Laser oxidative pyrolysis synthesis and annealing of TiO2 nanoparticles embedded in carbon-silica shells/matrix

Titania nanoparticles containing a mixture of anatase and rutile phases (with mean crystalline sizes up to 24 nm) covered with/embedded in carbon/silica thin layers or matrix were obtained in a single step using laser oxidative pyrolysis. Titanium tetrachloride and hexamethyldisiloxane (HMDSO) vapors were separately introduced into the reaction zone - both together with the laser-absorbing agent (sensitizer) ethylene - which acts also as carbon source - and the oxidant (air) - through the inner and the concentric nozzle, respectively. By increasing the air flow through the annular nozzle, while keeping constant the TiC4, inner air, HMDSO and C2H4 flows, the atomic carbon concentration as well as the rutile to anatase ratio in the resulted nanopowders decrease. A much brighter and extended flame was observed for the experiment involving the greatest air flow. The Ti/Si atomic ratio in the resulted nanocomposites was higher than that from the introduced precursors (1.8), indicating a partial siloxane conversion to silica. The annealed powders (at 450 °C to further carbon content reducing) exhibit a lower bandgap energy than those of the reference sample without silica (and also lower than the commercial Degussa P25 nano-TiO2).