Langmuir, Vol.25, No.13, 7623-7630, 2009
Role of Ti-O Bonds in Phase Transitions of TiO2
A phase transition was achieved from TiO2 particles to titanate nanotubes by the breakage of Ti-O bonds without using expensive precursors, high temperatures, high chemical concentrations of alkaline solutions, and long synthesis times. The controlled preparation of one-dimensional nanostructures of titanates (H2Ti4O9 center dot H2O) has been conducted at a very low concentration of alkaline solution (1 M NaOH), and in a very short time (12 h) using TiO2 anatase and TiO2 P-25 (precursors) and a microwave enhanced soft chemical process. Temperature was used as a variable, and only low process temperatures (100-110 degrees C) were used. A combination of anatase nanoparticles/hydrogen tetratitanate nanotubes was synthesized using TiO2 (anatase) and a temperature of only 100 degrees C. When TiO2 (P-25) was used with the same concentration of alkaline solution (I M NaOH), the same processing time of 12 h, and a higher temperature at 110 degrees C, only hydrogen tetratitanate nanotubes were observed. The linkages of "Ti-O" play a very important role in the structural features of different phases, X-ray diffraction (XRD) showed two crystalline phases (tetragonal and monoclinic) in the case of TiO2 (anatase) and one crystalline phase (monoclinic) for products of TiO2 (P-25). The role of Ti-O linkages is obvious in the Raman spectra as revealed by a shift in peak positions for a layered structure of the hydrogen tetratitanate and a nanosphere structure of the resulting TiO2. An X-ray pholoelectron spectroscopy (XPS) study showed a shift to a lower binding energy of the 2p peaks (2p(1/2, 3/2)) in the Ti region for titanate and confirmed the formation of titanate nanostructures. Transmission electron microscopy (TEM) revealed nanotubes of hydrogen tetratitanates (H2Ti4O9 center dot H2O) in the form of bundles. High-resolution TEM (HRTEM) data supported findings of X-ray diffraction results of the products of TiO2 (anatase) and TiO2 (P-25).