Journal of Nanoparticle Research 3: 141147, 2001.

2001 Kluwer Academic Publishers. Printed in the Netherlands.

Effect of particle size and phase composition of titanium dioxide

nanoparticles on the photocatalytic properties

Hee Dong Jang1 , Seong-Kil Kim2 and Seung-Jin Kim3

1
Division of Materials Development, Korea Institute of Geoscience and Mineral Resources, Taejeon, 305-350,
Korea (E-mail: hdjang@kigam.re.kr); 2 R&D Center, Samhwa Paint Industry, Ansan, 425-110, Korea; 3 R&D
division, Korea Institute of Construction Materials, Seoul, 137-070, Korea

Received 1 December 2001; accepted in revised form 22 March 2001

Key words: particle size, phase composition, titanium dioxide nanoparticles, photocatalytic property

Abstract

Titanium dioxide (TiO2 ) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl4 ) in a diffu-
sion flame reactor. The average diameter of particles was 1530 nm and mass fraction of anatase ranged from 40%
to 80%. Effects of particle size and phase composition of those TiO2 nanoparticles on photocatalytic properties such
as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition
of methylene blue by the TiO2 nanoparticles under the illumination of the black light was directly proportional to
the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by
the TiO2 nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the
methylene blue.

Introduction the destruction of organic compounds in polluted air

Particles smaller than several tens of nanometers in pri-
mary particle diameter (nanoparticles) are of interest
for the synthesis of new materials because of their low
melting point, special optical properties, high catalytic
activity, and unusual mechanical properties compared
with their bulk material counterparts (Siegel, 1991).
Fujishima and Honda (1972) discovered the photo-
catalytic splitting of water on titanium dioxide (TiO2 )
electrodes. Their results marked the beginning of a new
era in the field of photocatalysis. Since then, extensive
research efforts to understand the fundamental process
and to enhance the photocatalytic efficiency of TiO2
have been made by chemists, physicists, and chemi-
cal engineers. Such studies are often related to energy
renewal and energy storage (Bard, 1980; Parmon &
Zamareav, 1989). In recent years, applications to the
environmental cleanup have been one of the most
active areas in photocatalysis. This is inspired by the
potential application of TiO2 -based photocatalysts for
and wastewaters (Ollis & Al-Ekabi, 1993) because
TiO2 nanoparticles have high photoactivity on the
decomposition of organic materials, and chemically
stable properties, etc.
In a photocatalytic system, photo-induced molecu-
lar transformation or reaction takes place at the sur-
face of catalyst. A basic mechanism of photocatalytic
reaction on the generation of electron-hole pairs and
its destiny is as follows; when a photocatalyst is illu-
minated by the light stronger than its band gab energy,
electron-hole pairs diffuse out to the surface of the
photocatalyst and participates in the chemical reaction
with electron donor and acceptor. To achieve a higher
photoactivity, it is essential to suppress the subsequent
recombination process and to increase the lifetime
of separated electron-hole pairs, so that fast electron
transfer occurs from the surface to the adsorbed inter-
mediates (Hoffman et al., 1995; Kominami et al., 1997).
There are many variables that affect the photoactivity
such as particle size, crystal structure, incident light
142
intensity, pH of solution, and preparation method of
particles. Crystal structure and particle size are con-
sidered as important factors that determine photoac-
tivity. Many researchers reported that anatase titania
nanoparticles have higher photoactivity than the rutile
one (Nishimoto, 1985; Sclafani et al., 1990; Fox &
Dulay, 1993; Jung & Park, 1999). Fotou et al. (1994)
prepared TiO2 nanoparticles using a flame reactor and
reported that the anatase phase TiO2 containing a
small amount of rutile phase had higher photoactiv-
ity than that of pure anatase for the decomposition of
phenol and salicylic acid. Lee et al. (1992) also pre-
pared TiO2 nanoparticles using a flame reactor and
a tube furnace reactor and measured the decomposi-
tion of dichlorobenzene. However, effects of the crys-
tal structure and particle size of the TiO2 nanoparticles
on the photocatalytic properties have not performed
quantitatively.
In this work, TiO2 nanoparticles having different
phase compositions and particle sizes were prepared
by the gas phase oxidation of titanium tetrachloride
(TiCl4 ) in a flame reactor. The effect of the particle
size and phase composition of TiO2 nanoparticles on
the photocatalytic properties such as decomposition of
methylene blue, bacteria, and ammonia gas were inves-
tigated quantitatively.
Experiments
Preparation of TiO2 nanoparticles
To prepare the TiO2 nanoparticles, the vapor-phase syn-
thesis from TiCl4 in a flame reactor was adopted in
Figure 1. A schematic of experimental apparatus for the synthesis of TiO2 nanoparticles.
the present study. Through the combustion of hydro-
gen, water vapor and oxygen exist in the flame. Thus,
TiCl4 is converted to TiO2 in two ways: hydrolysis and
oxidation (Jang, 1997).
Hydrolysis of TiCl4 takes place according to the
overall reaction as follows:
TiCl4 (g) + 2H2 O(g) TiO2 (s) + 4HCl(g) (1)
Oxidation of TiCl4 takes place according to the over-
all reaction as follows:
TiCl4 (g) + O2 (g) TiO2 (s) + 2Cl2 (g) (2)
A scheme of the experimental apparatus for the
generation of TiO2 nanoparticles is shown in Figure 1.
A diffusion flame burner (3.4 cm in outside diameter
and 45 cm in length) composed of five concentric stain-
less tubes (10, 16, 22, 28, and 34 mm in outside diam-
eter) was installed. A quartz tube of 10 cm in diameter
and 120 cm in length was also installed to preserve the
flame and particles. Liquid phase TiCl4 was injected
to the evaporator by using the syringe pump. The tem-
perature of the evaporator was maintained above the
boiling point of the TiCl4 . The liquid TiCl4 injected
into the evaporator was instantly evaporated. Then
this TiCl4 was completely carried into the central tube
of the burner with 2 l/min of dry argon (Ar) gas. The
evaporation and transportation of TiCl4 in the evapora-
tor was confirmed through the pre-test by observation
of the TiCl4 vapor having white color in the atmosphere
without the combustion flame. Hydrogen (H2 ) was
used as a fuel and oxygen (O2 ) and air as oxidants.
A PtRh R type thermocouple (Omega Engineering)

was used to measure the flame temperature of the
burner. TiO2 nanoparticles generated from TiCl4 by the
gas phase reaction were collected with a bag filter that
was made of teflon fiber (Tefaire, Dupont Co.). The
particle morphology and size were observed by trans-
mission electron microscopy (TEM, Philips Model
CM12). The average particle diameter was determined
by counting more than 200 particles from TEM pic-
tures (Jang & Jeong, 1995). The specific surface area
of the powders was measured by nitrogen adsorption
at 196 C using the BET equation (Micrometrics
Model ASAP 2400). Assuming spherical particles,
the average particle size dp was calculated from mea-
sured specific surface area A and particle density p
by dp = 6/(p A), and observed particle sizes and
calculated ones were compared. X-ray diffractometer
(XRD, Rigaku Co. Model RTP 300 RC) was used to
analyze X-ray diffraction patterns. The phase compo-
sition of TiO2 particles was calculated from relative
intensities of the strongest peaks corresponding to
anatase and rutile (Spurr & Myers, 1957).
Determination of photocatalytic properties
The photocatalytic properties of TiO2 nanoparti-
cles were characterized through the decomposi-
tion of methylene blue, bacteria, and ammonia gas.
Experimental methods to determine these properties
are as follows.
Figure 2. A schematic of PEC for the measurement of the decomposition of the methylene blue.
143
Decomposition of methylene blue
Decomposition of methylene blue (C16 H18 CIN3 S) was
determined by a photocatalysis evaluation checker
(PEC, Ulvac Co., Model PCC-1). PEC consists of a
light emitting element and receiving element that are
connected to a black light (UV quantity about 1 mW)
by means of a fiber. The absorbance change (ABS)
between two elements with decomposition of colored
film (methylene blue) by photocatalysis can be deter-
mined relatively with PEC (Figure 2). Large absolute
value of the ABS means the high decomposition
of methylene blue by photocatalyst. Experimental
procedure was as follows: one gram of TiO2 nanopar-
ticles were put into one liter of coating agent, and
agitated to obtain full suspension. Then thin TiO2 film
was prepared with coating solution including TiO2
nanoparticles on the surface of stainless steel plate of
10 20 cm in dimension by using a bar coater, and
dried for 24 h. TiO2 coated plate was covered with
methylene blue solution of 1 mmol/L by dipping, and
dried for 2 h. Then, the decomposition of methylene
blue was measured by PEC.
Decomposition of bacteria
Escherichia coli and Pseudomonas areruginosa were
chosen as bacteria to determine the decomposition of
bacteria. The growth in the number of each bacte-
ria without addition of TiO2 nanoparticles under the
illumination of a fluorescent light (UV quantity about
144

1 W) was measured with the lapse of time. After the

addition of 0.1 g of TiO2 at the known number of bac-
teria, the change of the number of bacteria was mea-
sured with the lapse of time under the illumination of
fluorescent light.
Decomposition of ammonia gas
TiO2 nanoparticles (0.2 g) was put into a closed cylin-
drical glass chamber that was 15 cm in diameter and
30 cm in length. The chamber was illuminated with
the fluorescent light (UV quantity about 1 W) that
was installed at 2 cm apart from the top of the cham-
ber. Thin foils (4 4 cm in dimension) made of TiO2
nanoparticles were prepared for the experiment, and
placed on the center of the chamber floor. Ammonia
gas was fed into the chamber to maintain the initial Figure 3. Effect of TiCl4 concentration on BET surface area
concentration of 500 ppm in the chamber. The varia- (O2 : 15 l/min, Air: 60 l/min, H2 : 6 l/min, and Ar: 5 l/min, Carrier
tion of concentration of ammonia in the chamber was gas (Ar): 2 l/min).
measured with a gas detector (Cole-Parmer, Model
P81900) in course of time.

Results and discussion

Preparation of TiO2 nanoparticles

For the preparation of TiO2 nanoparticles having dif-

ferent particle sizes at the constant anatase mass frac-
tion, TiCl4 concentration in the flame was varied from
8.90 106 to 5.54 105 mol/l by changing the feed
rate of TiCl4 at the maximum flame temperature of
1700 C. Gas flow rates of the burners to synthesize
the TiO2 particles are as follows; 1st : 2 l/min of Ar,
2nd : 5 l/min of Ar, 3rd : 6 l/min of H2 , 4th : 15 l/min
of O2 , and 5th : 60 l/min of air. As TiCl4 concentra-
tion increased, the specific surface area decreased from
102 to 50 m2 /g (Figure 3). The average diameter from
the BET analysis was 15 nm at 8.90 106 mol/l and
increased to 30 nm at 5.54 105 mol/l. The aver- Figure 4. TEM image of TiO2 nanoparticles generated at
age diameter obtained from TEM picture was 13 nm 8.9 106 mol/l of TiCl4 concentration.
at 8.9 106 mol/l and increased to 28 nm at 5.54
105 mol/l. Geometric standard deviations at different In order to change anatase mass fractions keeping
concentrations of TiCl4 were nearly constant; it was particle size constant, TiCl4 concentration and gas flow
about 1.6. The average particle sizes calculated from rate in the 4th and 5th tube of the burner were varied.
BET-adsorption areas were nearly the same as those As the oxygen flow rate decreased from 15 to 5 l/min at
obtained from TEM study. Figure 4 shows TEM image fixed total gas flow rates, and 2.27105 mol/l of TiCl4
of TiO2 nanoparticles generated at 8.9 106 mol/l concentration, the average particle diameter calculated
of TiCl4 concentration. From the analysis of X-ray from the BET data also decreased from 23 to 14 nm.
diffraction patterns, the crystalline phases of the TiO2 The maximum flame temperature was lowered from
nanoparticles generated from different TiCl4 concen- 1700 C to 1400 C along with the decrease in the oxy-
trations were found nearly the same; it was 45% anatase gen flow rate. This decrease of particle diameter is con-
in mass fraction. sidered to be due to low coagulation and sintering rate

Figure 5. X-ray diffraction patterns of TiO2 nanoparticles
((a): 80%, (b): 61%, (c): 48%, (d): 45% of anatase mass fraction).
of particles in lower flame temperature. The anatase
mass fraction of TiO2 nanoparticles increased from
41% to 80% as the oxygen flow rate decreased from 15
to 5 l/min. When 10 l/min of air was introduced into the
4th tube of the burner while holding the constant total
gas flow rates and 2.27 105 mol/l of TiCl4 concen-
tration, the average particle diameter of product par-
ticles was 14 nm and anatase mass fraction was 61%.
When the total gas flow rate was changed from 65 to
70 l/min by decreasing the air flow rate in 5th tube of
the burner, particle size and anatase mass fraction were
15 nm and 48%, respectively. In this case, the feed rate
was held at 2.0 103 mol/min and the gas flow rate of
the burners as follows; 1st : 2 l/min of Ar, 2nd : 5 l/min
of Ar, 3rd : 6 l/min of H2 , and 4th : 10 l/min of air.
Figure 5 shows that the X-ray diffraction pattern of
TiO2 nanoparticles indicates different anatase mass
fraction even at the constant particle size (about 15 nm).
Determination of photocatalytic properties
Decomposition of methylene blue
Specific surface area and phase composition of TiO2
particles are known as the most important properties
for a photocatalyst. Higher photocatalytic activity can
be obtained with higher surface area and anatase mass
fraction of TiO2 particles. Larger surface area can be
obtained by decreasing the particle size of the photo-
catalyst when the particle has a single domain size. As
the surface area increases, larger contact area between
the photocatalyst and target material can be obtained.
In a photocatalysis system, photo-induced molecular
reaction takes place at the surface of the photocatalyst.
145
Figure 6. Effect of particle size of TiO2 nanoparticles on the
decomposition of methylene blue ((a): without TiO2 , (b): dp =
30 nm, (c): dp = 26 nm, (d): dp = 23 nm, (e): dp = 15 nm).
Then, the higher yield of photocatalytic reaction could
be obtained from the high surface area of the photocat-
alyst. In the case of higher anatase mass fraction that
could be prepared by the control of reactant concen-
tration and flame temperature, higher level of photon
induced electron or energy transfer to the target mate-
rial is generated and then it enhances the photocatalytic
activity of TiO2 particles.
Figure 6 shows the effect of particle size on the
decomposition of methylene blue at the constant phase
composition of TiO2 . The phase composition of TiO2
nanoparticles in Figure 6 was 45% anatase in mass frac-
tion. As the particle size decreased, the absolute value
of ABS, which represents the degree of the decompo-
sition of methylene blue, increased. The decomposition
of methylene blue by the commercial TiO2 nanoparti-
cles (Degussa, P25) was also measured for comparison.
Properties of the P25 are as follows; average diameter
is 25 nm, and the phase composition is 75% anatase.
When the particle size was less than 23 nm, the absolute
value of ABS of methylene blue by TiO2 nanopar-
ticles prepared in the present study was a little higher
than that of the P25. It was considered that the degree of
decomposition became larger owing to larger surface
area even though anatase mass fraction of synthesized
powder was smaller than that of the P25.
Figure 7 shows the effect of the phase composition at
the fixed particle size on the decomposition of methy-
lene blue. The particle size of TiO2 nanoparticles was
about 15 nm in average diameter. As the phase compo-
sition of anatase increased, the absolute value of ABS
of methylene blue also increased and the degree of
decomposition became larger than that of the variation
146
of the particle size. The degrees of the decomposi-
tion of methylene blue by TiO2 nanoparticles having
different phase composition were higher than that of
the P25. From the above results, the decomposition of
methylene blue was affected by the particle size and
anatase mass fraction. The effect of anatase mass frac-
tion played a more important role in enhancing the
degrees of decomposition of methylene blue than that
of particle size.
Decomposition of bacteria
The initial numbers of bacteria (Escherichia coli and
Pseudomonas areruginosa) prepared were about 400.
The degree of decomposition of bacteria was observed
after 30 min, 1 h, and 3 h. The number of bacteria was
Figure 7. Effect of anatase mass fraction on the decomposition
of methylene blue ((a): without TiO2 , (b): with P25, (c): 45%, (d):
48%, (e): 61%, (f): 80%).
Figure 8. Images of Escherichia coli before and after the addition of TiO2 nanoparticles into the bacteria ((a) before the addition of TiO2
nanoparticles, (b) after the addition of TiO2 nanoparticles).
not changed after 1 h. The effect of particle size keeping
constant anatase mass fraction (45%) on the decompo-
sition of the Escherichia coli was found to be 93.2% at
the particle size of 30 nm and 97.6% at the particle size
of 15 nm, respectively. As the anatase mass fraction
increased from 45% to 80%, the degree of decomposi-
tion of the Escherichia coli also increased from 97.6%
to 99.1%. Figure 8 shows the image of Escherichia
coli before and after the addition of TiO2 nanoparticles
to the bacteria. The same trend of the decomposition
of the Pseudomonas areruginosa was obtained as in
the case of the Escherichia coli. As previously stated,
the decomposition of bacteria with P25 was observed
for comparison; it was 98.6% for the Escherichia coli
and 99.6% for the Pseudomonas areruginosa. From
this result, it was found that TiO2 nanoparticles hav-
ing smaller size and higher anatase mass fraction were
more effective in the decomposition of the bacteria
under the illumination of very low intensity of UV light,
and anatase mass fraction was much more effective in
the decomposition of the bacteria than the particle size.
Decomposition of ammonia gas
The decomposition of ammonia gas by the TiO2
nanoparticles was also investigated by varying particle
size and anatase mass fraction. The decomposition of
the ammonia gas of initial concentration of the 500 ppm
was measured at every 30 min for 2 h. The degree of
decomposition became constant after 1 h in all sam-
ples. As the particles containing 45% anatase became
smaller from 30 to 15 nm, the degree of decomposition
of ammonia slightly increased from 8% to 10%. When

Figure 9. Effect of anatase mass fraction on the decomposition
of the ammonia gas.
the phase composition was varied at the constant parti-
cle size (15 nm) the degree of decomposition of ammo-
nia gas increased from 10% to 13% (Figure 9) while
9% of ammonia in the chamber gas was decomposed
by the P25.
Conclusions
Photocatalytic TiO2 nanoparticles having various par-
ticle sizes and phase compositions were prepared
through the control of TiCl4 concentration and gas
flow rate in the diffusion flame reactor; the particle
size ranged from 15 to 30 nm and anatase mass frac-
tion from 45% to 80%. Photocatalytic properties of
TiO2 nanoparticles such as decomposition of methy-
lene blue, bacteria and ammonia gas were investigated
in terms of the particle size and anatase mass fraction.
As the particle size decreased and anatase mass fraction
increased, a higher degree of decomposition of methy-
lene blue by the TiO2 nanoparticles under the illumi-
nation of the black light was obtained. The higher
147
degree of decomposition of bacteria and ammonia gas
by the TiO2 nanoparticles under the illumination of
the fluorescent light was found at the smaller particle
size and the higher phase composition of anatase. The
effect of anatase mass fraction played a more important
role in enhancing photocatalytic properties than that of
particle size.
Acknowledgements
This study was supported by the Korea Institute of
Industrial Technology Evaluation & Planning.
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