Emulsion templating presently extends far beyond the original hydrophobic porous polymers that were synthesized within surfactant-stabilized water-in-oil high internal phase emulsions (HIPEs) by using free radical polymerization. This Perspective presents the extraordinary versatility of emulsion templating that has emerged with the growing numbers of HIPE systems, HIPE stabilization strategies, monomers, polymerization chemistries, multicomponent materials, and surface functionalities. Emulsion templating now goes far beyond "porous polymers" by encompassing the encapsulation of aqueous solutions, ionic melts, and organic liquids as well as by encompassing porous carbons and porous inorganics. Herein, we present comprehensive pictures of the state-of-the-art, of the prospective large-scale and niche applications, of the advantages and challenges for industrial scale-up, and of the crucial directions that should be pursued in future work. We demonstrate that it is emulsion templating's considerable and versatile parameter space that offers opportunities for pioneering work, breakthrough innovations, scientific/engineering achievements, and industrial adoption.

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Hierarchically porous polymers combine microporosity, mesoporosity, and macroporosity to enhance pore accessibility and transport. This work describes generating hierarchically porous polymers and carbons derived therefrom by combining emulsion-templated macroporous polymers bearing novel macromolecular structures with simultaneous Friedel−Crafts hyper-cross-linking and porogen removal. The hyper-cross-linking was based on a copolymer of vinylbenzyl chloride and divinylbenzene, while the porogen was based on poly(εcaprolactone) (PCL). The two polymer systems were combined using one-pot syntheses of either simultaneous interpenetrating polymer networks (IPNs) containing a PCL-based poly(urethane urea) (PUU) or a PCL-based semi-IPN. In the semi-IPN, the microporosity was enhanced through hyper-cross-linking and through porogen removal during carbonization. The effects of incorporating a PCL-based PUU depended upon the diisocyanate. Unexpectedly, mesoporosity was generated from hyper-cross-linking an IPN synthesized with an aliphatic diisocyanate. On the other hand, the formation of interconnected networks from hyper-cross-linking an IPN synthesized with an aromatic diisocyanate enhanced both the microporosity and thermal stability.

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