Impact of the Precursor on the Physicochemical Properties and Photoactivity of TiO2 Nanoparticles Produced in Supercritical CO2.

Abstract

The synthesis of TiO2 nanoparticles (NPs) in supercritical media has been reported over the last two decades. However, very few studies have compared the physicochemical characteristics and photoactivity of the TiO2 powders produced from different precursors, and even fewer have investigated the effect of using different ratios of hydrolytic agent/precursor (HA/P) on the properties of the semiconductor. To bridge this knowledge gap, this research focuses on the synthesis and characterization of TiO2 NPs obtained in a supercritical CO2 medium from four different TiO2 precursors, namely diisopropoxytitanium bis (acetylacetonate) (TDB), titanium (IV) isopropoxide (TIP), titanium (IV) butoxide (TBO), and titanium (IV) 2-ethylhexyloxide (TEO). Further, the effect of various HA/P ratios (10, 20, 30, and 40 mol/mol) when using ethanol as a hydrolytic agent has also been analyzed. Results obtained have shown that the physicochemical properties of the catalysts are not significantly affected by these variables, although some differences do exist between the synthesized materials and their catalytic performances. Specifically, photocatalysts obtained from TIP and TEO at the higher HA/P ratios (HA/P = 30 and HA/P = 40) led to higher CO2 photoconversions (6.3-7 µmol·g-1·h-1, Apparent Quantum Efficiency < 0.1%), about three times higher than those attained with commercial TiO2 P-25. These results have been imputed to the fact that these catalysts exhibit appropriate values of crystal size, surface area, light absorption, and charge transfer properties.