Two-Dimensional Titanium Dioxide-Surfactant Photoactive Supramolecular Networks: Synthesis, Properties, and...

The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core-shell hybrid photocatalysts in the form of a 2D-TiO₂-surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host-guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO₂ core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO₂ but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO₂ confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO₂-surfactant supramolecular photocatalysts.