Continuous supercritical hydrothermal synthesis of controlled size and highly crystalline anatase TiO 2 nanoparticles

Abstract

The production of size-controlled and highly crystalline anatase titanium dioxide (TiO 2) nanoparticles was carried out under supercritical hydrothermal conditions (400 °C and 30 MPa) in a continuous flow apparatus with a residence time of 1.7 s. An industrially useful titanium sulfate (Ti(SO 4) 2) solution was used as the starting solution. KOH was used to change TiO 2 solubility and pH and thereby control the particle size. The apparatus comprised two micromixers operating at high temperature. The first mixer was configured to prepare a supercritical aqueous KOH solution from supercritical water (SC-H 2O) and KOH. The second mixer combined this KOH solution with aqueous Ti(SO 4) 2. In situ pH control and homogeneous nucleation were achieved in the second mixer. This two-step high-temperature micromixing process produced reasonably small and homogeneous particles. The particles were characterized by transmission electron microscopy (TEM) on the basis of morphology, average size, and size distribution, together with the coefficient of variation (CV). Powder X-ray diffraction (XRD) was used to determine the crystal structure and crystalline size. The weight loss of material was found through thermogravimetric (TG) measurement. The crystal structure of the product was assigned to the anatase single phase. The average particle size could be adjusted in the range 13–30 nm while maintaining a CV of 0.5 by changing the KOH concentration. At low pH, the powder XRD results for crystallite size were in good agreement with the average particle size measured by TEM, confirming that the products were single crystals of TiO 2 nanoparticles. When the reactor temperature was increased from 400 to 500 °C, the weight loss decreased from 4.5 to 2.5%, keeping the average particle size and high crystallinity of the TiO 2 particles unchanged.