Chemically Nanostructured Organogel Monoliths for Selective Infusion Templating

Organogels with spatially defined mesoscale distinction of chemical activity that guide and accelerate nanomaterial templating by chemical nanoconfinement are found ubiquitous in nature but inadequately studied in artificial systems. Herein, we introduce chemically nanostructured bulk organogels with two gyroidal three-dimensionally periodic network morphologies (alternating gyroid and double gyroid) as well as one- and two-dimensionally periodic structures from self-assembled block copolymer (BCP). Our rationally designed BCP bulk monoliths contain a single selectively crosslinked block and exhibit remarkable macroscopic and nanoscopic structural integrity upon swelling of up to 400 vol% and almost doubling of the nanoscale periodicity. These ordered organogels are a novel class of solvent-laden bulk materials with chemically distinct nano-environments on a periodic mesoscale lattice, which form a bio-inspired soft chemical template for structured functional materials. We demonstrate their use for selective infusion templating (SIT) with the nanoconfined synthesis of bulk monolithic polymer and functional inorganic materials of ordered gyroidal and mesoporous nanostructures. We believe that our bio-inspired nanostructured soft-gels applied to SIT will enable the fabrication of many traditionally hard-to-template materials as periodically nanostructured monolithic metamaterials due to the extensive tunability in their physico-chemical parameter space.