Professional Documents
Culture Documents
RSC Advances
Cite this: RSC Advances, 2012, 2, 22942301
PAPER
www.rsc.org/advances
Introduction
The solgel process offers many advantages for preparing oxide
materials such as low cost, high purity and a wide variety of
morphologies. The synthetic process of solgel materials in
general involves a wet-chemical process to form a precursor sol
or gel solution, which can be deposited on a substrate, followed
by a post heat treatment to convert the amorphous precursor
into crystalline particles or thin films.1 Typical solgel processing
of TiO2 nanocrystals includes the hydrolysis of titanium alkoxide
by water, which can react with alkoxyl groups, generating fully
or partially hydrolyzed (OR)42nTi(OH)n molecules. The (partially) hydrolyzed molecules can react with each other or with
other alkoxides or hydroxides, forming an oxo bridge (O)
between Ti atoms (oxolation) together with an elimination of a
water molecule, as shown below. Briefly, the hydrolysis of Ti
alkoxides leads to hydroxyl groups, which is able to change
Ti(OR)4 to TiOTi via the condensation (i.e., olation or
oxolation process), and produces Ti-oxo-alkoxy or polyoxotitanate molecular clusters, for example, [Ti12O16](OPri)16,
[Ti11O13](OPri)18 and Ti16O16(OEt)32.2 The Tioxoalkoxy clusters can further grow to larger denser nanoparticles (NPs)
dispersing in a solution (i.e. sol). The sol particles can further
associate with each other via collisions after aging for a certain
period of time and thus form bigger isolate gel particles, gel
network, or porous films depending on experimental conditions.
For the hydrolysis of titanium alkoxides, it is known that the
amount of water strongly affects the morphology of final
products. According to the molar ratio of water to titanium
alkoxides (h), the solgel processing of TiO2 may be classified
into two regimes; low H2O/Ti molar ratio (h , 10) and high
H2O/Ti molar ratio (h . 10). At low h values, spherical
TiO2 particles with relatively uniform size about 0.51 mm are
Department of Materials Science and Metallurgy, University of
Cambridge, Pembroke Street, Cambridge, CB2 3QZ, U.K.
E-mail: sean.chen@cantab.net
Experimental
Materials
Titanium(IV) tetra-isopropoxide (TTIP, 97%) and absolute
ethanol (analytical reagent grade) were purchased form
Aldrich. All reagents were used without any further purification.
Doubly distilled water was used to initiate the hydrolysis and the
condensation process.
Synthesis of TiO2 by general approach
5 ml absolute ethanol was first used to modify TTIP (5 ml) using
magnetic stirring for 20 min in an argon atmosphere. Then, 5 ml
doubly distilled water was slowly added into the mixture of
ethanol and TTIP at room temperature to form a sol solution.
The molar ratio of water/TTIP is 15.4. Gel solution was obtained
by aging the sol for 18 h at room temperature. Annealing process
This journal is The Royal Society of Chemistry 2012
Fig. 4 (a) Normal solgel process of TiO2 particles. (b) TiO2 prepared
by solgel process in the vapour hydrolysis design.
Fig. 5 SEM images of TiO2 dried at room temperature (a), 500 uC (b),
600 uC (c), and 600 uC for 15 h (d). Samples were prepared by vapourhydrolyzing pure TTIP.
Fig. 12 SEM images of TiO2 secondary particles produced by hydrolyzing pure TTIP with vapour input rates of 3.47 6 1026 mol s21 (a) and
8.68 6 1026 mol s21 (b).
Conclusion
TiO2 was prepared in a self-organization process with an ultraslow
hydrolysis rate via a vapour hydrolysis system without mixing and
in a normal solgel process for reference. Experimental results
from both methods suggest that solgel TiO2 were secondary
particles composed of primary particles, which were amorphous
before an annealing process was performed. The crystalline
anatase primary particles were generated at 100 uC and became
single crystalline at around 600 uC. The ethanol effect on solgel
TiO2 was proved to aid aggregation and packing of TiO2 primary
particles. This phenomenon leads to a size enlargement of the
secondary particles when the post annealing temperature is above
500 uC. A plausible model considering that TiO2 secondary
particles are the result of the nucleation of the primary particles is
attempted to qualitatively describe to the growth of solgel TiO2.
Experimental results show that the secondary particles size
reduces with increasing vapour input rate, which is consistent
with the prediction of the growth model.
References
1 P. Periyat, F. Laffir, S. A. M. Tofail and E. Magner, RSC Adv., 2011, 1, 1794.
2 (a) V. W. Day, T. A. Eberspacher, W. G. Klemperer and C. W. Park, J.
Am. Chem. Soc., 1993, 115, 8469; (b) G. Fornasieri, L. Rozes, S. L.
Calve, B. Alonso, D. Massiot, M. N. Rager, M. Evain, K. Boubekeur
and C. Sanchez, J. Am. Chem. Soc., 2005, 127, 4869; (c) A. Senouci, M.
Yaakoub, C. Huguenard and M. Henry, J. Mater. Chem., 2004, 14,
3215; (d) J. V. Barkley, J. C. Cannadine, I. Hannaford, M. M. Harding,
A. Steiner, J. Tallon and R. Whyman, Chem. Commun., 1997, 1653.
3 (a) E. A. Barringer and H. K. Bowen, Langmuir, 1985, 1, 414; (b)
E. A. Barringer and H. K. Bowen, Langmuir, 1985, 1, 420; (c) J. H.
Jean and T. A. Ring, Langmuir, 1986, 2, 251; (d) J. L. Look and C. F.
Zukoski, J. Am. Ceram. Soc., 1992, 75, 1587; (e) J. L. Look and C. F.
Zukoski, J. Am. Ceram. Soc., 1995, 78, 21.
4 Q. Xu, M. J. Gieselmann and M. A. Anderson, Polym. Mater. Sci.
Eng., 1989, 61, 889.
5 (a) H. S. Chen, R. V. Kumar and B. A. Glowacki, Mater. Chem.
Phys., 2010, 122, 305; (b) H. S. Chen, R. V. Kumar and B. A.
Glowacki, J. Sol-Gel Sci. Technol., 2009, 51, 102.
6 H. K. Park, D. K. Kim and C. H. Kim, J. Am. Ceram. Soc., 1997, 80, 743.
7 D. Vorkapic and T. Matsoukas, J. Am. Ceram. Soc., 1998, 81, 2815.
8 D. C. Hague and M. J. Mayo, Nanostruct. Mater., 1993, 3, 61.
9 G. Oskam, Z. Hu, R. L. Penn, N. Pesika and P. C. Searson, Phys.
Rev. E, 2002, 66, 011403.
10 R. Azouani, A. Soloviev, M. Benmami, K. Chhor, J. F. Bocquet and
A. Kanaev, J. Phys. Chem. C, 2007, 111, 16243.
11 J. Livage, M. Henry and C. Sanchez, Prog. Solid State Chem., 1988, 18, 259.
12 (a) L. Rozes, N. Steunou, G. Fornasieri and C. Sanchez, Monatsh.
Chem., 2006, 137, 501; (b) L. Rozes and C. Sanchez, Chem. Soc. Rev.,
2011, 40, 1006.
13 J. Blanchard, F. Ribot, C. Sanchez, P. Bellot and A. Trokiner, J.
Non-Cryst. Solids, 2000, 265, 83.
14 Y. T. Moon, H. K. Park, D. K. Kim and C. H. Kim, J. Am. Ceram.
Soc., 1995, 78, 2690.
15 (a) M. L. Shepotko and A. A. Davydov, Theor. Exp. Chem., 1991, 27,
210; (b) S. Pilkenton, S. J. Hwang and D. Raftery, J. Phys. Chem. B,
1999, 103, 11152.
16 S. Tieng, R. Azouani, K. Chhor and A. Kanaev, J. Phys. Chem.C,
2011, 115, 5244.
17 A. Soloviev, D. Ivanov, R. Tufeu and A. V. Kanaev, J. Mater. Sci.
Lett., 2001, 20, 905.
18 M. Kallala, C. Sanchez and B. Cabane, Phys. Rev. E, 1993, 48, 3642.
19 M. Volmer and A. Z. Weber, Phys. Chem., 1926, 119, 227.
20 (a) X. Peng, J. Wickham and A. P. Alivisatos, J. Am. Chem. Soc.,
1998, 120, 10937; (b) Y. Chen, E. Johnson and X. Peng, J. Am. Chem.
Soc., 2007, 129, 10937; (c) H. S. Chen and R. V. Kumar, Cryst.
Growth Des., 2009, 9, 5343; (d) H. S. Chen and R. V. Kumar, J. Phys.
Chem. C, 2009, 113, 31; (e) H. S. Chen and R. V. Kumar, J. Phys.
Chem. C, 2009, 113, 12236.