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Particuology 7 (2009) 204210

Contents lists available at ScienceDirect

Particuology
journal homepage: www.elsevier.com/locate/partic

Synthesis of TiO2 nanoparticles by propane/air turbulent ame CVD process

Hongyong Xie , Guilan Gao, Zhen Tian, Naici Bing, Lijun Wang
School of Urban Development and Environmental Engineering, Shanghai Second Polytechnic University, 2360 Jin Hai Road, Pudong, Shanghai 201209, China

a r t i c l e i n f o a b s t r a c t

Article history: Synthesis of TiO2 nanoparticles by the oxidation of titanium tetrachloride (TiCl4 ) in high-strength
Received 6 July 2008 propane/air turbulent ame is investigated tentatively for mass production of TiO2 nanoparticles. Effects of
Accepted 4 March 2009 reactor heat ux varying from 247 to 627 kJ/m2 s, initial TiO2 number density from 2 1020 to 1 1021 m3 ,
and apparent residence time of TiO2 nanoparticles in reactor from 0.06 to 0.9 s, on particle morphology,
Keywords: phase composition, UV absorption and photoluminescence (PL) spectra are studied. The TiO2 nanoparti-
CVD
cles synthesized, with mean size of 3080 nm and rutile mass fraction from 0.155 up to 0.575, exhibited
Turbulent ame
a strong PL signal at the wavelength of 370450 nm, with a wide peak signal at 400420 nm, reecting
TiO2 nanoparticles
PL spectra
signicant oxygen vacancies on the surface of the TiO2 nanoparticles.
2009 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Sciences. Published by Elsevier B.V. All rights reserved.

1. Introduction
Particles smaller than several tens of nanometers are considered
nanoparticles, which have unusual structural, electronic, optical,
magnetic and chemical properties, leading to many important
applications, e.g., titanium dioxide nanoparticles activated by near-
ultraviolet (UV) light constitute by far the most widely studied
photocatalytic material for the purication of polluted water and
air (Goswami, Trivedi, & Block, 1997; Ollis & Al-Ekabi, 1993).
There are several methods to prepare nanosized TiO2 particles,
such as solgel process (Pierre, 1991), microemulsion-mediated
method (Shi, Hua, & Zhang, 1998a), and aerosol chemical reaction
(Fissan & Schoonman, 1988; Shi, Li, & Fang, 1998b), the last having
the advantages of high purity, high yield, and easy separation of the
product from the exhaust (Fissan & Schoonman, 1988). Moreover,
the gas phase processes have the advantage of rapid mixing on a
molecular scale and are thus energy efcient (Osterwalder, Capello,
Hungerbuhler, & Stark, 2006; Shi et al., 1998a, 1998b).
Various aerosol processes have been developed for the prepa-
ration of nanoparticles on a laboratory scale, such as ame, tube
furnace, gas-condensation, thermal plasma, laser, and sputtering.
Since the ame chemical vapor deposition (CVD) process has been
scaled up to produce commercial quantities of sub-micron ceramic
particulates, such as silica and titania, at low cost (Zhu & Pratsinis,
1996), it has received intensive investigations on preparing TiO2
nanoparticles using different fuels, e.g. hydrogen (Formenti, Juillet,
Corresponding author. Fax: +86 021 50217725.
E-mail addresses: hyxie@eed.sspu.cn, hyxie@163.com (H. Xie).
Meriaudeau, Teichner, & Vergnon, 1972; Shi et al., 1998a, 1998b),
methane (Pratsinis, Zhu, & Vemury, 1996), carbon monoxide and
propane (Xie, Ning, Mao, Wang, & Sun, 2002; Zhang, Sun, & Xie,
2004).
To lower cost, industrial propane was used as fuel in the synthe-
sis of TiO2 nanoparticles by laminar-ame propane/air oxidation
of titanium tetrachloride (TiCl4 ) (Zhang et al., 2004), to yield TiO2
nanoparticles which compared favorably with Degusa P25 TiO2
nanoparticles in terms of photodegradation of formaldehyde (Xie,
2007a), benzene (Zhang, Xie, & Xu, 2007), methanol (Xie, Zhang, &
Xu, 2007) and toluene (Xie, Zhang, & Xu, 2008).
However, laminar-ame has low combustion strength and is dif-
cult to scale up for mass production of TiO2 nanoparticles. In this
study, an industrial propane/air turbulent ame CVD process was
studied for mass production of TiO2 nanoparticles by the oxidation
of TiCl4 . Effects of reactor heat ux varying from 247 to 627 kJ/m2 s,
together with initial TiO2 number density and apparent residence
time of TiO2 nanoparticles in reactor, on particle size, phase com-
position, UV absorption and photo-luminescence (PL) spectra are
reported.
2. Experimental
A schematic diagram of the experimental apparatus is shown
in Fig. 1. The reactor or combustion chamber is a 0.50-m long,
157 mm 3.5 mm stainless steel pipe. The burner is a Honeywell
2000 kcal combustion burner. Industrial propane and air are used as
fuel and oxidant, respectively, to generate a propane/air turbulent
ame. TiO2 particles are generated in the reactor by the oxidation
of TiCl4 , which is carried into the reactor through tappings or the
burner by dry air passing through a TiCl4 bubbler.

1674-2001/$ see front matter 2009 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.partic.2009.03.003
 Author's personal copy

H. Xie et al. / Particuology 7 (2009) 204210 205

Fig. 1. Schematic diagram of experimental apparatus.

TiCl4 is carried into the reactor at three different positions to
examine the effect of residence time of TiO2 nanoparticles in the
reactor on particle size, phase composition, UV absorption and PL
spectra. Position 1 is that the tapping at the level of 50 mm to the
top of the reactor, position 2, at the level of 192 mm, and position 3
is for the entry of TiCl4 through the burner.
Temperature proles in the reactor are measured by using S-
type thermocouples at eight tappings at the levels of 43, 116, 197,
236, 275, 315, 336 and 360 mm from the top of the reactor, each
with eight radial positions of 0, 6, 12, 18, 24, 39, 54 and 69 mm
from the central axis.
Product TiO2 particles are collected by a device at the top end
of the reactor consisting of a 200-mesh stainless steel sieve with
a cross-section of 300 mm 300 mm, and the exhaust gas is then
vented by a fan.
Air from a screw air compressor, controlled by a pressure regu-
lator, and dried by refrigeration and silicon gel, and propane were
precisely controlled by mass ow controllers. During experiment,
the target ow rates of air and propane were set by mass ow
controllers for ignition to set up a turbulent ame to heat up the
experimental equipment. The carrier air for precursor TiCl4 was
then set to a target value by a mass ow controller to rst dry the
conveying pipeline before introducing the TiCl4 through the bub-
bler. After the temperature in particle collection device attained
373 K, precursor TiCl4 was poured into the bubbler while stopping
the carrier air. The carrier air was then restarted and the exhaust
fan was switched on. The pressure of the reactor increased as TiO2
nanoparticles continued depositing on the stainless steel sieve of
the particle collection device. After each experimental run, the ow
rate of TiCl4 was calibrated.

Table 1
Operational conditions in the experimentsa .

Run no. Flow rate (mol/s) Excess air ratio Reactor heat ux (kJ/m2 s) TiCl4 ow rate (g/min) n0 b 1020 (m3 ) Feed positionc

C3 H8 Air (oxidant) Air (carrier gas)

1 0.00583 0.119 0.0372 1.072 626.9 2.6 5.710 1

2 0.00531 0.119 0.0372 1.177 520.1 2.6 6.419 1
3 0.00479 0.119 0.0372 1.304 423.2 2.6 6.745 1
4 0.00497 0.104 0.0372 1.136 504.0 2.6 7.739 1
5 0.00419 0.104 0.0372 1.348 358.2 2.6 8.566 1
6 0.00419 0.0908 0.0372 1.222 395.1 2.6 8.708 1
7 0.00419 0.0908 0.0521 1.364 353.9 3.2 9.915 1
8 0.00350 0.0908 0.0372 1.436 275.7 2.6 9.713 1
9 0.00350 0.0908 0.0521 1.633 247.0 3.2 10.020 1
10 0.00479 0.119 0.0372 1.304 423.2 2.6 6.745 2
11 0.00479 0.119 0.0223 1.180 467.8 1.075 3.011 2
12 0.00479 0.119 0.0149 1.118 493.7 0.740 2.151 2
13 0.00419 0.0908 0.0372 1.222 395.1 2.6 8.708 3
a
Experiments were performed under atmospheric pressure and ambient temperature of 289 K.
b
Initial TiO2 particle number density.
c
Feed positions of TiCl4 carried into the reactor.
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206 H. Xie et al. / Particuology 7 (2009) 204210

Fig. 2. Measured temperatures versus radial position at different height levels (runs 1, 5 and 9).

3. Results and discussion from their TEM pictures to be in the range from 30 to 80 nm as
shown in Table 2. The apparent residence time of TiO2 in reactor
3.1. Temperature proles is such obtained that the distance of a tapping for TiCl4 to the top
end of reactor divide by supercial gas velocity in reactor. Details
Thirteen experimental runs under different conditions were car- about the method was described elsewhere (Xie & Hao, 2007). Fig. 5
ried out as tabulated in Table 1, with excess air ratio, , in the range shows a typical particle size distribution curve in terms of number
of 1.071.6, reactor heat ux, LHV/A (heat input, LHV of the fuel frequency and cumulative fraction undersize versus size, indicat-
propane divided by reactor cross-sectional area A and excess air ing a near normal distribution. A normal size distribution is also
ratio ) ranging from 247 to 627 kJ/m2 s, and ow rate of precursor obtained for TiO2 nanoparticles synthesized by laminar-ame CVD
TiCl4 ranging from 0.74 to 3.2 g/min.
Fig. 2 plots the measured temperature against radial position at
different height levels for test runs 1, 5 and 9, to show that tempera-
ture increases as reactor heat ux increases, decreases signicantly
towards the reactor wall, but becomes more uniform towards the
top end of the reactor. Fig. 3 shows that the average temperatures in
the core region and the entire reactor space, taken as the algebraic
mean of entropy, against reactor heat ux, indicating that the aver-
age temperature increases almost linearly with heat ux. The core
region refers to a diameter of 48 mm, while the burner diameter is
about 24 mm. The average temperature in the core region ranges
from 1046 to 1285 K while the average temperature in the entire
reactor space, from 753 to 1067 K, corresponding to a reactor heat
ux of 247 to 627 kJ/m2 s.

3.2. Particle morphology

Spherical TiO2 nanoparticles are produced under different con-

ditions, as shown typically in the TEM picture (by FEI TECNAI G2
S-TWIN) of Fig. 4. The median sizes (d50 ) for different operational Fig. 3. Average temperatures in core region and entire reactor space versus reactor
conditions are determined by counting more than 100 particles heat ux.
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H. Xie et al. / Particuology 7 (2009) 204210 207

Fig. 6. Mean particle size versus particle growth number Ngrw .

process (Xie & Hao, 2007). Of the mean particle sizes of test runs 2
and 13 obtained by BET method by nitrogen adsorption, those for
run 2 obtained by both methods, are in good agreement.
Fig. 4. A typical TEM picture (run 4). Table 2 shows that when TiCl4 is carried into the reactor at Posi-
tion 3, which gives the apparent residence time of TiO2 in reactor
about 0.883 s, particle size is larger than when TiCl4 is carried into
the reactor at Position 2, which gives the apparent residence time of
TiO2 in reactor in a range of 0.2630.294 s; and for Position 2, par-
ticle size is larger than that for Position 1, which gives the apparent
residence time of TiO2 in reactor in a range of 0.0570.0985. This
is because of particle growth due to particle coalescence as parti-
cle residence time in the reactor increases (Xie, 2007b, 2008). For
the same residence time, particle size increases as TiCl4 ow rate
increases, again due to particle coalescence, because TiO2 particle
number density increases as TiCl4 ow rate increases and thus col-
lision between TiO2 particles becomes more frequent (Xie, 2007a,
2007b, 2008).
Fig. 6 shows mean particle size versus particle growth number,
which is the apparent residence time of TiO2 in reactor divided by
the characteristic time of particle coalescence (Xie, 2007a, 2007b,
2008), Ngrw , including the data from Xie and Hao (2007) for TiO2
nanoparticles synthesized by laminar-ame CVD process, showing
that mean particle size is grossly correlated with particle growth
number, Ngrw , that is,
Fig. 5. Particle size distribution of number frequency and cumulative fraction (run
4). d50 = (1 + Ngrw )1/3 , (1)

Table 2
Experimental results.

Run no. Ta (K) Apparent residence timeb (s) UV adsorptivity (Abs/nm) Particle size (nm) Rutile mass fraction

1 1067 0.0579 1.374/270 47.5 0.487

2 953 0.0651 1.412/261 44.4/39.1c 0.427
3 909 0.0684 1.407/260 37.6 0.424
4 873 0.0785 1.163/296 42.0 0.401
5 793 0.0868 1.168/292 31.6 0.345
6 858 0.0883 1.159/295 30.5 0.363
7 833 0.0817 1.159/295 33.8 0.259
8 773 0.0985 1.142/300 31.6 0.231
9 753 0.0908 37.0 0.155
10 909 0.263 1.398/267 76.3 0.424
11 929 0.283 1.341/262 60.4 0.523
12 943 0.294 1.307/265 46.4 0.551
13 858 0.883 1.098/287 75.9c 0.575
a
Average temperatures taken as algebraic mean of entropy in reactor.
b
Apparent residence time of TiO2 in reactor.
c
Obtained by BET method.
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208 H. Xie et al. / Particuology 7 (2009) 204210

Fig. 8. Rutile mass fraction versus reactor heat ux.

Fig. 7. Typical XRD patterns.

where the particle growth number is


kT L
Ngrw = n0 , (2)
P u

in which  is the mean free path of gas molecules, k is the Boltz-

mann constant, T is ame temperature which is taken as the average
temperature in the entire reactor space, P is particle density, L is
the height level of the position of TiCl4 carried into reactor, u is
supercial gas velocity in the reactor, and n0 is the initial particle
number density (Xie, 2007a, 2007b):

6 MTiCl4 w TiCl4
n0 = 1027 , (3)
 MTiO2 V P

where MTiCl4 and MTiO2 are the molecular weights of TiCl4 and TiO2 ,
respectively, V is the total gas volume ow rate, and w TiCl4 is the
mass ow rate of the precursor TiCl4 . The initial particle number
density n0 for the 13 test runs is also given in Table 1. It could be seen
that when particle growth number is smaller than 1 105 particles Fig. 9. Rutile mass fraction versus particles size.

with mean particle size less than 50 nm can be produced.

values varying from 1.1 to 1.4 corresponding to wavelengths from
3.3. Phase composition 260 to 300 nm. All the TiO2 nanoparticles produced by the 13 exper-
imental runs show typical ultraviolet absorption spectra for TiO2
The typical XRD patterns given in Fig. 7 show that the intensity nanoparticles.
of rutile phase rises as reactor heat ux increases. Mass fraction of
rutile phase is obtained by the relative intensity corresponding to
anatase 1 0 1 and rutile 1 1 0 reections (Spurr & Myers, 1957),
as shown for test runs given in Table 2.
Corresponding to reactor heat ux from 247 to 627 kJ/m2 s, rutile
mass fraction varies from 0.155 to 0.575, as plotted in Fig. 8, which
shows that the mass fraction of rutile phase also depends on the
residence time of TiO2 in the reactor (MacKenzie, 1975; Morooka,
Yasutake, Kobata, Ikemizu, & Kato, 1989). Fig. 9 shows rutile mass
fraction grossly increases with increasing mean particle size, imply-
ing that anatase transforms to rutile as particles coalesce and grow.

3.4. UV absorptivity

Fig. 10 shows UV absorption spectra as measured by a Shi-

madzu UV-2450 spectrophotometer, indicating that absorptivity
rst starts to increase with wavelength and then decreases as wave-
length increases to about 400 nm, eventually to reach some rather
low constant value. The peak values of absorptivity and their cor-
responding wavelengths are given in Table 2, showing their peak Fig. 10. Typical UV absorption spectra.
 Author's personal copy
H. Xie et al. / Particuology 7 (2009) 204210
Fig. 11. Measured PL spectra (266 nm of excited wavelength).
3.5. PL spectra
PL spectrum provides an effective way to investigate the
electronic structure and optic characteristics of semiconductor
nano-materials, by which information such as surface oxygen
vacancies and defects as well as separation and recombination of
photo-induced charges can be obtained (Jing et al., 2004). Results
of photodegradation of phenol by TiO2 nanoparticles have shown
that their photocatalytic activity is strongly related to the intensity
of PL spectra (Jing et al., 2004).
Fig. 11 shows the PL spectra of test runs 2, 3, 5 and 9 as mea-
sured by Accent RPM2000, indicating that all the TiO2 nanoparticles
exhibit strong PL signals at wavelengths of 370450 nm, with wide
peak signals from 400 to 420 nm which result mainly from band
edge free excitons, reecting signicant oxygen vacancies on the
surface of TiO2 nanoparticles (Jing et al., 2004). The excited wave-
length of 266 nm is used in the measurement.
4. Conclusion
Synthesis of TiO2 nanoparticles by the oxidation of titanium
tetrachloride (TiCl4 ) in industrial propane/air turbulent ame has
been investigated, and the results show that reactor heat ux, ini-
tial TiO2 particle number density, and apparent residence time of
TiO2 in reactor are vital parameters to control rutile mass fraction,
particle morphology, UV absorptivity and PL spectra.
Under the operational conditions of reactor heat ux of
247627 kJ/m2 s, initial TiO2 number density of 2 1020 to
1 1021 m3 , and apparent residence time of TiO2 in reactor of
0.060.9 s, TiO2 nanoparticles with mean size of 3080 nm and
rutile mass fraction of 0.1550.575 are synthesized. The TiO2
nanoparticles exhibit strong PL signals at the wavelength from 370
209
to 450 nm, with a wide peak signal from 400 to 420 nm, reecting
signicant oxygen vacancies on the surface of TiO2 nanoparticles.
Acknowledgments
The authors are grateful for a research grant from Shanghai Edu-
cation Committee (07ZZ180) and fund from the Second Shanghai
Key Discipline Construction Plan of Shanghai Municipal Education
Commission (P1701). Prof. H.F. Yang of Shanghai Normal Univer-
sity and Mr. Z.W. Li of Rainbow Optoelectronic Material Shanghai
Co., Ltd. are acknowledged for their help and discussion on the
measurements of UV and PL spectra.
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