Size, composition and structural changes of TiO2 rutile nanoparticles by pulsed laser ablation in water

The rutile-type TiO2 powders originally whitish and micrometer in size were successfully reduced in size with accompanied structure, composition and optical property change to become dark bluish by pulsed laser ablation in liquid under 532 nm excitation and 400 mJ per pulse at a specified water depth (5 or 15 mm) for up to 30 min. Transmission electron microscopic observations indicated the newly formed anatase nanoparticles are ca. 5 nm in size with spindle-like shape having well-developed {101} faces and -(001) facets for mutual coalescence into unity. The -(001)-specific coalescence twin of anatase was also observed. There are also amorphous nanoparticles in association with anatase, minor brookite and relic rutile with 2 x (110) superstructure. The resultant colloidal TiO2 nanoparticles are (Ti3+, Ti2+, H+) co-signified according to optical spectroscopic results and have a bimodal minimum band gaps 3.12 and 2.66 eV due to nanocrystals and amorphous phase, respectively, for potential optocatalytic applications in UV-visible range.