Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

Creation of porous polymeric membranes by accumulation of water nanodroplets in a miniemulsion system

Abstract

We developed a miniemulsion templating method to prepare porous polymeric membranes. First, water nanodroplets were suspended in an oil phase by using a nonionic and polymeric surfactant to form a water-in-oil (W/O) miniemulsion. After the nanodroplets accumulated by centrifugation, a small amount of monomer was added as an oil phase to resuspend the water nanodroplets in a monomer phase. Then, photopolymerization of the monomer phase was conducted to generate pores in the polymeric matrix. The size of the nanodroplets was tuned by the surfactant concentration to control the pore size of the membranes. We could produce pore morphologies such as closed-cellular, open-cellular, and bicontinuous structures by tuning the volume fraction of the nanodroplets. Alternatively, nanodroplets were accumulated by centrifugation, and then further surfactants were added to the monomer to suppress the coalescence of nanodroplets. This enabled us to generate a highly porous open-cellular structure while maintaining the size and spherical shape. Next, HAuCl4 was reduced by using the surfactant displayed at the inner surface of the pore wall as the reducing agent. Gold nanoparticles were produced in the inner pores of the polymeric membrane, showing coloration derived from local surface plasmon resonance.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Scheme 1
Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Wu DC, Xu F, Sun B, Fu RW, He HK, Matyjaszewski K. Design and preparation of porous polymers. Chem Rev. 2012;112:3959–4015.

    Article  CAS  Google Scholar 

  2. Okada K, Nandi M, Maruyama J, Oka T, Tsujimoto T, Kondoh K, et al. Fabrication of mesoporous polymer monolith: a template-free approach. Chem Commun. 2011;47:7422–4.

    Article  CAS  Google Scholar 

  3. Feinle A, Elsaesser MS, Husing N. Sol–gel synthesis of monolithic materials with hierarchical porosity. Chem Soc Rev. 2016;45:3377–99.

    Article  CAS  Google Scholar 

  4. Burgess IB, Loncar M, Aizenberg J. Structural colour in colourimetric sensors and indicators. J Mater Chem C. 2013;1:6075–86.

    Article  CAS  Google Scholar 

  5. Phillips KR, England GT, Sunny S, Shirman E, Shirman T, Vogel N, Aizenberg J. A colloidoscope of colloid-based porous materials and their uses. Chem Soc Rev. 2016;45:281–322.

    Article  CAS  Google Scholar 

  6. Silverstein MS. PolyHIPEs: recent advances in emulsion-templated porous polymers. Prog Polym Sci. 2014;39:199–234.

    Article  CAS  Google Scholar 

  7. Zhang T, Sanguramath RA, Israel S, Silverstein MS. Emulsion templating: porous polymers and beyond. Macromolecules. 2019;52:5445–79.

    Article  CAS  Google Scholar 

  8. Barbetta A, Cameron NR. Morphology and surface area of emulsion-derived (PolyHIPE) solid foams prepared with oil-phase soluble porogenic solvents: Span 80 as surfactant. Macromolecules. 2004;37:3188–201.

    Article  CAS  Google Scholar 

  9. Luo YW, Wang AN, Gao X. Miniemulsion template polymerization to prepare a sub-micrometer porous polymeric monolith with an inter-connected structure and very high mechanical strength. Soft Matter. 2012;8:7547–51.

    Article  CAS  Google Scholar 

  10. Antonietti M, Landfester K. Polyreactions in miniemulsions. Prog Polym Sci. 2002;27:689–757.

    Article  CAS  Google Scholar 

  11. Landfester K. Synthesis of colloidal particles in miniemulsions. Annu Rev Mater Res. 2006;36:231–79.

    Article  CAS  Google Scholar 

  12. Fukui Y, Takamatsu H, Fujimoto K. Creation of hybrid polymer particles through morphological tuning of CaCO3 crystals in miniemulsion system. Colloids Surf A Physicochemical Eng Asp. 2017;516:1–8.

    Article  CAS  Google Scholar 

  13. Livshin S, Silverstein MS. Enhancing hydrophilicity in a hydrophobic porous emulsion-templated polyacrylate. J Polym Sci A Polym Chem. 2009;47:4840–5.

    Article  CAS  Google Scholar 

  14. Lei L, Zhang Q, Shi SX, Zhu SP. Highly porous poly(high internal phase emulsion) membranes with “open-cell” structure and CO2-switchable wettability used for controlled Oil/Water separation. Langmuir. 2017;33:11936–44.

    Article  CAS  Google Scholar 

  15. White RJ, Luque R, Budarin VL, Clark JH, Macquarrie DJ. Supported metal nanoparticles on porous materials. Methods and applications. Chem Soc Rev. 2009;38:481–94.

    Article  CAS  Google Scholar 

  16. Sarkar S, Guibal E, Quignard F, SenGupta AK. Polymer-supported metals and metal oxide nanoparticles: synthesis, characterization, and applications. J Nanoparticle Res. 2012;14:1–24.

  17. Ye YL, Jin M, Wan DC. One-pot synthesis of porous monolith-supported gold nanoparticles as an effective recyclable catalyst. J Mater Chem A. 2015;3:13519–25.

    Article  CAS  Google Scholar 

  18. Liu Y, Guerrouache M, Kebe SI, Carbonnier B, Le Droumaguet B. Gold nanoparticles-supported histamine-grafted monolithic capillaries as efficient microreactors for flow-through reduction of nitro-containing compounds. J Mater Chem A. 2017;5:11805–14.

    Article  CAS  Google Scholar 

  19. Khalil AM, Georgiadou V, Guerrouache M, Mahouche-Chergui S, Dendrinou-Samara C, Chehimi MM, Carbonnier B. Gold-decorated polymeric monoliths: In-situ vs ex-situ immobilization strategies and flow through catalytic applications towards nitrophenols reduction. Polymer. 2015;77:218–26.

    Article  CAS  Google Scholar 

  20. Fukui Y, Fujimoto K. Bio-inspired nanoreactor based on a miniemulsion system to create organic-inorganic hybrid nanoparticles and nanofilms. J Mater Chem. 2012;22:3493–9.

    Article  CAS  Google Scholar 

  21. Capek I. On inverse miniemulsion polymerization of conventional water-soluble monomers. Adv Colloid Interface Sci. 2010;156:35–61.

    Article  CAS  Google Scholar 

  22. Landfester K, Willert M, Antonietti M. Preparation of polymer particles in nonaqueous direct and inverse miniemulsions. Macromolecules. 2000;33:2370–6.

    Article  CAS  Google Scholar 

  23. Li CC, Shuford KL, Chen MH, Lee EJ, Cho SO. A facile polyol route to uniform gold octahedra with tailorable size and their optical properties. ACS Nano. 2008;2:1760–9.

    Article  CAS  Google Scholar 

  24. Li CC, Shuford KL, Park QH, Cai WP, Li Y, Lee EJ, Cho SO. High-yield synthesis of single-crystalline gold nano-octahedra. Angew Chem Int Ed. 2007;46:3264–8.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Keiji Fujimoto.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fukui, Y., Fujino, R., Sugaya, Y. et al. Creation of porous polymeric membranes by accumulation of water nanodroplets in a miniemulsion system. Polym J 52, 1077–1083 (2020). https://doi.org/10.1038/s41428-020-0361-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-020-0361-6

Search

Quick links