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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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A polyHIPE is a highly porous polymer synthesized from monomers within the external phase of a high internal phase emulsion (HIPE). The large amount of difficult to remove surfactant needed for HIPE stabilization can affect the properties of the resulting polymer. A Pickering emulsion is a surfactant‐free emulsion stabilized by solid particles that preferentially migrate to the interface. In this article, the synthesis of crosslinked polyacrylate polyHIPEs based on Pickering HIPEs stabilized using silane‐modified silica nanoparticles is described and the effects of the synthesis parameters on the porous structure are discussed. The silane chemistry, silane content, and nanoparticle content had significant effects on the size of the polyhedral, relatively closed‐cell polyHIPE voids that resulted from aqueous‐phase initiation. Increasing the mixing intensity reduced the wall thickness and produced a more open‐cell structure. The locus of initiation had a significant effect on polyHIPE morphology. Organic‐phase initiation yielded larger, more spherical voids from the more extensive coalescence before the structure could be “locked‐in” at the gel point. Most significantly, the nanoparticles were located within the polymer walls rather than at the interface, as might be expected. The void walls were shown to be an assembly of nanoparticle agglomerate shells that become embedded within the polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1516–1525, 2010

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