Journal of the American Chemical Society, Vol.125, No.21, 6553-6557, 2003
Multigrarn scale synthesis and characterization of monodisperse tetragonal zirconia nanocrystals
A new and simple method has been developed to synthesize large quantities of highly monodisperse tetragonal zirconia nanocrystals. In this synthesis, a nonhydrolytic sol-gel reaction between zirconium(IV) isopropoxide and zirconium(IV) chloride at 340 degreesC generated 4 nm sized zirconia nanoparticles. A high-resolution transmission electron microscopic (HRTEM) image showed that the particles have a uniform particle size distribution and that they are highly crystalline. These monodisperse nanoparticles were synthesized without any size selection process. X-ray diffraction studies combined with Rietveld refinement revealed that the ZrO2 nanocrystals are the high-temperature tetragonal phase, and very close to a cubic phase. When zirconium(IV) bromide is used as a precursor instead of zirconium chloride, zirconia nanoparticles with an average size of 2.9 nm were obtained. The UV-visible absorption spectrum of 4 nm sized zirconia nanoparticles exhibited a strong absorption starting at around 270 nm. A fluorescence spectrum with excitation at 300 nm showed a broad fluorescence band centered around 370 nm. FTIR spectra showed indication of TOPO binding on the ZrO2 nanoparticle surface. These optical studies also suggest that the nanoparticles are of high quality in terms of narrow particle size distribution and relatively low density of surface trap states.