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Monomicellar assembly to synthesize structured and functional mesoporous carbonaceous nanomaterials

Nature Protocols volume 18, pages 1155–1178 (2023)Cite this article

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Abstract

The large pores of functional mesoporous carbonaceous nanomaterials have broad accessibility, making them efficient substrates for the mass transport of chemicals in biomedical applications, gas separation, catalysis, sensing, and energy storage and conversion. Recently, the assembly of monomicelles has been used to control the nanostructure and mesoporosity of carbonaceous nanomaterials, where the structure-oriented unit is a single micelle made up of block copolymers/surfactants and of precursor species (via hydrogen bonds, Coulombic and/or other noncovalent interactions). Each monomicelle then represents a template for a single mesopore, and multiple monomicelles can be stacked like LEGO blocks. After polymerization of the precursor species (in this case dopamine), carbonization results in the carbonaceous nanomaterial. The micellar size, structure and shape can be easily tuned by altering the synthetic conditions, providing a high degree of control over the structure of the final product, which can therefore be shaped into original nanostructures otherwise difficult to synthesize using conventional templating methods. Here we provide a detailed procedure for the preparation of the monomicelles, the monomicellar assembly into mesostructured polymeric samples and the conversion of polymeric samples to carbonaceous frameworks. We describe the functional characterization of two mesoporous carbonaceous nanomaterials that demonstrate excellent sodium-ion storage performance and oxygen reduction reactivity, respectively. The monomicellar assembly process for the synthesis of the ordered mesoporous polymers requires ~5 h; the synthesis, including subsequent centrifugation, freeze drying and carbonization, requires 2 d, whereas the entire procedure, including the characterization of the nanomaterials, requires ~4 d.

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Fig. 1: The principal formation mechanisms for the synthesis of mesoporous carbonaceous nanomaterials.
Fig. 2: Photographs and corresponding models of the synthesis stages of the mesoporous carbonaceous nanomaterials.
Fig. 3: Template-directed pore structures obtained in mesoporous carbon nanospheres.
Fig. 4: Dependences of pore size of the mesoporous carbon nanospheres on the hydrophobic organic molecules.
Fig. 5: Dependences of the pore location for the mesoporous carbon nanospheres on the stirring rate.
Fig. 6: Spectroscopic characterizations of the mesoPDA nanospheres.
Fig. 7: Variability of the monomicellar assembly approach.
Fig. 8: Physicochemical characterizations of the mesoporous carbon nanospheres.
Fig. 9: Sodium-ion storage study of the mesoporous carbon nanospheres.
Fig. 10: ORR study of the mesoporous carbon nanospheres.

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All data supporting the findings of this study are included in the article and its Supplementary Information.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0209401, 2018YFE0201701 and 2017YFA0207303), National Natural Science Foundation of China (grant nos. 22105041, 21733003 and U21A20329 21975050), Program of Shanghai Academic Research Leader (21XD1420800) and Shanghai Pilot Program for Basic Research-Fudan University 21TQ1400100 (21TQ008) and Science and Technology Commission of Shanghai Municipality (19JC1410700).

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Authors and Affiliations

  1. Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, iChEM and State Key Laboratory of Molecular Engineering of Polymers, College of Chemistry and Materials, Fudan University, Shanghai, P. R. China

    Liang Peng, Huarong Peng, Wei Li & Dongyuan Zhao

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  2. Huarong Peng
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L.P., W.L. and D.Z. developed the protocol and co-drafted the manuscript. H.P. contributed to the discussion and manuscript modification.

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Correspondence to Wei Li or Dongyuan Zhao.

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Key reference using this protocol

Zhao, T. et al. J. Am. Chem. Soc. 140, 10009–10015 (2018): https://doi.org/10.1021/jacs.8b06127

Zhu, X. et al. J. Mater. Chem. A 7, 8975–8983 (2019): https://doi.org/10.1039/C9TA01478K

Peng, L. et al. J. Am. Chem. Soc. 141, 7073–7080 (2019): https://doi.org/10.1021/jacs.9b02091

Peng, L. et al. Sci. Adv. 7, eabi7403 (2021): https://www.science.org/doi/10.1126/sciadv.abi7403

Peng, L. et al. Chem 7, 1020–1032 (2021): https://doi.org/10.1016/j.chempr.2021.01.001

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Peng, L., Peng, H., Li, W. et al. Monomicellar assembly to synthesize structured and functional mesoporous carbonaceous nanomaterials. Nat Protoc 18, 1155–1178 (2023). https://doi.org/10.1038/s41596-022-00784-6

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