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This work demonstrates a phenomenon that preserves the traditionally metastable anatase crystal structure of thin titania (TiO2) films along a two-dimensional oxide interface at temperatures well in excess of those that normally trigger a full polymorphic transformation to rutile in higher dimensionality crystalline powders. Whereas atomic surface mobility appears to dominate polymorph transformation processes within bulk TiO2 powders, a simple reduction in dimen-sionality to a two-dimensional TiO2 film (ca. 50−200 nm thick), supported upon a substrate, leads to a remarkable resistance to the calcination-induced anatase-to-rutile transformation. This stabilization does not appear to be specifically reliant on substrate character given its persistence for TiO2 films prepared on amorphous silica (SiO2) as well as crystalline TiO2 substrates. Instead, interface-mediated coordination of the TiO2 film with the substrate, and the inherent confinement of crystallites in two dimensions, is believed to resist polymorph transformation by mitigation of the atomic surface mobility. Only when temperatures (i.e., >800 °C) that are conducive to bulk atomic mobilization are reached does reconstructive grain growth convert the film into the thermodynamically stable rutile crystal structure.

Convectively assembled colloidal crystal templates, composed of size-tunable (ca. 15-50 nm) silica (SiO) nanoparticles, enable versatile sacrificial templating of three-dimensionally ordered mesoporous (3DOm) metal oxides (MO) at both mesoscopic and microscopic size scales. Specifically, we show for titania (TiO) and zirconia (ZrO) how this approach not only enables the engineering of the mesopore size, pore volume, and surface area but can also be leveraged to tune the crystallite polymorphism of the resulting 3DOm metal oxides. Template-mediated volumetric (i.e., interstitial) effects and interfacial factors are shown to preserve the metastable crystalline polymorphs of each corresponding 3DOm oxide (i.e., anatase TiO (A-TiO) and tetragonal ZrO (t-ZrO)) during high-temperature calcination. Mechanistic investigations suggest that this polymorph stabilization is derived from the combined effects of the template-replica (MO/SiO) interface and simultaneous interstitial confinement that limit the degree of coarsening during high-temperature calcination of the template-replica composite. The result is the identification of a facile yet versatile templating strategy for realizing 3DOm oxides with (i) surface areas that are more than an order of magnitude larger than untemplated control samples, (ii) pore diameters and volumes that can be tuned across a continuum of size scales, and (iii) selectable polymorphism.

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