The predictive self-assembly of tunable nanostructures is important for broad nanomaterial investigations and energy applications. The equilibrium self-assembly of block polymer templates has been broadly investigated, however this approach fundamentally prevents independent control over the resulting feature sizes. Kinetic-controlled methods such as persistent micelle templates (PMT) overcome this limitation and maintain constant template size by imposing a large thermodynamic barrier to chain exchange processes. Thus, PMTs enables tailored wall-thickness control independent from pore size control. Furthermore, due to the simple packing of spherical micelles, PMT series give rise to tunable isomorphic architectures that enable the investigation of energy devices with a single spatial variable. One limitation of early PMT demonstrations was that water-reactive material precursors were added directly to aqueous micelle solutions. That approach however depleted the thermodynamic barrier to chain exchange and thus limited the range of micelle control. Here we show that an <i>ex situ</i> hydrolysis method for TiO<sub>2</sub> mitigates this depletion of water and nearly decouples materials chemistry from micelle control. This approach enables the widest reported PMT range that spans the gamut from sparse walls to nearly isolated pores. Remarkably, this improved PMT approach enables ~2 Å precision adjustment of the wall thickness. This high-resolution nanomaterial series exhibited monotonic trends where nanoscale confinement determined the crystallite dimension as well as the resulting nanomaterial lithiation behavior. An unexpected nanostructure-properties relationship was identified and was attributed to a size-dependent strain mismatch between polymorphs. This precision and independent control of architectures also opens new opportunities for nano-optimized devices.

Polymer-derived tunable isomorphic architectures for energy applications

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.