Ordered Mesoporous to Macroporous Oxides with Tunable Isomorphic Architectures: Solution Criteria for Persistent Micelle Templates

Porous and nanoscale architectures of inorganic materials have become crucial for a range of energy and catalysis applications, where the ability to control the morphology largely determines the transport characteristics and device performance. Despite the availability of a range of block copolymer self-assembly methods, the conditions for tuning the key architectural features such as the inorganic wall-thickness have remained elusive. Toward this end, we have developed solution processing guidelines that enable isomorphic nanostructures with tunable wall-thickness. A new poly(ethylene oxide- b -hexyl acrylate) (PEO- b -PHA) structure-directing agent (SDA) was used to demonstrate the key solution design criteria. Specifically, the use of a polymer with a high Flory–Huggins effective interaction parameter, χ, and appropriate solution conditions leads to the kinetic entrapment of persistent micelle templates (PMT) for tunable isomorphic architectures. Solubility parameters are used to predict conditions for maintaining persistent micelle sizes despite changing equilibrium conditions. Here, the use of different inorganic loadings controls the inorganic wall-thickness with constant pore size. This versatile method enabled a record 55 nm oxide wall-thickness from micelle coassembly as well as the seamless transition from mesoporous materials to macroporous materials by varying the polymer molar mass and solution conditions. The processing guidelines are generalizable and were elaborated with three inorganic systems, including Nb 2 O 5, WO 3, and SiO 2, that were thermally stable to 600 °C for access to crystalline materials.