The predictive self-assembly of tunable nanostructures is of great utility for broad nanomaterial investigations and applications. The use of equilibrium-based approaches however prevents independent feature size control. Kinetic-controlled methods such as persistent micelle templates (PMTs) overcome this limitation and maintain constant pore size by imposing a large thermodynamic barrier to chain exchange. Thus, the wall thickness is independently adjusted via addition of material precursors to PMTs. Prior PMT demonstrations added water-reactive material precursors directly to aqueous micelle solutions. That approach depletes the thermodynamic barrier to chain exchange and thus limits the amount of material added under PMT-control. Here, an ex situ hydrolysis method is developed for TiO 2 that mitigates this depletion of water and nearly decouples materials chemistry from micelle control. This enables the widest reported PMT range (M:T = 1.6–4.0), spanning the gamut from sparse walls to nearly isolated pores with ≈2 Å precision adjustment. This high-resolution nanomaterial series exhibits monotonic trends where PMT confinement within increasing wall-thickness leads to larger crystallites and an increasing extent of lithiation, reaching Li 0.66 TiO 2 . The increasing extent of lithiation with increasing anatase crystallite dimensions is attributed to the size-dependent strain mismatch of anatase and bronze polymorph mixtures.
|State||Published - 3 May 2019|
- Li intercalation
- polymer micelles
- TiO nanomaterials