Selective infusion-templated polymerization in nanostructured organogels for ordered mesoporous materials

Abstract

Monolithic ordered mesoporous carbon materials with tunable porosity have drawn considerable attention for applications in energy storage, catalysis, and molecular separation attributed to their extraordinary physicochemical properties. Traditional fabrication methods have relied on hard templating in nano-molds that suffers from inefficient filling, or co-assembly with structure-directing agents that have sensitive composition-morphology correlations. Herein, we report selective infusion templating (SIT) inside ordered gels to achieve composition-insensitive and tunable synthesis of ordered gyroidal polymer hybrids and mesoporous carbon monoliths. Our SIT strategy involves the chemically confined polymerization of a carbon-forming polymer inside a nanostructured bulk organogel with gyroid morphology, which enables quantitative infusion efficiency to achieve percolated in-gel polymerized hybrids and continuous self-standing monolithic carbon nanonetworks. Dry and gel-state small-angle X-ray scattering confirms the formation and retention of a well-ordered gyroidal morphology during every step and demonstrates that fine-tuning of structural parameters is possible through the infusion composition without changing the ordered morphology. The distinct chemical interactions between the gel template and components of the infused reagent solution offers a complementary design principle and alternative bottom-up fabrication strategy for ordered hybrid and mesoporous materials with tailored architectures. Moreover, we demonstrate that SIT is amenable to lithographic patterning for the fabrication of hierarchically porous architectures with defined structural features spanning orders of magnitude in length scale.