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MOF-derived nanoporous carbons with diverse tunable nanoarchitectures

Nature Protocols volume 17, pages 2990–3027 (2022)Cite this article

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Abstract

Metal-organic frameworks (MOFs), or porous coordination polymers, are crystalline porous materials formed by coordination bonding between inorganic and organic species on the basis of the self-assembly of the reacting units. The typical characteristics of MOFs, including their large specific surface areas, ultrahigh porosities and excellent thermal and chemical stabilities, as well as their great potential for chemical and structural modifications, make them excellent candidates for versatile applications. Their poor electrical conductivity, however, has meant that they have not been useful for electrochemical applications. Fortuitously, the direct carbonization of MOFs results in a rearrangement of the carbon atoms of the organic units into a network of carbon atoms, which means that the products have useful levels of conductivity. The direct carbonization of zeolitic imidazolate framework (ZIF)-type MOFs, particularly ZIF-8, has successfully widened the scope of possible applications of MOFs to include electrochemical reactions that could be used in, for example, energy storage, energy conversion, electrochemical biosensors and capacitive deionization of saline water. Here, we present the first detailed protocols for synthesizing high-quality ZIF-8 and its modified forms of hollow ZIF-8, core-shell ZIF-8@ZIF-67 and ZIF-8@mesostuctured polydopamine. Typically, ZIF-8 synthesis takes 27 h to complete, and subsequent nanoarchitecturing procedures leading to hollow ZIF-8, ZIF-8@ZIF-67 and ZIF-8@mPDA take 6, 14 and 30 h, respectively. The direct-carbonization procedure takes 12 h. The resulting nanoporous carbons are suitable for electrochemical applications, in particular as materials for supercapacitors.

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Fig. 1: Setting up the three-electrode cell.
Fig. 2: Synthesis of ZIF-8 and its carbonization.
Fig. 3: Synthesis of HZIF-8 and its carbonization.
Fig. 4: Synthesis of core-shell ZIF-8@ZIF-67 and its carbonization.
Fig. 5: Direct carbonization and electron microscopy images of the products.
Fig. 6: mPDA coating of ZIF-8.
Fig. 7: Physical and electrochemical characterizations of NPCs obtained at different carbonization temperatures.
Fig. 8: Physical and electrochemical characterizations of NPC and HNPC.
Fig. 9: Physical and electrochemical characterizations of NC, GC and NC@GCs.
Fig. 10: Physical and electrochemical characterizations of NPC, HPC-2.5 and HPC-5.0.

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Data availability

The main data discussed in this protocol are available in the supporting primary research papers42,48,50,52. Datasets of Fig. 6d and g have been made openly accessible at Figshare (https://doi.org/10.6084/m9.figshare.18515858.v1). Source data are provided with this paper.

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Acknowledgements

This research was supported by the JST-ERATO Yamauchi Materials Space-Tectonics Project (JPMJER2003). This research was also supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2020R1A6A3A03039037). This work was also performed in part at the Queensland node of the Australian National Fabrication Facility (ANFF-Q), a company established under the National Collaborative Research Infrastructure Strategy to provide nano and microfabrication facilities for Australian researchers.

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Authors and Affiliations

  1. Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, Queensland, Australia

    Minjun Kim, Ruijing Xin, Jacob Earnshaw, Aditya Ashok, Ashok Kumar Nanjundan, Jongbeom Na & Yusuke Yamauchi

  2. School of Chemistry and Molecular Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, Shanghai, China

    Jing Tang

  3. International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, Japan

    Jonathan P. Hill & Christine Young

  4. JST-ERATO Yamauchi Materials Space-Tectonics Project and International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki, Japan

    Jonathan P. Hill & Yusuke Yamauchi

  5. Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, Republic of Korea

    Jeonghun Kim

  6. Department of Applied Chemistry, School of Advanced Science and Engineering, Waseda University, Tokyo, Japan

    Yoshiyuki Sugahara

  7. JST-ERATO Yamauchi Materials Space-Tectonics Project, Kagami Memorial Research Institute for Science and Technology, Waseda University, Tokyo, Japan

    Yoshiyuki Sugahara & Yusuke Yamauchi

  8. Research and Development (R&D) Division, Green Energy Institute, Mokpo, Republic of Korea

    Jongbeom Na

  9. Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul, Republic of Korea

    Jongbeom Na

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Contributions

Y.Y. and J.N. proposed the research direction and guided the project. Y.Y. and J.N. developed the protocol. M.K., J.T. and C.Y. performed the experiments. M.K. and J.P.H. drafted the manuscript. J.K., A.K.N. and Y.S. analyzed morphologies. R.K., J.E. and A.A. did formal analysis. All authors contributed to the final writing and editing of the manuscript.

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Correspondence to Jongbeom Na or Yusuke Yamauchi.

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Nature Protocols thanks Srinivas Gadipelli and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Related links

Key papers using this protocol

Young, C. et al. Phys. Chem. Chem. Phys. 18, 29308–29315 (2016): https://doi.org/10.1039/C6CP05555A

Kim, M. et al. ACS Appl. Mater. Interfaces 13, 52034–52043 (2021): https://doi.org/10.1021/acsami.1c09107

Tang, J. et al. J. Am. Chem. Soc. 137, 1572–1580 (2015): https://doi.org/10.1021/ja511539a

Kim, M. et al. ACS Appl. Mater. Interfaces 12, 34065–34073 (2020): https://doi.org/10.1021/acsami.0c07467

Extended data

Extended Data Fig. 1 Schematic illustration of different methods and their brief procedures to prepare porous carbon precursors.

a, Template-free method. b, Hard-template method. c, Soft-template method.

Extended Data Fig. 2 Scanning electron microscopy image of ZIF-8 of different particle sizes.

a, ZIF-8 of 50 nm in diameter. b, ZIF-8 of 120 nm in diameter. c, ZIF-8 of 200 nm in diameter. Scale bars in a–c: 100 nm. d, ZIF-8 of 500 nm in diameter. e, ZIF-8 of 1.5 µm in diameter. f, ZIF-8 of 4 µm in diameter. Scale bars in d–f: 2 µm. a, d and f adapted with permission from Tang, J. et al. Thermal conversion of core–shell metal–organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon. J. Am. Chem. Soc. 137, 1572–1580 (2015). Copyright 2015 American Chemical Society. b adapted with permission from Kim, M. et al. KOH activated hollow ZIF-8 derived porous carbon: nanoarchitectured control for upgraded capacitive deionization and supercapacitor. ACS Appl. Mater. Interfaces 13, 52034–52043 (2021). Copyright 2021 American Chemical Society. c adapted with permission from Kim, M. et al. Tailored nanoarchitecturing of microporous ZIF-8 to hierarchically porous double-shell carbons and their intrinsic electrochemical property. ACS Appl. Mater. Interfaces 12, 34065–34073 (2020). Copyright 2020 American Chemical Society. e adapted from ref. 45 with permission from the PCCP Owner Societies.

Extended Data Fig. 3 Physical characterization of ZIF-8 and mPDA-coated ZIF-8.

a, X-ray diffraction; b, XPS spectra; c, N2 adsorption-desorption isotherms; and d, NLDFT pore-size distributions of ZIF-8, ZIF-8@mPDA-2.5 and ZIF-8@mPDA-5.0. Adapted with permission from Kim, M. et al. Tailored nanoarchitecturing of microporous ZIF-8 to hierarchically porous double-shell carbons and their intrinsic electrochemical property. ACS Appl. Mater. Interfaces 12, 34065–34073 (2020). Copyright 2020 American Chemical Society.

Extended Data Fig. 4 Device-level demonstration of a symmetric supercapacitor by using NPC as electrode material.

a, Photograph of assembled HS test cell, schematic illustration of its cross-sectional view and SEM image of NPC on the current collector. b, Gravimetric capacitance of NPC-800, NPC-900, NPC-1,000 and activated carbon. c, Mean volumetric capacitance at 0.1 A/g (left) and mean retention of volumetric capacitance from 0.1 to 2 A/g (right) of NPC-800, NPC-900, NPC-1,000 and activated carbon, with the whiskers showing the range of data obtained from five different cells.

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Supplementary Method 1, Supplementary Tables 1 and 2 and Supplementary References.

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Pore size distribution of HPC-2.5 and HPC-5.0 (https://doi.org/10.6084/m9.figshare.18515858.v1)

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Kim, M., Xin, R., Earnshaw, J. et al. MOF-derived nanoporous carbons with diverse tunable nanoarchitectures. Nat Protoc 17, 2990–3027 (2022). https://doi.org/10.1038/s41596-022-00718-2

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