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Solution-based self-assembly synthesis of two-dimensional-ordered mesoporous conducting polymer nanosheets with versatile properties

Nature Protocols volume 18, pages 2459–2484 (2023)Cite this article

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Abstract

Conducting polymers with conjugated backbones have been widely used in electrochemical energy storage, catalysts, gas sensors and biomedical devices. In particular, two-dimensional (2D) mesoporous conducting polymers combine the advantages of mesoporous structure and 2D nanosheet morphology with the inherent properties of conducting polymers, thus exhibiting improved electrochemical performance. Despite the use of bottom-up self-assembly approaches for the fabrication of a variety of mesoporous materials over the past decades, the synchronous control of the dimensionalities and mesoporous architectures for conducting polymer nanomaterials remains a challenge. Here, we detail a simple, general and robust route for the preparation of a series of 2D mesoporous conducting polymer nanosheets with adjustable pore size (5–20 nm) and thickness (13–45 nm) and controllable morphology and composition via solution-based self-assembly. The synthesis conditions and preparation procedures are detailed to ensure the reproducibility of the experiments. We describe the fabrication of over ten high-quality 2D-ordered mesoporous conducting polymers and sandwich-structured hybrids, with tunable thickness, porosity and large specific surface area, which can serve as potential candidates for high-performance electrode materials used in supercapacitors and alkali metal ion batteries, and so on. The preparation time of the 2D-ordered mesoporous conducting polymer is usually no more than 12 h. The subsequent supercapacitor testing takes ~24 h and the Na ion battery testing takes ~72 h. The procedure is suitable for users with expertise in physics, chemistry, materials and other related disciplines.

Key points

  • The synthesis of two-dimensional mesoporous conducting polymer nanosheets, completed in aqueous solution at room temperature, entails micellar formation, followed by their ordered self-assembly on soft two-dimensional templates, the adsorption of monomers, the in situ polymerization of conducting polymer monomers and the removal of the templates.

  • The process is more flexible, tunable and cheaper than the alternative based on the reverse replication of hard templates.

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Fig. 1: Schematic diagram of 2D-ordered mesoporous CP nanosheets (top) and picture of the synthesis process of the mPPy@GO sandwich-structured hybrid (bottom).
Fig. 2: Illustration of the experimental setup.
Fig. 3: Schematic illustration of the construction of a mesoporous CP layer on 2D functionalized surfaces.
Fig. 4: Construct the mesoporous polymer layer on other functionalized free-standing surfaces.
Fig. 5: Illustration of the mPANi nanosheets.
Fig. 6: Structural characterizations of mPPy@GO nanosheets.
Fig. 7: Images of the mPPy@GO nanosheets.
Fig. 8: Electrochemical performance of 2D mPPy@GO nanosheets.
Fig. 9: Morphology and structure of mPPy nanosheets.
Fig. 10: Na ion battery performance of the mPPy nanosheets.
Fig. 11: Morphology and structure of mPANi nanosheets.
Fig. 12: Images of the mPANi nanosheets.

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Data availability

All data supporting the findings of this study are included in the article and the references listed in the Supplementary Information. Source data for the figures in this study are available at https://doi.org/10.6084/m9.figshare.22550017.

References

  1. Shirakawa, H. et al. Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x. J. Chem. Soc. Chem. Commun. 16, 578–580 (1977).

  2. Jia, S. et al. Hierarchical metal-polymer hybrids for enhanced CO2 electroreduction. Angew. Chem. Int. Ed. 60, 10977–10982 (2021).

    Article  CAS  Google Scholar 

  3. Liu, S. et al. Carbonized polyaniline activated peroxymonosulfate (PMS) for phenol degradation: role of PMS adsorption and singlet oxygen generation. Appl. Catal. B 286, 119921 (2021).

    Article  CAS  Google Scholar 

  4. Nezakati, T. et al. Conductive polymers: opportunities and challenges in biomedical applications. Chem. Rev. 118, 6766–6843 (2018).

    Article  CAS  PubMed  Google Scholar 

  5. Xu, X. et al. Thermal transport in conductive polymer-based materials. Adv. Funct. Mater. 30, 1904704 (2020).

    Article  CAS  Google Scholar 

  6. Luo, H. et al. Nanoarchitectured porous conducting polymers: from controlled synthesis to advanced applications. Adv. Mater. 33, 2007318 (2021).

    Article  CAS  Google Scholar 

  7. Qin, J. et al. Hierarchical ordered dual-mesoporous polypyrrole/graphene nanosheets as bi-functional active materials for high-performance planar integrated system of micro-supercapacitor and gas sensor. Adv. Funct. Mater. 30, 1909756 (2020).

    Article  CAS  Google Scholar 

  8. Tian, H. et al. General interfacial self-assembly engineering for patterning two-dimensional polymers with cylindrical mesopores on graphene. Angew. Chem. Int. Ed. Engl. 58, 10173–10178 (2019).

    Article  CAS  PubMed  Google Scholar 

  9. Yin, F. et al. Synthesis of mesoporous hollow polypyrrole spheres and the utilization as supports of high loading of Pt nanoparticles. Mater. Lett. 207, 225–229 (2017).

    Article  CAS  Google Scholar 

  10. Wang, Q. et al. Mesoporous polyaniline film on ultra-thin graphene sheets for high performance supercapacitors. J. Power Sources 247, 197–203 (2014).

    Article  CAS  Google Scholar 

  11. Wu, S. et al. Synthesis of mesoporous silica nanoparticles. Chem. Soc. Rev. 42, 3862–3875 (2013).

    Article  CAS  PubMed  Google Scholar 

  12. Park, S. et al. Hollow mesoporous functional hybrid materials: fascinating platforms for advanced applications. Adv. Funct. Mater. 28, 1703814 (2018).

    Article  Google Scholar 

  13. Ren, Y. et al. Ordered mesoporous metal oxides: synthesis and applications. Chem. Soc. Rev. 41, 4909–4927 (2012).

    Article  CAS  PubMed  Google Scholar 

  14. Malgras, V. et al. Coalescence-driven verticality in mesoporous TiO2 thin films with long-range ordering. J. Am. Chem. Soc. 142, 15815–15822 (2020).

    Article  CAS  PubMed  Google Scholar 

  15. Guo, B. et al. Controlled synthesis of porous carbon nanostructures with tunable closed mesopores via a silica-assisted coassembly strategy. CCS Chem. 3, 1410–1422 (2021).

    Article  CAS  Google Scholar 

  16. Dai, F. et al. Bottom-up synthesis of high surface area mesoporous crystalline silicon and evaluation of its hydrogen evolution performance. Nat. Commun. 5, 3605 (2014).

    Article  PubMed  Google Scholar 

  17. Zhao, T. et al. Interfacial assembly directed unique mesoporous architectures: from symmetric to asymmetric. Acc. Mater. Res. 1, 100–114 (2020).

    Article  CAS  Google Scholar 

  18. Li, Q. et al. Ordered bicontinuous mesoporous polymeric semiconductor photocatalyst. ACS Nano 14, 13652–13662 (2020).

    Article  CAS  PubMed  Google Scholar 

  19. Fang, Y. et al. Growth of single-layered two‐dimensional mesoporous polymer/carbon films by self‐assembly of monomicelles at the interfaces of various substrates. Angew. Chem. Int. Ed. 127, 8545–8549 (2015).

    Article  Google Scholar 

  20. Novoselov, K. S. et al. Room-temperature quantum Hall effect in graphene. Science 315, 1379–1379 (2007).

    Article  CAS  PubMed  Google Scholar 

  21. Li, W. et al. Phase transitions in 2D materials. Nat. Rev. Mater. 6, 829–846 (2021).

    Article  CAS  Google Scholar 

  22. Schulman, D. et al. Contact engineering for 2D materials and devices. Chem. Soc. Rev. 47, 3037–3058 (2018).

    Article  CAS  PubMed  Google Scholar 

  23. Boota, M. et al. Pseudocapacitive electrodes produced by oxidant‐free polymerization of pyrrole between the layers of 2D titanium carbide (MXene). Adv. Mater. 28, 1517–1522 (2016).

    Article  CAS  PubMed  Google Scholar 

  24. Wang, X. et al. Ultrathin polypyrrole nanosheets via space-confined synthesis for efficient photothermal therapy in the second near-infrared window. Nano Lett. 18, 2217–2225 (2018).

    Article  CAS  PubMed  Google Scholar 

  25. Wang, J. et al. Electrochemical energy storage performance of 2D nanoarchitectured hybrid materials. Nat. Commun. 12, 3563 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Tian, H. et al. Growth of 2D mesoporous polyaniline with controlled pore structures on ultrathin MoS2 nanosheets by block copolymer self-assembly in solution. ACS Appl. Mater. Interfaces 9, 43975–43982 (2017).

    Article  CAS  PubMed  Google Scholar 

  27. Liu, Z. et al. High power in‐plane micro‐supercapacitors based on mesoporous polyaniline patterned graphene. Small 13, 1603388 (2017).

    Article  Google Scholar 

  28. Zhang, Y. et al. Charge‐enriched strategy based on MXene-based polypyrrole layers toward dendrite-free zinc metal anodes. Adv. Energy Mater. 12, 2103979 (2022).

    Article  CAS  Google Scholar 

  29. Li, X. et al. Synthesis of graphene films on copper foils by chemical vapor deposition. Adv. Mater. 28, 6247–6252 (2016).

    Article  CAS  PubMed  Google Scholar 

  30. Yang, H. et al. Free-standing and oriented mesoporous silica films grown at the air-water interface. Nature 381, 589–592 (1996).

    Article  CAS  Google Scholar 

  31. Wei, F. et al. Soft template-mediated coupling construction of sandwiched mesoporous PPy/Ag nanoplates for rapid and selective NH3 sensing. J. Mater. Chem. A 9, 8308–8316 (2021).

    Article  CAS  Google Scholar 

  32. Qin, J. et al. Achieving stable Na metal cycling via polydopamine/multilayer graphene coating of a polypropylene separator. Nat. Commun. 12, 5786 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  33. Shi, H. et al. A two-dimensional mesoporous polypyrrole-graphene oxide heterostructure as a dual-functional ion redistributor for dendrite-free lithium metal anodes. Angew. Chem. Int. Ed. 132, 12245–12251 (2020).

    Article  Google Scholar 

  34. Li, W. et al. Ordered mesoporous materials based on interfacial assembly and engineering. Adv. Mater. 25, 5129–5152 (2013).

    Article  CAS  PubMed  Google Scholar 

  35. Liu, S. et al. Patterning two-dimensional free-standing surfaces with mesoporous conducting polymers. Nat. Commun. 6, 8817 (2015).

    Article  CAS  PubMed  Google Scholar 

  36. Liu, S. et al. Dual‐template synthesis of 2D mesoporous polypyrrole nanosheets with controlled pore size. Adv. Mater. 28, 8365–8370 (2016).

    Article  CAS  PubMed  Google Scholar 

  37. Liu, S. et al. Two‐dimensional mesoscale-ordered conducting polymers. Angew. Chem. Int. Ed. 128, 12704–12709 (2016).

    Article  Google Scholar 

  38. Wen, Y. et al. Constructing polymers towards ultrathin nanosheets with dual mesopores and intrinsic photoactivity. Chem. Commun. 56, 3191–3194 (2020).

    Article  CAS  Google Scholar 

  39. Ai, Y. et al. General construction of 2D ordered mesoporous iron-based metal-organic nanomeshes. Small 16, 2002701 (2020).

    Article  CAS  Google Scholar 

  40. Wei, F. et al. Controllably engineering mesoporous surface and dimensionality of SnO2 toward high‐performance CO2 electroreduction. Adv. Funct. Mater. 30, 2002092 (2020).

    Article  CAS  Google Scholar 

  41. Wei, D. et al. A nanostructured electrochromic supercapacitor. Nano Lett. 12, 1857–1862 (2012).

    Article  CAS  PubMed  Google Scholar 

  42. Meng, Q. et al. Research progress on conducting polymer based supercapacitor electrode materials. Nano Energy 36, 268–285 (2017).

    Article  CAS  Google Scholar 

  43. Hua, M. et al. Tough-hydrogel reinforced low-tortuosity conductive networks for stretchable and high-performance supercapacitors. Adv. Mater. 33, 2100983 (2021).

    Article  CAS  Google Scholar 

  44. Zhao, Z. et al. Designing flexible, smart and self-sustainable supercapacitors for portable/wearable electronics: from conductive polymers. Chem. Soc. Rev. 50, 12702–12743 (2021).

    Article  CAS  PubMed  Google Scholar 

  45. Kurra, N. et al. Conducting polymer micro-supercapacitors for flexible energy storage and Ac line-filtering. Nano Energy 13, 500–508 (2015).

    Article  CAS  Google Scholar 

  46. Goikolea, E. et al. Na‐ion batteries—approaching old and new challenges. Adv. Energy Mater. 10, 2002055 (2020).

    Article  CAS  Google Scholar 

  47. Xiang, X. et al. Recent advances and prospects of cathode materials for sodium‐ion batteries. Adv. Mater. 27, 5343–5364 (2015).

    Article  CAS  PubMed  Google Scholar 

  48. Deng, Y. et al. Ordered mesoporous silicas and carbons with large accessible pores templated from amphiphilic diblock copolymer poly (ethylene oxide)-b-polystyrene. J. Am. Chem. Soc. 129, 1690–1697 (2007).

    Article  CAS  PubMed  Google Scholar 

  49. Parviz, D. et al. Dispersions of non-covalently functionalized graphene with minimal stabilizer. ACS Nano 6, 8857–8867 (2012).

    Article  CAS  PubMed  Google Scholar 

  50. Shimizu, T. et al. Supramolecular nanotube architectures based on amphiphilic molecules. Chem. Rev. 105, 1401–1444 (2005).

    Article  CAS  PubMed  Google Scholar 

  51. Liu, S. et al. Soft-template construction of 3D macroporous polypyrrole scaffolds. Small 13, 1604099 (2017).

    Article  Google Scholar 

  52. Parvez, K. et al. Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J. Am. Chem. Soc. 136, 6083–6091 (2014).

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant nos. 51773062 and 61831021) and the ERC Grant on 2DMATER.

Author information

Authors and Affiliations

  1. State Key Laboratory of Precision Spectroscopy; Engineering Research Center for Nanophotonics & Advanced Instrument (Ministry of Education), School of Physics and Electronic Science, East China Normal University, Shanghai, P.R. China

    Facai Wei, Tingting Zhang, Yong Wu, Wenda Li, Chengbin Jing & Shaohua Liu

  2. Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Renhao Dong & Xinliang Feng

  3. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, P.R. China

    Jianwei Fu

  4. State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, P.R. China

    Jiangong Cheng

  5. Max Planck Institute of Microstructure Physics, Halle (Saale), Germany

    Xinliang Feng

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Contributions

S.L. and X.F. conceived and designed the experiments. S.L. performed the experiments. R.D. assisted the experiments. F.W., T.Z., Y.W. and W.L. drafted the manuscript and developed the protocol. All of the authors discussed the experiments and co-wrote the manuscript.

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Correspondence to Jiangong Cheng, Xinliang Feng or Shaohua Liu.

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Key references using this protocol

Liu, S. et al. Nat. Commun. 6, 8817 (2015): https://doi.org/10.1038/ncomms9817

Liu, S. et al. Adv. Mater. 28, 8365–8370 (2016): https://doi.org/10.1002/adma.201603036

Liu, S. et al. Angew. Chem. Int. Ed. 128, 12704–12709 (2016): https://doi.org/10.1002/ange.201606988

Supplementary information

Supplementary Information

Supplementary Table 1.

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Wei, F., Zhang, T., Dong, R. et al. Solution-based self-assembly synthesis of two-dimensional-ordered mesoporous conducting polymer nanosheets with versatile properties. Nat Protoc 18, 2459–2484 (2023). https://doi.org/10.1038/s41596-023-00845-4

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