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Photogated proton conductivity of ZIF-8 membranes co-modified with graphene quantum dots and polystyrene sulfonate

一种石墨烯量子点和聚苯乙烯磺酸共修饰的光控质子传导ZIF-8薄膜

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Abstract

Smart proton conductive metal-organic framework (MOF) membranes with dynamic remote control over proton conduction show high potential for use in advanced applications, such as sensors and bioprocesses. Here, we report a photoswitchable proton conductive ZIF-8 membrane by coencapsulating polystyrene sulfonate and graphene quantum dots into a ZIF-8 matrix (GQDs-PSS@ZIF-8) via a solid-confined conversion process. The proton conductivity of the GQDs-PSS@ZIF-8 membrane is 6.3 times higher than that of pristine ZIF-8 and can be reversibly switched by light due to photoluminescence quenching and the photothermal conversion effect, which converts light into heat. The local increase in temperature allows water molecules to escape from the porous channels, which cuts off the proton transport pathways and results in a decrease in proton conductivity. The proton conductivity is restored when the light is off owing to regaining water molecules, which act as proton carriers, from the surroundings. The GQDs-PSS@ZIF-8 membrane responds efficiently to light and exhibits an ON/OFF ratio of 12.8. This photogated proton conduction in MOFs has potential for the development and application of MOF-based protonic solids in advanced photoelectric devices.

摘要

可遥控的智能质子传导金属有机骨架(MOFs)薄膜在传感和生物过程等领域具有诱人的应用前景. 本文通过固态限制转换方法将聚苯乙烯磺酸(PSS)和石墨烯量子点(GQDs)共同封装到ZIF-8中, 成功制备了具有光控质子传导特性的ZIF-8薄膜(GQDs-PSS@ZIF-8). GQDs-PSS@ZIF-8膜的质子电导率是ZIF-8膜的6.3倍, 并且实现了其质子电导率的光可逆控制. 其机理主要是在荧光猝灭和光热转换效应下光能被转换为热, 使膜局部温度升高, 水分子从多孔通道中逸出, 从而切断质子传输路径, 导致质子电导率下降. 光照停止后, 水分子重新回到孔道中, 使质子传导率恢复. GQDs-PSS@ZIF-8膜具有较好的光响应性能, 其开关比为12.8. MOFs中的光控质子传导性能对促进MOF基质子传导固体的发展及其在先进光电设备中的应用具有潜在价值.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21875212), the Key Program of National Natural Science Foundation (51632008), the Major R&D Plan of Zhejiang Natural Science Foundation (LD18E020001), the National Key Research and Development Program (2016YFA0200204) and the Fundamental Research Funds for the Central Universities.

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Authors and Affiliations

  1. State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, ERC of Membrane and Water Treatment, Ministry of Education, Zhejiang University, Hangzhou, 310027, China

    Shuaikang Fan  (范帅康), Shilin Wang  (王世林), **aobin Wang  (王小彬), Zhuoyi Li  (**卓异), Xu Ma  (马旭), **nyi Wan  (万昕艺), Shabab Hussain & **nsheng Peng  (彭新生)

Authors
  1. Shuaikang Fan  (范帅康)
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  2. Shilin Wang  (王世林)
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  3. **aobin Wang  (王小彬)
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  4. Zhuoyi Li  (**卓异)
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  5. Xu Ma  (马旭)
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  6. **nyi Wan  (万昕艺)
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  7. Shabab Hussain
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  8. **nsheng Peng  (彭新生)
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Contributions

Author contributions Peng X supervised the project; Fan S performed the experiments, analyzed the results and wrote the manuscript; Wang S, Hussain S and Li Z assisted in the device fabrication and measurement; Ma X, Wang X and Wan X contributed to the theoretical and data analyses. All authors contributed to the general discussion.

Corresponding author

Correspondence to **nsheng Peng  (彭新生).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Shuaikang Fan received his Bachelor degree (2019) from the College of Materials Science and Engineering at Sichuan University. He is currently pursuing his Master degree at the School of Materials Science and Engineering at Zhejiang University under the supervision of Prof. **nsheng Peng. His present research interests mainly focus on the design and syntheses of proton conductive MOF membranes for energy conversion devices.

**nsheng Peng received his PhD degree in 2003 at the Institute of Solid State Physics, Chinese Academy of Sciences. He became a full professor at the School of Materials Science and Engineering at Zhejiang University in 2010. His research interests mainly focus on the design and syntheses of functional membranes and controlled mass transportation in energy and environmental science.

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Fan, S., Wang, S., Wang, X. et al. Photogated proton conductivity of ZIF-8 membranes co-modified with graphene quantum dots and polystyrene sulfonate. Sci. China Mater. 64, 1997–2007 (2021). https://doi.org/10.1007/s40843-020-1602-5

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