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Isotopological entanglement of a metal–organic framework and a hydrogen-bonded organic framework for proton conduction

Nature Synthesis volume 4, pages 622–631 (2025)Cite this article

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Abstract

Framework structures such as metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) can facilitate proton conduction through various proton-carrying sites within the pores or along the backbones, demonstrating their viability as proton-conducting materials for fuel cells. However, the lack of inherent proton-carrying sites on typical MOF backbones and the architectural instability of HOFs pose a challenge for further applications. Here we report the synthesis of a framework that complementarily entangles a MOF and HOF through meticulous control of the deprotonation equilibrium of the linker. The hybrid entangled framework shows higher architectural stability than the MOF net alone through the mutual support of the two isotopological nets. Furthermore, the HOF architecture and plentiful H2O molecules in the well-sized channels provide a proton conductivity of 1.1 × 10−2 S cm−1 at 95 °C and 100% relative humidity. The crossover of different porous frameworks provides a method to integrate various materials seamlessly into a cohesive and functional system.

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Fig. 1: Synthesis and structures of FDM-150 and FDM-151.
Fig. 2: Design principle for the synthesis of FDM-150 and FDM-151.
Fig. 3: Proton carriers in FDM-151.
Fig. 4: Proton conductivity of the MOFs.

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Data availability

All data that support the findings of this study are available in the paper and its Supplementary Information. X-ray crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 2384370 (FDM-150), 2384371 (FDM-150-hydrated), 2384372 (FDM-151-36H2O) and 2384373 (FDM-151-hydrated). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Project of China (grant no. 2018YFA0209401, Q.L.) and the National Natural Science Foundation of China (grant nos. 22088101, 21922103 and 21961132003, Q.L.). We thank X. Kong and J. Zhu for the NMR measurements and data analysis, M. Li for the structure topology analysis and Z. Zhang for assistance with the structure refinement.

Author information

Authors and Affiliations

  1. Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China

    Zhongwen Jiang, Yuqian Sun, Yin Rao, Lingyi Yang, Haozhi Xi & Qiaowei Li

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  1. Zhongwen Jiang
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Contributions

Q.L. conceived and supervised the project. Z.J. and Q.L. designed the experiments. Z.J. and Y.S. performed the syntheses, structural characterizations and proton conductivity studies. Y.R., L.Y. and H.X. also performed structural characterizations. Z.J. and Q.L. wrote the paper. All authors contributed to the data analysis, discussion and revision of the paper.

Corresponding author

Correspondence to Qiaowei Li.

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The authors declare no competing interests.

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Peer review information

Nature Synthesis thanks Banglin Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Discussion, Figs. 1–29 and Tables 1–12.

Supplementary Data 1

Crystallographic data for FDM-150, CCDC 2384370.

Supplementary Data 2

Crystallographic data for FDM-150-hydrated, CCDC 2384371.

Supplementary Data 3

Crystallographic data for FDM-151-36H2O, CCDC 2384372.

Supplementary Data 4

Crystallographic data for FDM-151-hydrated, CCDC 2384373.

Source data

Source Data Fig. 2

Source data for the PXRD patterns in Fig. 2a,c.

Source Data Fig. 3

Source data for the histogram in Fig. 3c and the water adsorption isotherm in Fig. 3d.

Source Data Fig. 4

Source data for the PXRD patterns in Fig. 4a, the Nyquist plots in Fig. 4b,c, the proton conductivity in Fig.4d,e and the activation energy fitting in Fig. 4f.

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Jiang, Z., Sun, Y., Rao, Y. et al. Isotopological entanglement of a metal–organic framework and a hydrogen-bonded organic framework for proton conduction. Nat. Synth 4, 622–631 (2025). https://doi.org/10.1038/s44160-025-00738-2

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