Zr doping on one-dimensional titania nanomaterials synthesized in supercritical carbon dioxide

The growth mechanism of one-dimensional metal oxide nanotubular structures is of tremendous current interest to tailor materials using "green" synthetic procedures for emerging industries in alternative energy and biomaterials. In this study, ZrO(2)-modified TiO(2) nanorods and tubular structures were successfully synthesized via a surfactant-free sol-gel route using supercritical carbon dioxide (scCO(2)) as the solvent/drying agent. The effect of metal alkoxide concentration (0.35-1.4 mol/L), acid/metal alkoxide ratio (R = 3-7), and Zr ratio (0-20%) was examined on the morphology and crystallinity of the resulting nanostructures as measured by electron microscopy (SEM and TEM), EDX, XPS, and XRD. The electron microscopy results showed that the crystal growth of the synthesized binary Ti-Zr nanomaterials could be tailored by changing the operating variables with nanotubular structure formed at metal alkoxide concentration of 1.2 mol/L, R = 5-6, and Zr ratio between 4% and 20%. Gelation kinetics for this new system was also studied and revealed that increasing alkoxide concentration and R value enhanced the gelation kinetics. In situ and powder FTIR results revealed that this Ti-Zr binary system follows a similar reaction scheme to that of either single-component system, showing the flexibility of this approach for tailoring nanotubular production.