic hydrogen evolution experiments and characterization of sonoCOFs.

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Data availability

Source Data are provided with this paper. All other data supporting the finding of this study are available within this article and its Supplementary Information. The experimental procedures and characterization of all the COFs are provided in the Supplementary Information.

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Acknowledgements

We acknowledge funding from the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design and the Engineering and Physical Sciences Research Council (EPSRC). P.Y., H.C., L.L. and B.L. thank the China Scholarship Council for PhD studentships. We thank the Materials Innovation Factory (MIF) team for help with instrument training. We thank M. Lightowler of Stockholm University for testing the feasibility of using 3D electron diffraction to solve the COF structures. The TEM analysis was performed in the Albert Crewe Centre for Electron Microscopy, a University of Liverpool Shared Research Facility.

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Authors and Affiliations

  1. Materials Innovation Factory and Department of Chemistry, University of Liverpool, Liverpool, UK

    Wei Zhao, Peiyao Yan, Haofan Yang, Alex M. James, Hongmei Chen, Lunjie Liu, Boyu Li, Zhongfu Pang, Rob Clowes, John W. Ward, Yue Wu & Andrew I. Cooper

  2. Leverhulme Research Centre for Functional Materials Design, Materials Innovation Factory and Department of Chemistry, University of Liverpool, Liverpool, UK

    Wei Zhao, Haofan Yang, Zhongfu Pang, John W. Ward & Andrew I. Cooper

  3. Albert Crewe Centre for Electron Microscopy, University of Liverpool, Liverpool, UK

    Mounib Bahri & Nigel D. Browning

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Contributions

W.Z. synthesized and characterized the materials, performed photocatalytic experiments and analysed the photocatalysis results with H.Y. P.Y. performed the scanning electron microscopy, time-correlated single photon counting and FTIR measurements. H.Y. performed the ultraviolet measurements. R.C. performed thermogravimetric analysis. A.M.J. and W.Z. performed gas adsorption measurements. H.C. and L.L. performed electrochemical measurements. M.B. and N.D.B. performed TEM measurements. W.Z. conceived the modelling strategy. B.L. and Z.P. provided useful advice in the structural simulation of COFs. Y.W. and J.W.W. conceived the project. A.I.C., Y.W. and J.W.W. directed the research. Data were interpreted by all the authors and the manuscript was prepared by A.I.C., Y.W., J.W.W. and W.Z.

Corresponding authors

Correspondence to John W. Ward, Yue Wu or Andrew I. Cooper.

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The authors declare no competing interests.

Peer review information

Nature Synthesis thanks Donglin Jiang, Qihua Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Alison Stoddart was the primary editor on this article and managed its editorial process and peer review in collaboration with the rest of the editorial team.

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Extended data

Extended Data Fig. 1 A comparison of BET surface areas and total pore volumes of sonoCOFs synthesized in aqueous and organic solvents.

The Brunauer–Emmett–Teller (BET) surface area (dark shading) and pore volume (light shading) of all the synthesized sonoCOFs in aqueous solvent (blue bars) are greater than or equal to the equivalent sonoCOFs synthesized in organic solvent (pink bars).

Source data

Supplementary information

Source data

Source Data Fig. 5

Raw data for Fig. 5a,b.

Source Data Fig. 5

Full-size TEM images supporting Fig. 5d,e.

Source Data Extended Data Fig. 1

Raw data for Extended Data Fig. 1.

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Zhao, W., Yan, P., Yang, H. et al. Using sound to synthesize covalent organic frameworks in water. Nat Synth 1, 87–95 (2022). https://doi.org/10.1038/s44160-021-00005-0

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