Critical size of crystalline ZrO2 nanoparticles synthesized in near- and supercritical water and supercritical isopropyl alcohol

Nanocrystalline ZrO2 samples with narrow size distributions and mean particle sizes below 10 nm have been synthesized in a continuous flow reactor in near and supercritical water as well as supercritical isopropyl alcohol using a wide range of temperatures, pressures, concentrations and precursors. The samples were comprehensively characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TVA), and small-angle X-ray scattering (SAXS), and the influence of the synthesis parameters on the particle size, particle size distribution, shape, aggregation and crystallinity was studied. On the basis of the choice of synthesis parameters either monoclinic or tetragonal zirconia phases can be obtained. The results suggest a critical particle size of 5-6 nm for nanocrystalline monoclinic ZrO2 under the present conditions, which is smaller than estimates reported in the literature. Thus, very small monoclinic ZrO2 particles can be obtained using a continuous flow reactor. This is an important result with respect to improvement of the catalytic properties of nanocrystalline ZrO2.