Materials Research Bulletin 48 (2013) 3144–3148

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Materials Research Bulletin

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Preparation, characterization, and photocatalytic studies on anatase

nano-TiO2 at internal air lift circulating photocatalytic reactor
Hang Xu *, Mei Li, Zhang Jun
Chemical Engineering and Pharmaceutics School, Henan University of Science and Technology, Luoyang 471023, PR China

A R T I C L E I N F O A B S T R A C T

Article history: Anatase nano-titania (TiO2) powder was prepared by using a sol–gel process mediated in reverse
Received 10 November 2012 microemulsion combined with a solvent thermal technique. The structures of the obtained TiO2 were
Received in revised form 25 April 2013 characterized by TG-DSC, XRD, TEM. The photocatalytic decomposition of methylene blue (MB) on
Accepted 26 April 2013
nano-TiO2 was studied by using an internal air lift circulating photocatalytic reactor. The results
Available online 10 May 2013
show that the anatase structure appears in the calcination temperature range of 400–510 8C, while
the transformation of anatase into rutile takes place above 510 8C. The homogeneous microstructure
Keywords:
of nano-TiO2 particles was obtained with a size of around 10–15 nm. In the photocatalytic
A. Semiconductors
A. Nanostructures
performance, degradation process follows pseudo first order kinetics with different dosages of
A. Oxides photocatalyst and initial MB concentrations and optimal TiO2 dosage is 0.1 g/L with neutral medium.
B. Sol–gel chemistry ß 2013 Elsevier Ltd. All rights reserved.
D. Catalytic properties

1. Introduction limits particle nucleation, growth and agglomeration [9,10]. The

Photo-catalytic process (PCP) plays an important role in
wastewater treatment and is seriously affected by contaminants,
catalyst, photo-reactor and so on. Semiconductor material, TiO2, is
an efficient photocatalyst and widely applied for prevention and
control of pollution. The TiO2 catalytic efficiency is greatly
influenced by the crystal structure, particle size, and effective
surface area, et al. Nano-TiO2 presents excellent catalytic activity
because of the quantum size effect when the particle size becomes
extremely small [1].
Many techniques are developed to synthesize various types of
nano-TiO2 in recent decades, such as direct hydrolysis of titanium
salt [2], sol–gel (SG) [3], microemulsion (ME) [4,5], solvent-
thermal (ST) technique [6], and so on. The direct hydrolysis of
titanium salt is difficult to control the morphology of TiO2 particles
because of the fast hydrolytic reaction rates of titanium salt and
corpuscle agglomeration. The sol–gel method has a great advan-
tage to slow up the hydrolytic rate of titanium salt and obtains
ultra-fine powders [7,8]. The microemulsion can provide micro-
water core which nano-particles are generated in. The growth of
nano-particles can be controlled by the reactant distribution in the
droplets and by the dynamics of inter-droplet exchange. The
surfactant-stabilized micro-cavities provide a cage-like effect that
* Corresponding author. Tel.: +86 379 64232193; fax: +86 379 64232193.
E-mail addresses: xhinbj@126.com, xhbit2005@eyou.com (H. Xu).
microemulsion method has been employed successfully to obtain
ultrafine particles of controlled size of TiO2 [11]. In a general
microemulsion system, however, the reactions at the initial stage
of the formation of nano-particles, which depend on the
characteristics of precursors, are similar as the bulk precipitation
or co-precipitation process in an aqueous phase. Thus, their
reaction rates are hard to control effectively. The sol–gel process
has the advantages of controllable reaction rate during the
preparation of TiO2 powders. However, a long aging time for
gelling is required and the secondary size of particles may be out of
control. The solvent thermal method is an effective way to
diminish the gel time [1] for reduction of particle agglomeration.
Design of high efficiency photocatalytic reactor is very
important in photocatalytic field. Air lift circulating reactor was
widely used in chemical engineering and environment industry
because of its upstanding characteristic such as low shear force,
simple construction, easy magnification and high efficiency [12–
14]. Therefore, air lift circulating photocatalytic reactor is a good
fluidized bed reactor to treat wastewater.
In this study, the complex technique of sol–gel process mediated
in reverse microemulsion combining with a solvent-thermal
technique (denoted as SG-ME-ST) was used to prepare TiO2 nano-
particles. The sol–gel process takes place in microemulsion water
cores to limit formantion and germination of nano-TiO2 and the
solvent thermal can reduce the gel time. The prepared nano-TiO2
was characterized by transmission electron microscope (TEM),
thermogravimetric analysis (TG), X-ray diffraction (XRD). The

0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2013.04.075
 H. Xu et al. / Materials Research Bulletin 48 (2013) 3144–3148
photocatalytic performance of methylene blue (MB) by nano-TiO2
was studied in air lift circulating photocatalytic reactor.
2. Experimental
2.1. Nano-TiO2 preparation
Tetrabutyl titanate (n-TBT), acetyl acetone, TX-100, n-hexanol,
methylamine solution and acetone employed in the preparation of
TiO2 were analytically pure, purchased from Beijing Chemical
Agent Company. n-TBT was used as a precursor to prepare TiO2
nanoparticles in microemulsions without further purification. n-
hexane, TX-100 and n-hexanol were used as an organic solvent, a
surfactant and a co-surfactant, respectively. Water used in
experiments was de-ionized. Wastewater was prepared by
methylene blue (MB) dissolving de-ionized water. The maximum
absorbance of MB is 665 nm and the calibration curve is
A = 0.06333 + 0.2224 C, R2 = 0.9993. The MB concentration (C) of
the samples after centrifugation was analyzed at 665 nm by UV–
vis spectrophotometer. C0 was the initial concentration of MB. The
MB removal (R) can be calculated as follows:
C0  C
R¼
C0
The scheme for preparing TiO2 nanoparticles by using the ME-
SG-ST is illuminated in Fig. 1. At first, a reverse microemulsion was
prepared by ultrasonic dissolving TX-100 and n-hexanol in n-
hexane by adding a required amount of water with pH value of 9
regulated by methylamine saturated solution (25–30wt%). The
water-clear appearance of the mixture indicated the formation of
the microemulsion. The water/TX-100 molar ratio and n-hexanol/
TX-100 molar ratio were of 3 and 4, respectively. Then, by adding
an n-TBT solution of n-hexane into the reverse microemulsion with
the water/n-TBT molar ratio of 4, the hydrolysis of n-TBT was
carried out at 35 8C for 90 min to form the sol. In the n-TBT
solution, acetyl acetone was employed to regulate the reactivity of
n-TBT with an acetyl acetone/n-TBT molar ratio of 0.45. The
obtained sols were transferred to rotated solvent-thermal auto-
claves and continued to react at 120 8C for 90 min. During the
solvent-thermal process, the sols were transformed to gels and
TiO2 particles were formed. The TiO2 particles were separated in a
centrifuge at 12,000 rpm for 2 min and were then washed with
acetone to remove organics and surfactants from the particles. The
particles were dried at 105 8C for 12 h and then calcined at 300–
600 8C for 4 h.
Fig. 1. Scheme for preparing TiO2 nanoparticles.
3145
2.2. Characterization
Transmission electron microscope (TEM) with low energy
electron diffraction (LEED) was carried out using JEM-2010 (JEOL,
Japan). The crystal phases of TiO2 nanoparticles were analyzed by
X-ray diffraction (XRD) on PaNalytical X-ray diffractometer (X’Pert
Pro MPD, Dutch) using Cu Ka radiation with a scanning range from
108 to 908, a step width of 0.028 and a scanning rate of 48/min [15].
The thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) for TiO2 predecessors were performed on a STA-
409 PC TG-DSC/DTA thermal analyzer (NETZSCH-Gerätebau,
Germany), with a heating rate of 15 8C/min from 50 8C to
600 8C. The concentration of methylene blue (MB) in treated
wastewater samples was analyzed by a UV-2102PC UV–vis
spectrophotometer (UNICO, China).
2.3. Air lift circulating slurry photocatalytic reactor
An air lift circulating slurry photocatalytic reactor was employed
in the photocatalytic decomposition of MB solution as shown in
Fig. 2. Reactor is constituted by main body (a diameter of 160 mm, an
altitude of 1000 mm), guide shell, quartz tube and UV-lamp (a length
of 800 mm, a diameter of 12 mm, a power of 40 W, and Guangdong
Bright Star Co.) with an excitation wavelength of 254 nm. In
experimental process, 15 L wastewater was added in reactor and air
pump was opened. Air was blasted by the air pump into the reactor
through air distributors at the bottom. Water was arisen in inner
guide shell and fallen in outer guider shell to form a circulation
because of air impetus. Next, nano-TiO2 was added in water. Under
the motivation of air pump, the wastewater was looped to keep
catalyst particles, wastewater and air well-dispersed in the
wastewater during the experiments. After the adsorption–desorp-
tion equilibrium reaching for 30 min, the UV-lamp was switched on
and the photo-catalytic reaction was beginning. At a certain interval
of about 10 min, samples of about 10 ml were taken out and
centrifuged at 12,000 rpm to remove solid particles.
3. Results and discussions
3.1. TG-DSC analysis
Fig. 3 presented the TGA and DSC thermo-diagrams for the TiO2
gel. The weight of the gel slowly decreased from 100 to 250 8C,
sharply decreased from 250 to 340 8C, and slowly decreased from
340 to 550 8C, and no more decrease were observed up to 600 8C.
The weight losses of the TiO2 gel are 70%. The DSC of the gels
showed two exothermic peaks at approximately 338 8C and 507 8C.
3146 H. Xu et al. / Materials Research Bulletin 48 (2013) 3144–3148

o
+
o Rutile-TiO2
+ Anatase-TiO2

CPS
o +
+ oo
++ o
+
o oo +
o
610 C
o
510 C
o
450 C
o
340 C
o
240 C
o
100 C

10 20 30 40 50 60 70 80 90
2θ / o
Fig. 4. XRD patterns of TiO2 samples calcined at different temperatures.

obvious peak detected for the sample calcined at less than 340 8C
suggested no crystalline phase formed. The peaks around 25.38,
38.18, 48.18, 54.38, 55.28, 62.38, and 75.28 for the sample calcined at
450 8C revealed the formation of anatase TiO2. The appearance of
the peak at 68.88, 70.68 for the sample calcined at 510 8C indicated
that the gel began to transform the anatase phase into the rutile
phase [15,16]. The results are consistent with those obtained by
TG-DSC. As a photocatalytic material, TiO2 has two crystalline
structures, anatase and rutile. The surface adsorptive capability of
the anatase to organic pollutants is higher than the rutile and the
recombination between electron and hole on the anatase is slower
[17]. These cause that the anatase has a higher photocatalytic
activity than the rutile [18]. Therefore, in this work, the optimal
calcination temperature for preparing anatase TiO2 is about 450 8C.
Fig. 2. Schematic diagram of airlift photo-catalytic reactor.

3.3. TEM

The weight loss up to 250 8C was due to the removal of the water
and the organic solvent adsorbed on the dried gels. The exothermic
peak at 338 8C was due to the decomposition of residual surfactant,
OH group and alkoxy group. The crystallization of the amorphous
phase into the anatase phase took place from 340 to 450 8C. The
exothermic peak at 510 8C was owed to the transform of the
anatase phase to the rutile phase.
3.2. XRD analysis
The results were confirmed by the XRD analyses of the samples
calcined the TiO2 dried gel at different temperatures (Fig. 4). No
100
TG
80 338.1
506.6
The micro morphological structure of the nano-TiO2 particles
was also observed with TEM, as shown in Fig. 5. The TEM images
clearly exhibited the homogeneous microstructure of particles
with a size of around 10–15 nm. From the TEM images at a higher
magnification, it can be found that the TiO2 nano-crystals were
generated and connected together.
3.4. Effect of calcined temperature
The photo-catalytic activity of nano-TiO2 particles which is
prepared at different calcined temperature is shown in Fig. 6 with
0.1 g/L of TiO2, 5.27 mg/L of MB, 7 of pH value and 40 min of photo-
catalytic time. It is clearly seen that 450 8C is the best calcined
temperature. When the calcined temperature is below 450 8C, the
1.00
anatase TiO2 is not completely formed. The calcined temperature is
above 450 8C, the rutile TiO2 is appeared and crystal grain is
increased in higher temperature. So, the photo-activity is lower at
0.75
DSC / mW/mg

higher temperature.
TG / %

60
0.50 3.5. Effect of TiO2 dosage
40
To avoid excess use of catalyst in the air lift photocatalytic
0.25 reactor, the nano-TiO2 dosage should be optimized. A series of
20
DSC experiments were carried out with varying the loading of TiO2
concentrations from 0 to 0.3 g/L in order to determine the effect of
0 0.00 TiO2 catalyst amounts. MB removal is depicted at different TiO2
100 200 300 400 500 600 700
temperature / C
o concentrations in Fig. 7. From the Fig. 7, there is no any MB removal
without catalyst after 40 min. The MB removal increases with the
Fig. 3. TG-DSC curves of the TiO2 dried gel. addition of TiO2 dosage from 0.03 g/L to 0.1 g/L. But degradation
 H. Xu et al. / Materials Research Bulletin 48 (2013) 3144–3148 3147

100

80 0
0.03 g/L
0.05 g/L
60 0.07 g/L
0.10 g/L

R /%
0.10
0.9961 0.15 g/L
0.09
0.9956 0.9952 0.20 g/L
40 0.08
0.30 g/L

k /min
0.9934 0.9965
0.07

0.06
20 0.05 0.9916 0.9800
0.00 0.05 0.10 0.15 0.20 0.25 0.30
TiO dosage / g/L
0
0 10 20 30 40 50
Fig. 5. TEM images of nano-TiO2 particles. Time /min
Fig. 7. Effect of TiO2 catalyst loadings (MB: 5.27 mg/L and pH 7).

efficiency is slightly reduced when TiO2 catalyst is increased to

0.3 g/L. Thus, optimum catalyst dosage is 0.1 g/L with 98% of MB
removal at 40 min.
UV/TiO2 process follows pseudo one order kinetics, ln(C/
C0) = kapt. The slope kap represents apparent constant. MB removal
at different TiO2 loading follows pseudo one order kinetics and kap
is shown in Fig. 7. The biggest kap at best catalyst dosage is
0.9277 min1. The regression coefficient R2 is used to reveal linear
fitting quality. From the Fig. 7, all the R2 is above 0.98. So, photo-
catalytic process is good for one order kinetics.
The phenomenon indicates that more available active sites on
the catalyst surface can absorb more photons from the UV-lamp,
promoting the valence band electron to move to the conduction
band to oxidize methylene blue [19]. On the other hand, at higher
loading levels, the nano-TiO2 particles may reflect, screen and
scatter the radiation from the UV-lamp [20] and reduce the
photonic flux within the irradiated solution. Another reason is that
the catalyst surface probably becomes unavailable for photo
absorption because of the agglomeration and sedimentation of
nano-TiO2 particles [21].
Effect of TiO2 amount on pseudo-first order rate constant (kap) is
fitted with a Langmuir type expression [22]:
where, k0 is the TiO2 surface reaction rate constant; K TiO2 is the
adsorption equilibrium constant. Values of k0 and K TiO2 are
obtained from the linear regression between k1ap and C 1 as k0 is
TiO2
0.1529 min1 and K TiO2 is 17.07 L/g, respectively.
3.6. Effect of MB initial concentration
Fig. 8 shows nano-TiO2 degradation performance at varying MB
initial concentration from 4.08 to 6.73 mg/L. MB decomposition
efficiency is decreased with increasing MB initial dosage at the
certain TiO2. More contaminant is decomposed with a certain TiO2
dosage. Obviously, the degradation efficiency is lower. Another
reason is that the more hydroxyl radicals are produced to lead to
more rapid reaction because of more water molecules absorbed on
the surface of TiO2 at the lower concentration than the higher.
Oppositely, if the wastewater contains more MB molecules, it is a
competitive adsorption between the dye molecules and water and
then leads to a decrease in the removal of dye.
3.7. Effect of pH value

k0 K TiO2 C TiO2 In the photocatalytic process, pH plays an important role. Fig. 9

kap ¼ shows photocatalytic process at acidic, neutral and alkaline
1 þ K TiO2 C TiO2
aqueous environment. Neutral medium is obviously better than

100 100

80 80
4.08 mg/L
5.27 mg/L
60 60 6.00 mg/L
R /%

6.73 mg/L
R /%

0.20 0.9938
0.16
40 40
k /min

0.12 0.9961
0.08
0.9980

20 0.04
20 0.9974
0.00
4.0 4.5 5.0 5.5 6.0 6.5 7.0
MB dosage / mg/L
0
100 200 300 400 500 600 700 0
o 0 10 20 30 40 50
Calcining Temperature / C -1
Time /min
Fig. 6. The photocatalytic activity of nano-TiO2 particles at different calcined
temperatures. Fig. 8. Effect of MB initial concentration (TiO2: 0.1 g/L and pH 7).
3148 H. Xu et al. / Materials Research Bulletin 48 (2013) 3144–3148

100 performance of recycled nano-TiO2 had no visible change after

several cycles. This phenomenon indicates that nano-TiO2
prepared in this study is very stable and high effective for the
80 removal of contaminants in aqueous.

60 4. Conclusions
R /%

Anatase nano-titania (TiO2) powder was prepared by using a

40 sol–gel process mediated in reverse microemulsion combined with
pH=4 a solvent thermal technique. The photocatalytic decomposition of
pH=7 methylene blue (MB) on nano-TiO2 was studied by using an
20 pH=10 internal air lift circulating photocatalytic reactor. The anatase
structure appears in the calcination temperature range of 400–
510 8C, while the transformation of anatase into rutile takes place
0
0 10 20 30 40 above 510 8C. The uniform microstructure of nano-TiO2 particles
Time / min was obtained with a size of around 10–15 nm. In the photocatalytic
performance, degradation process follows pseudo first order
Fig. 9. Effect of pH value (TiO2: 0.1 g/L and MB: 5.27 mg/L). kinetics with different dosages of photocatalyst and initial MB
concentrations and optimal TiO2 dosage is 0.1 g/L with neutral
medium. According to the Langmuir model, the surface reaction
cycle 1 cycle 2 cycle 3
100 rate constant (k0) and adsorption equilibrium constant ðK TiO2 Þ are
0.1529 min1 and 17.07 L/g, respectively.

80 Acknowledgments

This work is supported by the National Nature Science

60
Foundations of China (No: 21006057 and 21076063), China
R /%

Postdoctoral Science Foundation (No: 20100470351), Provincial

40 Science and Technology Foundation of Henan (No: 122102310568)
and State Key laboratory of Inorganic Synthesis and Preparative
Chemistry Opening Topic Foundation (No: 2012–24)
20

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