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Proton conduction in crystalline and porous covalent organic frameworks

Nature Materials volume 15, pages 722–726 (2016)Cite this article

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Abstract

Progress over the past decades in proton-conducting materials has generated a variety of polyelectrolytes1,2,3,4,5 and microporous polymers6,7,8,9,10. However, most studies are still based on a preconception that large pores eventually cause simply flow of proton carriers rather than efficient conduction of proton ions, which precludes the exploration of large-pore polymers for proton transport. Here, we demonstrate proton conduction across mesoporous channels in a crystalline covalent organic framework. The frameworks are designed to constitute hexagonally aligned, dense, mesoporous channels that allow for loading of N-heterocyclic proton carriers. The frameworks achieve proton conductivities that are 2–4 orders of magnitude higher than those of microporous and non-porous polymers. Temperature-dependent and isotopic experiments revealed that the proton transport in these channels is controlled by a low-energy-barrier hopping mechanism. Our results reveal a platform based on porous covalent organic frameworks for proton conduction.

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Figure 1: Proton conduction across 1D mesopores of crystalline COFs.
Figure 2: Crystal structure and porosity of the mesoporous COF.
Figure 3: Impedance spectroscopy.
Figure 4: Arrhenius plots.

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  • 12 April 2016

    In the version of the Letter originally published, a word was erroneously repeated in the sentence beginning 'Our results reveal...' in the first paragraph. This has been corrected in all versions of the Letter.

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Acknowledgements

D.J. acknowledges the support of a Grant-in-Aid for Scientific Research (A) (24245030) from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT).

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Authors and Affiliations

  1. Department of Materials Molecular Science, Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama, Myodaiji, Okazaki 444-8787, Japan

    Hong Xu, Shanshan Tao & Donglin Jiang

  2. Academic Field of Energy and Environment, School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi 923-1292, Japan

    Donglin Jiang

Authors
  1. Hong Xu
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Contributions

D.J. supervised and supported the project. H.X. conducted the experiments and computational calculations. S.T. performed porosity, conductivity and durability experiments. D.J. and H.X. wrote the manuscript.

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Correspondence to Donglin Jiang.

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The authors declare no competing financial interests.

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Xu, H., Tao, S. & Jiang, D. Proton conduction in crystalline and porous covalent organic frameworks. Nature Mater 15, 722–726 (2016). https://doi.org/10.1038/nmat4611

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