Low-pressure flame synthesis of carbon-stabilized TiO2-II (srilankite) nanoparticles

Abstract

Nanoparticulate (3–10 nm) TiO2 polymorphs, i.e., rutile, anatase, and srilankite (also known as TiO2-II or α-PbO2-type TiO2) phases are produced via low-pressure (e.g., 20 torr) flame synthesis at temperatures ranging from 1560K to 2650K, with burner flow velocities varying from 150 to 300 cm/s, using titanium tetra-isopropoxide (TTIP) as precursor. Interestingly, added carbon (i.e., ethylene) in the feed stream produces nanoparticles of the generally characteristic low-temperature high-pressure metastable srilankite phase. The as-synthesized nanopowder is composed of either rutile or srilankite phase, with composition dependent on particle residence time in the flow field. Under the same conditions, feed gas without carbon, e.g., hydrogen, yields anatase phase TiO2. Post heat treatment up to 773K in thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) highlights the thermal stability of the samples, while x-ray photoelectron spectroscopy (XPS) indicates the presence of carbon, with absences of Ti3+, Ti–C, and nitrogen. Microscopy reveals morphology on both the micrometer scale (scanning electron microscopy, SEM) and nanometer scale (transmission electron microscopy, TEM), while x-ray diffraction (XRD) and selected area electron diffraction (SAED) confirm polymorph variation under different synthesis conditions. CHN analysis determines that the synthesized srilankite contains a greater weight percentage of carbon than does anatase. Excess carbon doped into the lattice during low-pressure flame synthesis seems to be the key in stabilizing the high-pressure srilankite phase for such nanoparticles.