Constructing Three-Dimensional Mesoporous Bouquet-Posy-like TiO2 Superstructures with Radially Oriented Mesochannels and Single-Crystal Walls

Constructing three-dimensional (3-D) hierarchical mesostructures with unique morphology, pore orientation, single-crystal nature, and functionality remains a great challenge in materials science. Here, we report a confined microemulsion self-assembly approach to synthesize an unprecedented type of 3-D highly ordered mesoporous TiO₂ superstructure (Level-1), which consists of 1 spherical core and 12 symmetric satellite hemispheres epitaxially growing out of the core vertices. A more complex and asymmetric TiO₂ superstructure (Level-2) with 13 spherical cores and up to 44 symmetric satellite hemispheres can also be well manipulated by increasing the size or content of impregnated TiO₂ precursor emulsion droplets. The obtained 3-D mesoporous TiO₂ superstructures have well-defined bouquet-posy-like topologies, oriented hexagonal mesochannels, high accessible surface area (134-148 m²/g), large pore volume (0.48-0.51 cm³/g), and well single-crystalline anatase walls with dominant (001) active facets. More interestingly, all cylindrical mesopore channels are highly interconnected and radially distributed within the whole superstructures, and all TiO₂ nanocrystal building blocks are oriented grown into a single-crystal anatase wall, making them ideal candidates for various applications ranging from catalysis to optoelectronics. As expected, the bouquet-posy-like mesoporous TiO₂ superstructure supported catalysts show excellent catalytic activity (≥99.7%) and selectivity (≥96%) in cis-semihydrogenation of various alkynes, exceeding that of commercial TiO₂ (P25) supported catalyst by a factor of 10. No decay in the activity was observed for 25 cycles, revealing a high stability of the mesoporous TiO₂ superstructure supported catalyst.