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.
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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