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A high-performance hydroxide exchange membrane enabled by Cu2+-crosslinked chitosan

Nature Nanotechnology volume 17, pages 629–636 (2022)Cite this article

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Abstract

Ion exchange membranes are widely used to selectively transport ions in various electrochemical devices. Hydroxide exchange membranes (HEMs) are promising to couple with lower cost platinum-free electrocatalysts used in alkaline conditions, but are not stable enough in strong alkaline solutions. Herein, we present a Cu2+-crosslinked chitosan (chitosan-Cu) material as a stable and high-performance HEM. The Cu2+ ions are coordinated with the amino and hydroxyl groups of chitosan to crosslink the chitosan chains, forming hexagonal nanochannels (~1 nm in diameter) that can accommodate water diffusion and facilitate fast ion transport, with a high hydroxide conductivity of 67 mS cm−1 at room temperature. The Cu2+ coordination also enhances the mechanical strength of the membrane, reduces its permeability and, most importantly, improves its stability in alkaline solution (only 5% conductivity loss at 80 °C after 1,000 h). These advantages make chitosan-Cu an outstanding HEM, which we demonstrate in a direct methanol fuel cell that exhibits a high power density of 305 mW cm−2. The design principle of the chitosan-Cu HEM, in which ion transport channels are generated in the polymer through metal-crosslinking of polar functional groups, could inspire the synthesis of many ion exchange membranes for ion transport, ion sieving, ion filtration and more.

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Fig. 1: Converting chitin biowaste to a chitosan-Cu HEM.
Fig. 2: Fabrication and characterization of the chitosan-Cu membrane.
Fig. 3: The crystalline structure of chitosan and chitosan-Cu.
Fig. 4: The OH− conductivity and alkali stability of chitosan-Cu.
Fig. 5: Applying the chitosan-Cu membrane in a DMFC.

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Data availability

The data that support the findings of this study are available within the paper and the Supplementary Information. Source data are provided with this paper. Other relevant data are available from the corresponding authors on reasonable request.

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Acknowledgements

L.H. and M.W. acknowledge support from the University of Maryland A. James Clark School of Engineering and Maryland Nanocenter, its Surface Analysis Center and AIMLab. R.M.B. and X.Z. acknowledge support from the US National Institute of Standards and Technology under cooperative agreement no. 70NANB15H261. The NMR work at Hunter College is supported by the US Office of Naval Research under grant no. N00014-20-1-2186. XAS research conducted at beamline 9-BM used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Research used resources of the Center for Functional Nanomaterials and the SMI beamline (12-ID) of the National Synchrotron Light Source II, both supported by US DOE Office of Science Facilities at Brookhaven National Laboratory under contract no. DE-SC0012704.

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Author notes

  1. These authors contributed equally: Meiling Wu, Xin Zhang, Yun Zhao.

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Meiling Wu, Xin Zhang, Chunpeng Yang, Shuangshuang Jing, Alexandra Brozena, Robert M. Briber & Liangbing Hu

  2. Centre for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Yun Zhao & Yushan Yan

  3. School of Engineering, Brown University, Providence, RI, USA

    Qisheng Wu & Yue Qi

  4. Davidson School of Chemical Engineering, University of Purdue, West Lafayette, IN, USA

    Jeffrey T. Miller & Nicole J. Libretto

  5. Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Tianpin Wu

  6. Hunter College of City University of New York, New York, NY, USA

    Sahana Bhattacharyya, Mounesha N. Garaga & Steven G. Greenbaum

  7. Center for Functional Nanomaterials, Brookhaven National Laboratories, Upton, NY, USA

    Yugang Zhang

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Contributions

L.H. and M.W. conceived the idea and designed the experiments. M.W. performed and interpreted the chitosan-Cu membrane fabrication, characterization and conductivity studies. X.Z., Y. Zhang and R.M.B. conducted and interpreted the aligned chitosan-Cu fabrication and X-ray diffraction measurements. Y. Zhao and Y.Y. performed the single fuel cell studies and the methanol permeability measurements. M.W. and S.J. took the digital photographs, zeta potential measurements and performed the tensile strain–stress tests. Q.W. and Y.Q. performed the AIMD and DFT simulations. S.B., M.G. and S.G.G. conducted the NMR measurements. T.W., N.L. and J.T.M. performed and interpreted the XAS measurements. M.W., X.Z., C.Y., A.B. and L.H. collectively wrote the paper. All authors commented on the final manuscript.

Corresponding author

Correspondence to Liangbing Hu.

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The authors declare no competing interests.

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Nature Nanotechnology thanks Dario Dekel and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–25, Tables 1–12 and Discussion.

Source data

Source Data Fig. 2

XPS and XAS spectra of chitosan-Cu.

Source Data Fig. 3

X-ray diffraction of chitosan-Cu membrane and aligned chitosan-Cu.

Source Data Fig. 4

EIS, conductivity evolution with relative humidity, stability of conductivity and simulated bond distance evolution.

Source Data Fig. 5

Methanol permeability, tensile stress–strain, single-cell polarization and power density, power density comparation, etc.

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Wu, M., Zhang, X., Zhao, Y. et al. A high-performance hydroxide exchange membrane enabled by Cu2+-crosslinked chitosan. Nat. Nanotechnol. 17, 629–636 (2022). https://doi.org/10.1038/s41565-022-01112-5

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