Photocatalytic Surface-Initiated Polymerization on TiO₂ toward Well-Defined Composite Nanostructures

We demonstrate the use of TiO2 nanospheres as the photoinitiator for photocatalytic surface-initiated polymerization for the synthesis of various inorganic/polymer nanocomposites with well-defined structures. The excitation of TiO2 by UV-light irradiation produces electrons and holes which drive the free radical polymerization near its surface, producing core/shell composite nanospheres with eccentric or concentric structures that can be tuned by controlling the surface compatibility between the polymer and the TiO2. When highly porous TiO2 nanospheres were employed as the photoinitiator, polymerization could disintegrate the mesoporous framework and give rise to nanocomposites with multiple TiO2 nanoparticles evenly distributed in the polymer spheres. Thanks to the well-developed sol-gel chemistry of titania, this synthesis is well-extendable to the coating of the polymers on many other substrates of interest such as silica and ZnS by simply premodifying their surface with a thin layer of titania. In addition, this strategy could be easily applied to coating of different types of polymers such as polystyrene, poly(methyl methacrylate), and poly(N-isopropylacrylamide). We expect this photocatalytic surface-initiated polymerization process could provide a platform for the synthesis of various inorganic/polymer hybrid nanocomposites for many interesting applications.