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Nacre-inspired underwater superoleophobic films with high transparency and mechanical robustness

Abstract

Underwater superoleophobic materials have attracted increasing attention because of their remarkable potential applications, especially antifouling, self-cleaning and oil–water separation. A limitation of most superoleophobic materials is that they are non-transparent and have limited mechanical stability underwater. Here, we report a protocol for preparing a transparent and robust superoleophobic film that can be used underwater. It is formed by a hydrogel layer prepared by the superspreading of chitosan solution on a superhydrophilic substrate and biomimetic mineralization of this layer. In contrast to conventional hydrogel-based materials, this film exhibits significantly improved mechanical properties because of the combination of high-energy, ordered, inorganic aragonite (one crystalline polymorph of calcium carbonate) and homogeneous external hierarchical micro/nano structures, leading to robust underwater superoleophobicity and ultralow oil adhesion. Moreover, the mineralized film is suitable for neutral and alkaline environments and for containing organic solvent underwater and can be coated on different transparent materials, which has promising applications in underwater optics, miniature reactors and microfluidic devices. In this protocol, the time for the whole biomimetic mineralization process is only ~6 h, which is significantly shorter than that of traditional methods, such as gas diffusion and the Kitano method. The protocol can be completed in ~2 weeks and is suitable for researchers with intermediate expertise in organic chemistry and inorganic chemistry.

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Fig. 1: Schematic of the fabrication procedure of the nacre-inspired mineralized (NIM) film based on superspreading and biomimetic mineralization.
Fig. 2: The NIM film is similar to natural nacre in both chemical composition and physical structure.
Fig. 3: Morphology characterization of the NIM film.
Fig. 4: Transparency of NIM films and their potential applications as underwater transparent oil-repellent coatings.
Fig. 5: NIM coatings for oil–water separation.
Fig. 6: The NIM coating for anti-oil in microfluidic channels.
Fig. 7: Chemical stability of the NIM film.
Fig. 8: The influence of biomimetic mineralization on surface wettability and underwater oil adhesion.
Fig. 9: Mechanically robust underwater superoleophobicity of NIM films.

Data availability

The main data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

We acknowledge support from the Key Research Program of the Chinese Academy of Sciences (XDPB24), the National Natural Science Foundation of China (21875269, 22035008, 31771026 and 51403158) and the International Partnership Program of the Chinese Academy of Sciences (1A1111KYSB20200010).

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Contributions

W.C., S.W., B.W. and J.M. conceived and designed the experiments. W.C., P.Z., S.Y., R.Z. and L.X. performed experiments. W.C., P.Z., S.W. and J.M. analyzed and interpreted the data, developed the methodology and wrote the manuscript. S.W., B.W. and J.M. performed data interpretation, method development and editing of the manuscript.

Corresponding authors

Correspondence to Shutao Wang, Bailiang Wang or Jingxin Meng.

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Key references using this protocol

Chen, W. et al. Adv. Mater. 32, 1907413 (2020): https://doi.org/10.1002/adma.201907413

Yu, S. et al. Adv. Mater. Interfaces 8, 2100852 (2021): https://doi.org/10.1002/admi.202100852

Key data used in this protocol

Chen, W. et al. Adv. Mater. 32, 1907413 (2020): https://doi.org/10.1002/adma.201907413

Yu, S. et al. Adv. Mater. Interfaces 8, 2100852 (2021): https://doi.org/10.1002/admi.202100852

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Chen, W., Zhang, P., Yu, S. et al. Nacre-inspired underwater superoleophobic films with high transparency and mechanical robustness. Nat Protoc 17, 2647–2667 (2022). https://doi.org/10.1038/s41596-022-00725-3

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