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Efficient proton exchange membranes based on bifunctional metal–organic frameworks

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Abstract

An efficient strategy for increasing the proton conductivity of proton exchange membranes (PEMs) is the introduction of functionalized metal–organic frameworks (MOFs) to establish efficiency proton conduction channels. In this work, a sub-structure fragment flexible bifunctional MOFs UiO-66-NH-SO3H was successfully prepared. Next, UiO-66-NH-SO3H was filled with sulfonated poly (ether ether ketone) (SPEEK) to prepare composite PEMs. The sub-structure fragment of the UiO-66-NH-SO3H functioning as both a donor and an acceptor can promote rapid proton conduction. Furthermore, an effective channel for proton conductivity might be constructed by creating acid–base pairing interaction between the –NH/–NH2 on the UiO-66-NH-SO3H sub-structure fragment and the –SO3H on the backbone of SPEEK. At 80 °C and 100% relative humidity (RH), the UiO-66-NH-SO3H/SPEEK = 30% composite PEMs has the maximum proton conductivity of 0.273 S cm−1, which is 84% higher than the SPEEK membrane. Finally, because of the remarkable compatibility between UiO-66-NH-SO3H and SPEEK, the UiO-66-NH-SO3H/SPEEK = 40% composite PEMs had the maximum proton conductivity of 0.232 S cm−1, the lowest methanol permeability of 4.67 × 10–7 cm2 s−1 and the highest proton selectivity of 21.79 × 104 S s cm−3. This work offers a design and construction method for MOFs with precise structural functionalization to enhance proton conductivity and prevent methanol permeability in PEMs. Thus, the prepared composite PEMs is promising for DMFCs applications.

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Acknowledgements

The authors acknowledge this work was supported by the Science and Technology Plans of Tianjin (No. 20YFZCSN00930). We would like to thank the Analytical & Testing Center of Tiangong University for the Characterization Instruments such as Transmission Electron Microscope and Field Emission Scanning Electron Microscope. They have provided strong support for our work.

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Authors and Affiliations

  1. School of Materials Science and Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, 300387, China

    Pengfei Li, Yingbo Chen, Fan Xiao, Ming Cao, Jingfeng Zheng, Hao Li, Ke Zhao, Xianglin Zhang & Yuanyuan Zhang

  2. School of Textile Science and Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, 300387, China

    Jingyu Pan

Authors
  1. Pengfei Li
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  2. Yingbo Chen
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  3. Fan Xiao
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  4. Ming Cao
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  6. Jingfeng Zheng
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  7. Hao Li
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Contributions

PL contributed to methodology, validation, formal analysis, data curation and writing- original draft preparation. YC contributed to conceptualization, software, resources and writing—review & editing. FX contributed to methodology, software and validation. MC contributed to methodology, software and validation. JP contributed to electrochemical test. JZ contributed to methanol permeability test. HL, KZ, XZ and YZ contributed to investigation.

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Correspondence to Yingbo Chen.

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Li, P., Chen, Y., Xiao, F. et al. Efficient proton exchange membranes based on bifunctional metal–organic frameworks. J Mater Sci 58, 14154–14176 (2023). https://doi.org/10.1007/s10853-023-08903-8

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