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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).

Author information

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.

Corresponding author

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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