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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References
Liu, M., Wang, S. & Jiang, L. Nature-inspired superwettability systems. Nat. Rev. Mater. 2, 17036 (2017).
Yong, J., Chen, F., Yang, Q., Huo, J. & Hou, X. Superoleophobic surfaces. Chem. Soc. Rev. 46, 4168–4217 (2017).
Jiang, T., Guo, Z. & Liu, W. Biomimetic superoleophobic surfaces: focusing on their fabrication and applications. J. Mater. Chem. A 3, 1811–1827 (2015).
Ge, M. et al. Rational design of materials interface at nanoscale towards intelligent oil-water separation. Nanoscale Horiz. 3, 235–260 (2018).
Liu, X. et al. Clam’s shell inspired high-energy inorganic coatings with underwater low adhesive superoleophobicity. Adv. Mater. 24, 3401–3405 (2012).
Guo, T., Heng, L., Wang, M., Wang, J. & Jiang, L. Robust underwater oil-repellent material inspired by columnar nacre. Adv. Mater. 28, 8505–8510 (2016).
Cai, Y. et al. Salt-tolerant superoleophobicity on alginate gel surfaces inspired by seaweed (Saccharina japonica). Adv. Mater. 27, 4162–4168 (2015).
Cai, Y. et al. Filefish-inspired surface design for anisotropic underwater oleophobicity. Adv. Funct. Mater. 24, 809–816 (2014).
Wang, C., Zhang, F., Yu, C. & Wang, S. Durable underwater superoleophobic coatings via dispersed micro particle-induced hierarchical structures inspired by pomfret skin. ACS Appl. Mater. Interfaces 12, 42430–42436 (2020).
Liu, M., Wang, S., Wei, Z., Song, Y. & Jiang, L. Bioinspired design of a superoleophobic and low adhesive water/solid interface. Adv. Mater. 21, 665–669 (2009).
Yong, J. et al. Bioinspired transparent underwater superoleophobic and anti-oil surfaces. J. Mater. Chem. A 3, 9379–9384 (2015).
Xu, L. et al. Nacre-inspired design of mechanical stable coating with underwater superoleophobicity. ACS Nano 7, 5077–5083 (2013).
Meng, X. F., Wang, M. M., Heng, L. P. & Jiang, L. Underwater mechanically robust oil-repellent materials: combining conflicting properties using a heterostructure. Adv. Mater. 30, 1706634 (2018).
Teng, C., Xie, D., Wang, J., Zhu, Y. & Jiang, L. A strong, underwater superoleophobic PNIPAM–clay nanocomposite hydrogel. J. Mater. Chem. A 4, 12884–12888 (2016).
Li, M. et al. Seeded mineralization leads to hierarchical CaCO3 thin coatings on fibers for oil/water separation applications. Langmuir 34, 2942–2951 (2018).
Li, W. et al. Microfluidic fabrication of microparticles for biomedical applications. Chem. Soc. Rev. 47, 5646–5683 (2018).
Chen, W. et al. Nacre-inspired mineralized films with high transparency and mechanically robust underwater superoleophobicity. Adv. Mater. 32, 1907413 (2020).
Wu, D. et al. Facile creation of hierarchical PDMS microstructures with extreme underwater superoleophobicity for anti-oil application in microfluidic channels. Lab Chip 11, 3873–3879 (2011).
Su, B., Wang, S., Song, Y. & Jiang, L. Utilizing superhydrophilic materials to manipulate oil droplets arbitrarily in water. Soft Matter 7, 5144–5149 (2011).
Yong, J., Chen, F., Yang, Q. & Hou, X. Femtosecond laser controlled wettability of solid surfaces. Soft Matter 11, 8897–8906 (2015).
Li, F. et al. Bioinspired nonswellable ultrastrong nanocomposite hydrogels with long-term underwater superoleophobic behavior. Chem. Eur. J. 375, 122047 (2019).
Yao, X. et al. Hydrogel paint. Adv. Mater. 31, e1903062 (2019).
Lin, L. et al. Bio-inspired hierarchical macromolecule-nanoclay hydrogels for robust underwater superoleophobicity. Adv. Mater. 22, 4826–4830 (2010).
Li, H. et al. A robust double-network hydrogel with under sea water superoleophobicity fabricated via one-pot, one-step reaction. J. Mater. Chem. B 4, 4662–4666 (2016).
Yao, H. B., Ge, J., Mao, L. B., Yan, Y. X. & Yu, S. H. 25th anniversary article: artificial carbonate nanocrystals and layered structural nanocomposites inspired by nacre: synthesis, fabrication and applications. Adv. Mater. 26, 163–187 (2014).
Addadi, L., Joester, D., Nudelman, F. & Weiner, S. Mollusk shell formation: a source of new concepts for understanding biomineralization processes. Chem. Eur. J. 12, 980–987 (2006).
Gehrke, N. et al. Retrosynthesis of nacre via amorphous precursor particles. Chem. Mater. 17, 6514–6516 (2005).
DeVol, R. T. et al. Nanoscale transforming mineral phases in fresh nacre. J. Am. Chem. Soc. 137, 13325–13333 (2015).
Rudloff, J. & Cölfen, H. Superstructures of temporarily stabilized nanocrystalline CaCO3 particles: morphological control via water surface tension variation. Langmuir 20, 991–996 (2004).
Xu, X., Han, J. T. & Cho, K. Formation of amorphous calcium carbonate thin films and their role in biomineralization. Chem. Mater. 16, 1740–1746 (2004).
Chen, L. et al. Antiplatelet and thermally responsive poly(N-isopropylacrylamide) surface with nanoscale topography. J. Am. Chem. Soc. 131, 10467–10472 (2009).
Zang, D. et al. Interfacial engineering of hierarchically porous NiTi/hydrogels nanocomposites with exceptional antibiofouling surfaces. Adv. Mater. https://doi.org/10.1002/adma.201602869 (2017).
Ding, C. et al. PANI nanowire film with underwater superoleophobicity and potential-modulated tunable adhesion for no loss oil droplet transport. Soft Matter 8, 9064–9068 (2012).
Gao, S. et al. A robust polyionized hydrogel with an unprecedented underwater anti-crude-oil-adhesion property. Adv. Mater. 28, 5307–5314 (2016).
Yu, S. et al. Nacre-inspired biomineralized mesh toward scalable and robust oil–water separation with high efficiency. Adv. Mater. Interfaces 8, 2100852 (2021).
Fan, J. B. et al. Directly coating hydrogel on filter paper for effective oil-water separation in highly acidic, alkaline, and salty environment. Adv. Funct. Mater. 25, 5368–5375 (2015).
Zhang, F. et al. Nanowire-haired inorganic membranes with superhydrophilicity and underwater ultralow adhesive superoleophobicity for high-efficiency oil/water separation. Adv. Mater. 25, 4192–4198 (2013).
Urrios, A. et al. 3D-printing of transparent bio-microfluidic devices in PEG-DA. Lab Chip 16, 2287–2294 (2016).
Romanov, V. et al. FDM 3D printing of high-pressure, heat-resistant, transparent microfluidic devices. Anal. Chem. 90, 10450–10456 (2018).
Yong, J. et al. Bioinspired underwater superoleophobic surface with ultralow oil-adhesion achieved by femtosecond laser microfabrication. J. Mater. Chem. A 2, 8790–8795 (2014).
Sollier, E., Murray, C., Maoddi, P. & Di Carlo, D. Rapid prototyping polymers for microfluidic devices and high pressure injections. Lab Chip 11, 3752–3765 (2011).
Hou, X. et al. Interplay between materials and microfluidics. Nat. Rev. Mater. 2, 17016 (2017).
Kim, M. M., Huang, Y., Choi, K. & Hidrovo, C. H. The improved resistance of PDMS to pressure-induced deformation and chemical solvent swelling for microfluidic devices. Microelectron. Eng. 124, 66–75 (2014).
Xu, L. P. et al. An ion-induced low-oil-adhesion organic/inorganic hybrid film for stable superoleophobicity in seawater. Adv. Mater. 25, 606–611 (2013).
Halldorsson, J. A., Little, S. J., Diamond, D., Spinks, G. & Wallace, G. Controlled transport of droplets using conducting polymers. Langmuir 25, 11137–11141 (2009).
Yong, J., Chen, F., Yang, Q., Jiang, Z. & Hou, X. A review of femtosecond-laser-induced underwater superoleophobic surfaces. Adv. Mater. Interfaces 5, 1701370 (2018).
Gu, Y., Yang, J. & Zhou, S. A facile immersion-curing approach to surface-tailored poly(vinyl alcohol)/silica underwater superoleophobic coatings with improved transparency and robustness. J. Mater. Chem. A 5, 10866–10875 (2017).
Finnemore, A. et al. Biomimetic layer-by-layer assembly of artificial nacre. Nat. Commun. 3, 966 (2012).
Sugawara, A. & Kato, T. Aragonite CaCO3 thin-film formation by cooperation of Mg2+ and organic polymer matrices. Chem. Comm. 2000, 487–488 (2000).
Xu, G., Yao, N., Aksay, I. A. & Groves, J. T. Biomimetic synthesis of macroscopic-scale calcium carbonate thin films. Evidence for a multistep assembly process. J. Am. Chem. Soc. 120, 11977–11985 (1998).
Kitano, Y., Park, K. & Hood, D. W. Pure aragonite synthesis. J. Geophys. Res. 67, 4873–4874 (1962).
Kotachi, A., Miura, T. & Imai, H. Polymorph control of calcium carbonate films in a poly(acrylic acid)-chitosan system. Cryst. Growth Des. 6, 1636–1641 (2006).
Xiao, C. et al. Total morphosynthesis of biomimetic prismatic-type CaCO3 thin films. Nat. Commun. 8, 1398 (2017).
Raut, H. K. et al. Tough and strong: cross-lamella design imparts multifunctionality to biomimetic nacre. ACS Nano 14, 9771–9779 (2020).
Munro, N. H., Green, D. W. & McGrath, K. M. In situ continuous growth formation of synthetic biominerals. Chem. Commun. 49, 3407–3409 (2013).
Mao, L. B. et al. Synthetic nacre by predesigned matrix-directed mineralization. Science 354, 107–110 (2016).
Liu, Y. et al. Evaluation of the attachment, proliferation, and differentiation of osteoblast on a calcium carbonate coating on titanium surface. Mater. Sci. Eng. C. 31, 1055–1061 (2011).
Muderrisoglu, C. et al. Nanostructured biointerfaces based on bioceramic calcium carbonate/hydrogel coatings on titanium with an active enzyme for stimulating osteoblasts growth. Adv. Mater. Interfaces 5, 1800452 (2018).
Li, B. et al. Hydrosoluble, UV-crosslinkable and injectable chitosan for patterned cell-laden microgel and rapid transdermal curing hydrogel in vivo. Acta Biomater. 22, 59–69 (2015).
Oaki, Y., Kajiyama, S., Nishimura, T., Imai, H. & Kato, T. Nanosegregated amorphous composites of calcium carbonate and an organic polymer. Adv. Mater. 20, 3633–3637 (2008).
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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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.
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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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DOI: https://doi.org/10.1038/s41596-022-00725-3
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