Abstract
Nanoparticles and nanocrystalline particles of pure anatase titania (TiO2) were synthesized by solvothermal processing of TiCl4 ethanol and isopropanol solutions at 120 to 200 °C. This one-step and nonsurfactant approach is versatile and the morphology tuning can be achieved by manipulating the growth kinetics. Dispersed nanocrystals of spherical, cubic, and acicular shapes and hollow spherical and core-shell structured micrometer-sized particles were obtained under different experimental conditions. The obtained hollow spherical- and core-shell-structured particles have an average diameter of 700 nm to 1.0 μm, with an average crystallite size of 5 to 16 nm. The dependence of nucleation/crystal growth and morphology development on solvothermal medium, reaction temperature, and reactant concentration was investigated. The reaction mechanism was then suggested and tentatively discussed from coordination and solution chemistry.
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References
A.J. Nozik: Quantum dot solar cells. Physica E 14, 115 (2002).
R. Plass, S. Pelet, J. Krueger, M. Gratzel, U. Bach: Quantum dot sensitization of organic-inorganic hybrid solar cells. J. Phys. Chem. B 106, 7578 (2002).
T. Kitamura, M. Ikeda, K. Shigaki, T. Inoue, N.A. Anderson, X. Ai, T. Lian, S. Yanagida: Phenyl-conjugated oligoene sensitizers for TiO2 solar cells. Chem. Mater. 16, 1806 (2004).
In Hollow and Solid Spheres and Microspheres: Science and Technology Associated With Their Fabrication and Application edited by D.L. Wilcox, Sr., M. Berg, T. Bernat, D. Kellerman, and J.K. Cochran, Jr. (Mater. Res. Soc. Symp. Proc. 372, Pittsburgh, PA, 1995).
F. Caruso: Nanoengineering of particle surfaces. Adv. Mater. 13, 11 (2001).
W. Schartl: Crosslinked spherical nanoparticles with core-shell topology. Adv. Mater. 12, 1899 (2000).
P.D. Cozzoli, A. Kornowski, H. Weller: Low-temperature synthesis of soluble and processable organic-capped anatase TiO2 nanorods. J. Am. Chem. Soc. 125, 14539 (2003).
Z. Tang, J. Zhang, Z. Cheng, Z. Zhang: Synthesis of nanosized rutile TiO2 powder at low temperature. Mater. Chem. Phys. 77, 314 (2002).
K.C. Song, S.E. Pratsinis: Control of phase and pore structure of titania powders using HCl and NH4OH catalysts. J. Am. Ceram. Soc. 84, 92 (2001).
Y. Zhou, M. Antonietti: Synthesis of very small TiO2 nanocrystals in a room-temperature ionic liquid and their self-assembly toward mesoporous spherical aggregates. J. Am. Chem. Soc. 125, 14960 (2003).
J. Sun, L. Gao: pH effect on titania-phase transformation of precipitates from titanium tetrachloride solutions. J. Am. Ceram. Soc. 85, 2382 (2002).
S. Sivakumar, P.K. Pillai, P. Mukundan, K.G.K. Warrier: Sol-gel synthesis of nanosized anatase from titanyl sulfate. Mater. Lett. 57, 330 (2002).
S.J. Kim, S.D. Park, Y.H. Jeong: Homogeneous precipitation of TiO2 ultrafine powders from aqueous TiOCl2 solution. J. Am. Ceram. Soc. 82, 927 (1999).
A. Pottier, S. Cassaignon, C. Chaneac, F. Villain, E. Tronc, J.P. Jolivet: Size tailoring of TiO2 anatase nanoparticles in aqueous medium and synthesis of nanocomposites. Characterization by Raman spectroscopy. J. Mater. Chem. 13, 877 (2003).
A. Chemseddine, T. Moritz: Nanostructuring titania: Control over nanocrystal structure, size, shape, and organization. Eur. J. Inorg. Chem. 1999(2), 235 (1999).
B.L. Bischoff, M.A. Anderson: Peptization process in the sol-gel preparation of porous anatase (TiO2). Chem. Mater. 7, 1772 (1995).
M. Niederberger, M.H. Bartl, G.D. Stucky: Benzyl alcohol and titanium tetrachloride: A versatile reaction system for the nonaqueous and low-temperature preparation of crystalline and luminescent titania nanoparticles. Chem. Mater. 14, 4364 (2002).
S. Eiden-Assmann, J. Widoniak, G. Maret: Synthesis and characterization of porous and nonporous monodisperse colloidal TiO2 particles. Chem. Commun. 16, 6 (2004).
M.A. McLachlan, N.P. Johnson, R.M.D.L. Rue, D.W. McComb: Thin film photonic crystals: Synthesis and characterisation. J. Mater. Chem. 14, 144 (2004).
Y.V. Kolen’ko, A.A. Burukhin, B.R. Churagulov, N.N. Oleynikov: Synthesis of nanocrystalline TiO2 powders from aqueous TiOSO4 solutions under hydrothermal conditions. Mater. Lett. 57, 1124 (2003).
Y.V. Kolen’ko, V.D. Maximov, A.A. Burukhin, V.A. Muhanov, B.R. Churagulov: Synthesis of ZrO2 and TiO2 nanocrystalline powders by hydrothermal process. Mater. Sci. Eng. C 23, 1033 (2003).
M. Hirano, C. Nakahara, K. Ota, O. Tanaike, M. Inagaki: Photoactivity and phase stability of ZrO2-doped anatase-type TiO2 directly formed as nanometer-sized particles by hydrolysis under hydrothermal conditions. J. Solid State Chem. 170, 39 (2003).
T. Sugimoto, X. Zhou, A. Muramatsu: Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 3. Formation process and size control. J. Colloid Interface Sci. 259, 43 (2003).
T. Sugimoto, X. Zhou, A. Muramatsu: Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 4. Shape control. J. Colloid Interface Sci. 259, 53 (2003).
J. Yang, S. Mei, J.M.F. Ferreira: Hydrothermal synthesis of nanosized titania powders: Influence of tetraalkyl ammonium hydroxides on particle characteristics. J. Am. Ceram. Soc. 84, 1696 (2001).
J. Yang, S. Mei, J.M.F. Ferreira: Hydrothermal synthesis of nanosized titania powders: Influence of peptization and peptizing agents on the crystalline phases and phase transitions. J. Am. Ceram. Soc. 83, 1361 (2000).
S.T. Aruna, S. Tirosh, A. Zaban: Nanosize rutile titania particle synthesis via a hydrothermal method without mineralizers. J. Mater. Chem. 10, 2388 (2000).
J. Yang, S. Mei, J.M.F. Ferreira: In situ preparation of weakly flocculated aqueous anatase suspensions by a hydrothermal technique. J. Colloid Interface Sci. 260, 82 (2003).
H. Cheng, J. Ma, Z. Zhao, L. Qi: Hydrothermal preparation of uniform nanosize rutile and anatase particles. Chem. Mater. 7, 663 (1995).
S. Yin, Y. Fujishiro, J. Wu, M. Aki, T. Sato: Synthesis and photocatalytic properties of fibrous titania by solvothermal reactions. J. Mater. Process. Technol. 137, 45 (2003).
Z.X. Deng, C. Wang, Y.D. Li: New hydrolytic process for producing zirconium dioxide, tin dioxide, and titanium dioxide nanoparticles. J. Am. Ceram. Soc. 85, 2837 (2002).
C. Wang, Z.X. Deng, G. Zhang, S. Fan, Y. Li: Synthesis of nanocrystalline TiO2 in alcohols. Powder Technol. 125, 39 (2002).
B. Wen, C. Liu, Y. Liu: Solvothermal synthesis of ultralong single-crystalline TiO2 nanowires. New J. Chem. 29, 969 (2005).
B. Wen, C. Liu, Y. Liu: Controllable synthesis of one-dimensional single-crystalline TiO2 nanostructures. Chem. Lett. 34, 396 (2005).
S. Yin, Y. Aita, M. Komatsu v J. Wang, Q. Tang, T. Sato: Synthesis of excellent visible-light responsive TiO2-xNy photocatalyst by a homogeneous precipitation-solvothermal process. J. Mater. Chem. 15, 674 (2005).
K. Nagaveni, M.S. Hegde, N. Ravishankar, G.N. Subbanna, G. Madras: Synthesis and structure of nanocrystalline TiO2 with lower band gap showing high photocatalytic activity. Langmuir 20, 2900 (2004).
C.H. Cho, D.K. Kim: Phoocatalytic activity of monodispersed spherical TiO2 particles with different crystallization routes. J. Am. Ceram. Soc. 86, 1138 (2003).
T.J. Trentler, T.E. Denler, J.F. Bertone, A. Agrawal, V.L. Colvin: Synthesis of TiO2 nanocrystals by nonhydrolytic solution-based reactions. J. Am. Chem. Soc. 121, 1613 (1999).
P. Arnal, R.J.P. Corriu, D. Leclercq, P.H. Mutin, A. Vioux: A solution chemistry study of nonhydrolytic sol-gel routes to titania. Chem. Mater. 9, 694 (1997).
P. Arnal, R.J.P. Corriu, D. Leclercq, P.H. Mutin, A. Vioux: Preparation of anatase, brookite and rutile at low temperature by non-hydrolytic sol-gel methods. J. Mater. Chem. 6, 1925 (1996).
H. Kominami, M. Kohno, Y. Matsunaga, Y. Kera: Thermal decomposition of titanium alkoxide and silicate ester in organic solvent: A new method for synthesizing large-surface-area, silica-modified titanium(IV) oxide of high thermal stability. J. Am. Ceram. Soc. 84, 1178 (2001).
C.S. Kim, B.K. Moon, J.H. Park, B.C. Choi, H.J. Seo: Solvothermal synthesis of nanocrystalline TiO2 in tolene with surfactant. J. Cryst. Growth 257, 309 (2003).
M. Niederberger, M.H. Bartl, G.D. Stucky: Benzyl alcohol and transition metal chlorides as a versatile reaction system for the nonaqueous and low-temperature synthesis of crystalline nano-objects with controlled dimensionality. J. Am. Chem. Soc. 124, 13642 (2002).
A. Vioux: Nonhydrolytic sol-gel routes to oxides. Chem. Mater. 9, 2292 (1997).
X.M. Wang, P. Xiao: Non-template synthesis of titania hollow spheres and their thermal stability. J. Mater. Res. 20, 796 (2005).
T. Sugimoto, X. Zhou, A. Muramatsu: Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 1. Solution chemistry of Ti(OH)n(4-n)+ complexes. J. Colloid Interface Sci. 252, 339 (2002).
J. Widegren, L. Bergstrom: Electrostatic stabilization of ultrafine titania in ethanol. J. Am. Ceram. Soc. 85, 523 (2002).
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Wang, X.M., Xiao, P. Morphology tuning in nontemplated solvothermal synthesis of titania nanoparticles. Journal of Materials Research 21, 1189–1203 (2006). https://doi.org/10.1557/jmr.2006.0146
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DOI: https://doi.org/10.1557/jmr.2006.0146