Journal of Solid State Chemistry 158, 180}186 (2001)

doi:10.1006/jssc.2001.9090, available online at http://www.idealibrary.com on

Preparation, Characterization, and Spectral Studies

on Nanocrystalline Anatase TiO21
K. Madhusudan Reddy, C. V. Gopal Reddy, and S. V. Manorama
Materials Science Group, Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India

Received August 2, 2000; in revised form December 14, 2000; accepted January 19, 2001; published online March 27, 2001

A unique property of nanoparticulates is their extremely

Fine polycrystalline, nanoparticles of pure anatase titanium high surface area; they have many more sites for achieving
dioxide (average crystallite size &3+10 nm) with high surface property enhancements, making them ideal for a wide var-
area (&210 m2/g) have been synthesized in the pure anatase iety of applications. The synthesis of nanoparticles with
phase. Synthesized powder is characterized by DTA+TGA, controlled size and composition is of technological interest.
FT+IR, XRD, BET surface area, SEM, TEM, and UV+Visible The e!ort to understand the physics of ever-smaller struc-
absorption spectroscopy. Polymer capping of the synthesized
tures has kept pace with attempts to exploit their bene"cial
TiO2 particles showed an improved stability against agglomer-
ation and photo-degradation. The prepared nanoparticles showed
properties. The phenomena of semiconductor nanocrystals
a blue shift in the absorption spectra. Bandgap energy values showing size-tunable optical properties and metal nanopar-
observed for di4erent particle sizes are 3.167 (3 nm), 3.145 ticles that in#uence the activity and speci"city of catalysis
(6 nm), and 3.027 eV (39 nm) for commercial TiO2 . TiO2 is have been integrated into exploratory optical and electronic
encapped with eriochromcyanin dye; the nanoparticles showed devices (2). In particular, there has been a lot of emphasis on
a noticeable shift in the acquired color toward the blue region the production of nanoparticles of TiO for a wide variety of

with the decrease in the particle size.  2001 Academic Press applications.
Key Words: nanoparticles; titanium dioxide; semiconductor; Synthetic routes for TiO (titania or titanium dioxide)
hydrolysis; bandgap; UV+Vis spectroscopy; quantum size e4ect. 
production usually result in titanium hydroxide, amorph-
ous solid TiO or crystallites, anatase, or rutile depending

on the preparation route and experimental conditions. It is
1. INTRODUCTION
also known that the transformation behavior from the
amorphous to the anatase or rutile phase is in#uenced by
As materials science and engineering evolves we are wit- the synthesis conditions; however, most of the literature
nessing new approaches that provide increasingly precise shows that alkoxide-based sol}gel or precipitation pro-
control, at the atomic and molecular levels, over the struc- cesses yield amorphous titania precursors or powders
ture, properties, and function of materials. Although this is preferentially in the anatase phase (3}5).
The anatase phase of TiO , which is the stable phase at
largely driven by a recognition that familiar bulk proper- 
ties*mechanical, magnetic, electronic, and optoelec- low temperatures, has gained importance as a photo-cata-
tronic*depend upon atomic and molecular building lyst (6) for photodecomposition and solar energy conversion
because of its high photoactivity (7, 8). TiO shows di!erent
blocks, the same properties often di!er from bulk when 
examined on the nanometer scale. Smallness in itself is not electrical characteristics with oxygen partial pressure, be-
the goal. Instead, it is the realization, or now possibly even cause it has wide chemical stability and a nonstoichiometric
the expectation, that new properties intrinsic to novel struc- phase region. Because of this, it is suitable as a humidity
tures will enable breakthroughs in a multitude of technolo- sensor and high-temperature oxygen sensor (9}11). Further-
gically important areas (1). The impact of nanostructure on more, the properties of nanosized semiconductor particles
the properties of high surface area materials is an area of have long been known to depend very sensitively on the
increasing importance for understanding, creating, and particle size (12). As the diameter of crystallite approaches
improving materials for diverse applications. the exciton Bohr diameter, a splitting of the energy bands
into discrete quantised energy level occurs. This is the so-
 IICT Communication No. 4594.
called quantum size e+ect. Size quantization leads to a blue
 To whom correspondence should be addressed. E-mail: manorama@ shift in the absorption spectrum due to increased bandgap,
iict.ap.nic.in. nonlinear optical properties, and unusual luminescence.
180
0022-4596/01 $35.00
Copyright  2001 by Academic Press
All rights of reproduction in any form reserved.
 SPECTRAL STUDIES ON NANOCRYSTALLINE ANATASE TITANIA 181

2. EXPERIMENTAL was done to determine the temperatures of possible de-

composition and phase changes. The samples were heated at
2.1. Preparation of the Nanoparticles of Anatase TiO2 the rate of 203C/min and held at 2003C for 30 min and then
Various synthesis methods such as hydrolysis (14), sol}gel the heating was resumed up to 10003C.
(15}17), microemulsion or reverse micelles (18}21), and hy-
(b) XRD. Powder X-ray di!raction (XRD) was used for
drothermal (22}25) synthesis have been used to prepare
crystal phase identi"cation and estimation of the crystallite
nanoparticles of titanium dioxide. Compared to other
size. The X-ray Di!raction (XRD) measurements were per-
methods, hydrolysis could be carried out at conditions
formed on a Seimens/D5000 X-ray di!ractometer. From the
closer to ambient to produce nanoparticles of TiO . The
 line broadening of corresponding X-ray di!raction peaks
nanocrystalline anatase titanium dioxide powders reported
and using the Scherrer formula the crystallite size, ¸ has
in this study were prepared by TiCl hydrolysis. Titanium
 been estimated (26)
tetrachloride (98% TiCl ) (Loba Chemie) was used as the

starting material without any further puri"cation. When
¸"Kj/(b cos h),
TiCl is dissolved in water, the heat of the exothermic

reaction e!ects the formation of orthotitanic acid
[Ti(OH) ]. Since the formation of the species disturbed the where j is the wavelength of the X-ray radiation (CuKa"
 0.15406 nm), K is a constant taken as 0.89, b is the line width
homogenous precipitation, appreciated amount of TiCl
 at half maximum height, and h is the di!racting angle.
was initially digested in hydrochloric acid and then diluted
in distilled water, all this while keeping the reaction vessel in (c) Surface area. The Brunauer}Emmett}Teller (BET)
an ice-water bath. The concentration of titanium tetrachlor- surface area was determined using a Micromeritics Pulse
ide was adjusted to 3 M in water. The initial pH was found Chemisorb 2700 nitrogen adsorption apparatus. The sam-
to be about 1.8. A solution of hydrazine hydrate, H N O ples were dried in a #ow of inert gas (Helium) at 2503C and
 
(Ranbaxy) in water (5 M) was added drop wise to the solu- the surface area of the samples was estimated by N
tion until the "nal pH was about 7.5 to 8.0. The hydrolysis 
chemisorption.
and condensation reactions starts immediately upon mix-
ing, as indicated by the rapid increase in turbidity and the (d) IR spectroscopy. FT}IR studies were carried out in
formation of large, visible #ocs, which precipitated to the the 400}4000 cm\ frequency range. For the infrared ab-
bottom of the reaction vessel. The mixture was kept under sorption spectra, the samples were formed into pellets with
high-speed constant stirring on a magnetic stirrer for 1 h at KBr and the spectra were recorded on a Nicolet740 FTIR
room temperature. Subsequently, the precipitated titanium Spectrometer at ambient conditions. IR spectroscopy in
dioxide (TiO .nH O) was "ltered and repeatedly washed the transmission mode gives qualitative information about
  the way in which the adsorbed molecules are bonded to the
with hot distilled water to make TiO .nH O free of chloride
  surfaces as well as the structural information of solids.
ions. The hydrous oxide was dried at 90}1003C over night
and then ground to a "ne powder. The polycrystalline (e) SEM and ¹EM analysis. The samples calcined at
titanium dioxide powders were then calcined at 100, 200, 4003C were dispersed in distilled water and then sonicated
300, 400, 500, or 6003C for 2 h to observe the phase changes ultrasonically to separate out individual particles, for the
accompanying the heat treatments. determination of the particle size. The particle size and
Samples for UV}visible spectroscopy studies were pre- external morphology of the samples were observed on
pared starting with various concentrations of TiCl , 0.1 M
 a Hitachi S520 scanning electron microscope (SEM) and
(Sample A) and 0.05 M (Sample B). Commercial TiO from
 transmission electron micrographs (TEM) were recorded on
Aldrich (Sample C) was taken as reference. These three a JEOL JEM-100CX electron microscope.
samples (each of 0.4 g TiO ) were subsequently capped with

0.005 g of poly (ethylene glycol) (PEG) and sequentially ( f ) ;<}visible absorption spectrum. The samples were
labeled as Samples D, E, and F. All the samples were dispersed in distilled water and sonicated ultrasonically for
uniformly incorporated with 0.001 g eriochromcyanin dye. the absorption studies on a Shimadzu 240 (Japan) spectro-
The samples appeared in di!erent colors, which is attributed photometer. The quantum size e!ect is better understood
primarily to the particle size variation. from the UV absorption spectra. The absorption spectra
also give an estimate of the size distribution in the sample
from the sharpness of the absorption features. The salient
features of the absorption spectra can be clearly deciphered
2.2. Nanoparticle Characterization
from the second derivative spectra (13). The position of the
(a) D¹A}¹GA. The dried "ne powder of synthesized minima in the second derivative spectra gives a good ap-
TiO was subjected to thermo gravimetric}di!erential ther- proximation of the position of the shoulders that arise from

mal analysis (TG}DTA) (Mettler Toledo Star system). This the transitions to discrete higher electronic levels.
182 MADHUSUDAN REDDY, GOPAL REDDY, AND MANORAMA

FIG. 1. DTA}TGA curve of prepared nanocrystalline TiO : (*) DTA, (. . .) TGA.



3. RESULTS AND DISCUSSION data shows that TiO has been e!ectively capped with

poly(ethylene glycol).
3.1. DTA}TGA
Figure 1 shows the typical DTA and TGA thermo- 3.3. XRD
diagrams for the as prepared product. DTA analysis
of the product indicates a prominent endotherm below Figure 3 (lines a}g) shows the XRD patterns of samples
1003C due to free adsorbed water. The exothermic shoulder as synthesized and subsequently calcined at di!erent
around 3003C corresponds to the decomposition of resi-
dual }OH groups and the condensation of nonbonded
oxygen. The process continues with an exothermic peak
at about 3903C, which corresponds to the crystallization
of the anatase phase. At 5603C the product com-
pletely transforms into the anatase phase. At around
7003C the rutile phase starts appearing. Thereafter no
signi"cant thermal e!ects can be detected even up to
10003C.

3.2. FT}IR
Figure 2 (lines a and b) shows the spectra of prepared and
poly(ethylene glycol) (PEG) capped TiO , respectively.

Figure 2 (line a) shows the IR spectrum of the TiO in the

range of 400}4000 cm\, which agrees with the reported
data (27). Figure 2 (line b) is for the polymer capped TiO .

The bifurcated peak between 2800 and 2900 cm\ is due to
alkyl group of poly(ethylene glycol). The broad peak at
1100 cm\ is that of the ether linkage (}CH }O}CH })
 
and the peak between 3200 and 3600 cm\ suggests the FIG. 2. FT}IR spectrum of (a) nanocrystalline TiO and (b) nanocrys-

presence of hydroxyl groups in diblock at one terminal. This talline TiO capped with PEG.

 SPECTRAL STUDIES ON NANOCRYSTALLINE ANATASE TITANIA 183

TiO powders were calcined at higher temperatures, the


transformation such as amorphous to anatase phase occurs.
The amorphous}anatase transformation was complete in
the temperature range from 400 to 6003C as is evident from
the "gure. The XRD peaks of powder calcined at 100, 200,
or 3003C are weak in comparison to those of the samples
calcined at higher temperatures, which suggests that a sig-
ni"cant amount of amorphous phase still remains in the
powder at these temperatures. The crystallite size was esti-
mated by the Scherrer formula (26), which is generally the
accepted method to estimate the mean crystallite size. The
crystallite sizes were found to be in nanometer regime 6.1,
8.07, 8.50, and 12.10 nm for the samples calcined at 300, 400,
500, or 6003C respectively. The XRD patterns of the
amorphous TiO are in agreement with those reported (28),

so the e!ect of the amorphous material on the broadening of
the XRD patterns of nanosized TiO is negligible. There is

also a report by Sunstrom et al. (29) with a similar XRD
pattern for TiO prepared by the hydrodynamic cavitation

method. The particle size calculations were made from the
TEM micrographs and were found to be around 3}8 nm.
The particle size is uniform as seen from the micrographs in
Figs. 4a and 4b.

FIG. 3. XRD pattern of TiO calcined at (a) RT, (b) 1003C, (c) 2003C,

3.4. Surface Area
(d) 3003C, (e) 4003C, (f ) 5003C, and (g) 6003C.
The surface area measurements were carried out for
nanoparticles of TiO calcined at temperatures from 100 to

6003C. The as-prepared sample showed a BET surface area
temperatures from 100 to 6003C. The as-prepared sample is of 213 m/g and the one calcined at 6003C, 65 m/g. The
largely amorphous. Calcination is a common treatment results of surface area measurements and the crystallite size
used to improve the crystallinity of TiO powders. When are depicted in Fig. 5.


FIG. 4. Typical (a) scanning electron (;10K) and (b) transmission electron (;20K) micrographs of the synthesized TiO .

184 MADHUSUDAN REDDY, GOPAL REDDY, AND MANORAMA

FIG. 6. UV}vis absorption spectra of TiO showing the blue shift


with decrease in particle size (a) 0.1 M (E "3.145 eV), (b) 0.05 M

(E "3.167 eV), (c) commercial TiO (E "3.027 eV), (d) 0.1 M (E "
   
3.145 eV) capped with PEG, and (e) 0.05 M (E "3.167 eV) capped with

PEG.
FIG. 5. Variation of the crystallite size and surface area as a function
of the calcination temperature of TiO .


approximated using Eq. [1]. The samples obtained from

0.1 M titanium tetrachloride have an average particle size of
3.5. Quantum Size Ewect of the TiO2 Nanoparticles from
6 nm and those from 0.05 M titanium tetrachloride average
UV}Vis Spectroscopy
about 3 nm.
UV}vis spectroscopy has been used to characterize the The optical absorption threshold for nanocrystallites of
bulk structure of crystalline and amorphous titanium this size shifts to higher energies, i.e., toward the blue end of
dioxide. Titania is a semiconducting oxide with easily mea- the spectrum as the crystallite size decreases (31). The size-
sured optical bandgap. UV}vis di!use re#ectance spectro- dependent shift in the bandgap can be calculated as
scopy is used to probe the band structure or molecular
energy levels in the materials since UV}vis light excitation *E "
n/2R +1/m #1/m ,!1.786 e/eR (0.248 E ),
creates photo-generated electrons and holes. The UV}vis    07
absorption band edge is a strong function of titania cluster [1]
size for diameters less than 10 nm, which can be attributed
to the well-known quantum size e!ect for semiconductors where R, is the radius of the particle and E , is the e!ective
07
(30). Figure 6 (lines a}e) shows the UV}visible absorption Rydberg energy. This model predicts an increase in the
spectra of the sample (a) 0.1 M, (b) 0.05 M, (c) commercial, bandgap with decrease in particle dimensions. The size-
(d) 0.1 M with PEG capped, and (e) 0.05 M with PEG dependent shift in the bandgap is found to be 0.1}0.2 eV
capped titania nanoparticles. The M indicates the molarity (32).
of the starting material, titanium tetrachloride. When the The nature of the absorption spectra can be more clearly
concentration of starting material is varied, the absorption seen from the second derivative spectra. Figure 7 (lines a}e)
spectra of the synthesized nanoparticles show a di!erence. shows the double derivative of the absorption spectra of the
Extrapolating the curves in the plot we have the bandgap samples replotted using the data of Fig. 6. The position of
energy of the nanoparticles. The bandgap energies (E ) ob- the minima in the double derivative gives a good approxi-

tained are as follows: for the 0.1 M samples, it is 3.145 eV mation of the position of the shoulders of the absorption
(absorption edge at about 395 nm), for the 0.05 M samples, spectra. These shoulders arise from the transitions to dis-
it is 3.167 eV (absorption edge at 392 nm), and for (c) the crete higher electronic levels. The energies required for the
commercial sample the value is 3.027 eV (absorption edge is higher transitions gradually increase with decreasing par-
at 404 nm). It is clear that as the particle size decreases ticle size. This can be visualized from Fig. 7. Since the
the bandgap energies increase. Size quantization causes particle size of the sample (b) is 3 nm, the position of the
the absorption edge to be shifted to higher energies. From minima is toward the lower wavelength (higher energy)
the shift in the bandgap (*E ), the particle size can be compared with sample (a), which has particle size of 6 nm

 SPECTRAL STUDIES ON NANOCRYSTALLINE ANATASE TITANIA 185

FIG. 7. Second derivative of UV}vis absorption spectra of TiO


nanoparticles showing the position of shoulders, replotted using Fig. 6.

and has the minima toward higher wavelength. It is ob-

served that the energies required for the higher transitions
gradually increase with decreasing particle size, in agree-
ment with the theoretical predictions (13). FIG. 8. (I) UV}vis spectra of (A) 0.1 M and (B) 0.05 M TiO nanopar-

ticles and (A48) 0.1 M and (B48) 0.05 M TiO nanoparticles after 48 h.

(II) UV}vis spectra of PEG-capped (D) 0.1 M and (E) 0.05 M TiO nano-

particles, and PEG-capped TiO (D48) 0.1 M, (E48) 0.05 M stabilized after

3.6. Ewect of Polymer Capping on TiO2 Nanoparticles 48 h.

Figure 8 (I and II) shows the UV}visible absorption

spectrum for the nanoparticles of titanium dioxide (with
and without polymer capping). In Fig. 8(I), the curves A
3.7. Incorporation of Dye
and B give the absorption spectra of nanoparticles of TiO :

(A) for the particles synthesized from the 0.1 M solution, All of the samples are incorporated with 0.001 g of erioch-
(B) for the particles synthesized from 0.05 M solution of romcyanin. The prepared nanocrystalline sample 0.1 M
TiCl . The curves A48 and B48 give the absorption spectra gave pink color and the sample with 0.05 M gave light

of the samples A and B taken after 48 h. The observed orange. The photographs show a distinct color change with
shift in the absorption spectra of the latter samples can the change in the size of the particle. Since the particles
be attributed to the agglomeration of the nanopartic- prepared from 0.05 M solution of TiCl are comparatively

les with time. Figure 8(II) shows the absorption spectra smaller than those prepared from 0.1 M solution the color
of the samples with polymer}capped nanoparticles of TiO . pattern shows a blue shift: from pink to light yellow. This

Spectra D and E are for the samples A and B capped indicates a shift in the color toward the blue region.
with the polymer PEG correspondingly. In this latter
case we observed that even though we recorded the
absorption spectra after 48 h there is not much di!erence 4. CONCLUSIONS
in the intensities nor is there any shift. The two spectra
nearly overlap. This is as expected, since the PEG cap- The results presented in this paper bring out the following
ping of the nanoparticles prevents agglomeration of conclusions:
the particles. The polymer acts as a barrier between E A method for preparation of TiO nanoparticles with

the particles and prevents any kind of interaction between large surface area and exclusively anatase crystal structure
them. has been demonstrated.
186 MADHUSUDAN REDDY, GOPAL REDDY, AND MANORAMA

E Successfully characterized, the synthesized particles in 11. H. Tang, K. Prasad, R. Sanjjiness, and F. Levy, Sens. Actuators
the nanometre regime and the size of the crystals were found B 26+27, 71}75 (1995).
to be 3}10 nm as estimated from Scherrer formula. This 12. G. Schmid, M. Baumle, M. Greekens, I. Heim, C. Osemann, and
T. Sawitowski, Chem. Soc. Rev. 28, 179}185 (1999).
data is also supported by evidence from SEM and TEM 13. M. Sequeira and S. G. Dixit, Chemical Industry Digest, March/April
micrographs. p. 60 (1999).
E The TiO synthesized has a large surface area, 14. V. Chhabra, V. Pillai, B. K. Mishra, A. Morrone, and D. O. Shah,
 ¸angmuir 11, 3307}3311 (1995).
210 m/g as estimated by the BET method and this is a very
important property for catalytic, photocatalytic, and gas 15. M. Lal, V. Chhabra, P. Ayyub, and A. Maitra, J. Mater. Res. 13(5),
1249 (1988).
sensor applications. 16. L. K. Campbell, B. K. Na, and E. I. Ko, Chem. Mater. 4(6), 1329}1333
E The nanoparticles showed a concomitant blue shift in (1992).
the absorption spectrum with a decrease in the particle size. 17. U. Selvaraj, A. V. Prasadrao, S. Komerneni, and R. Roy, J. Am. Ceram.
E The bandgap energy values observed for di!erent par- Soc. 75(5), 1167}1170 (1992).
ticle sizes were 3.167 eV (3 nm), 3.145 eV (6 nm) for prepared 18. T. Sugimoto, K. Okada, and H. Itoh, J. Colloid. Interface Sci. 193, 140
(1997).
TiO and 3.027 eV (39 nm) for commercial titanium dioxide.
 19. H. Kumazava, H. Otuski, and E. Sada, J. Mater. Sci. ¸ett. 12, 839}841
These shifts are in good agreement with the calculated (1993).
values. 20. R. R. Basca and M. Gratzel, J. Am. Ceram. Soc. 79(8), 2185}2188
E Eriochromcyanin-incorporated nanoparticles di!ered (1996).
in color with the change in particle size. 21. H. Cheng, J. Ma, Z. Zhao, and L. Qi, Chem. Mater. 7, 663}667 (1995).
22. T. R. N. Kutty, R. Vivekanandan, and P. Murugaraj, Mater. Chem.
E The TiO capped with PEG restricted the agglomer-
 Phys. 19(6), 533}546 (1988).
ation of the particles. 23. Y. Qian, Q. Chen, Z. Chen, C. Fan, and G. Zhou, J. Mater. Chem.
3(2), 203}205 (1993).
24. T. Masui, K. Fujiwara, K. Machida, and G. Adachi, Chem. Mater.
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