Abstract. An Al2O3 overcoated TiO2:N layer was synthesized using the solgel
method. XRD, SEM and UV-vis measurements were used to study the structure and
optical properties of the material. The XRD results indicated that the TiO2:N layer
was identified only as an anatase phase. SEM images showed that the diameter of
particles was around 15-30 nm depending on the NH(C2H4OH)2 concentration
in the sol solution. UV-vis spectrums suggested that a TiO2:N/Al2O3 sample
can absorb visible light. These results indicate that fabricated material degrades
CO, NO better than Degussa P25 commercial TiO2 when exposed to natural light.
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JOURNAL OF SCIENCE OF HNUE
Mathematical and Physical Sci., 2013, Vol. 58, No. 7, pp. 94-99
This paper is available online at
FABRICATION AND STUDY ON STRUCTURE, PHOTOCATALYSIS
OF TiO2:N/Al2O3 MATERIAL FOR CO, NO DEGRADATION
Ma Thi Anh Thu1, Nguyen Manh Nghia2 and Nguyen Thi Hue3
1Faculty of Natural Sciences, Cao Bang Teacher Training College
2Faculty of Physics, Hanoi National University of Education
3Institute of Environmental Technology, Vietnam Academy of Science and Technology
Abstract. An Al2O3 overcoated TiO2:N layer was synthesized using the solgel
method. XRD, SEM and UV-vis measurements were used to study the structure and
optical properties of the material. The XRD results indicated that the TiO2:N layer
was identified only as an anatase phase. SEM images showed that the diameter of
particles was around 15-30 nm depending on the NH(C2H4OH)2 concentration
in the sol solution. UV-vis spectrums suggested that a TiO2:N/Al2O3 sample
can absorb visible light. These results indicate that fabricated material degrades
CO,NO better than Degussa P25 commercial TiO2 when exposed to natural light.
Keywords: TiO2, Al2O3, photocatalysis.
1. Introduction
Titanium dioxide is a catalytic material that is used to treat contaminants at
room temperature and normal atmospheric pressure [1, 5-7]. This material is a typical
photocatalyst which is capable of degrading contaminants with the aid of sunlight or
artificial illumination without requiring special conditions such as high temperature or
high pressure [2, 3]. However, the large bandgap of about 3.2 eV of pure TiO2 in the
anatase phase causes the photocatalytic property of TiO2 to be limited in the ultraviolet
radiation range. This is a major limitation because no more than 5% of solar radiation
can be used to stimulate photocatalysis of TiO2. Therefore, improving the efficiency of
TiO2 photocatalysis by expanding its absorption region to the visible radiation range has
potential and is therefore attracting the attention of scientists. Recent studies have shown
that TiO2 can absorb visible light by doping metallic elements such as Fe,Co,La,Zr and
Pt [1, 5, 6], or nonmetal elements such as N, S and C [1, 5, 6]. Among these elements, N
Received September 26, 2013. Accepted October 30, 2013.
Contact Nguyen Manh Nghia, e-mail address: nghianm@hnue.edu.vn
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Fabrication and study on structure, photocatalysis of TiO2: N/Al2O3 material...
seems to be a better choice to dope with TiO2 due to its potential to increase the strength
and uniformity of materials, and to show stronger catalytic properties under natural light
conditions.
In this paper we present the synthesis and structural studies, as well as the optical
properties, of nano TiO2:N/Al2O3 materials. The study also focuses on testing the
photochemical catalytic ability of materials to decompose the pollutants CO and NO in
natural light conditions.
2. Content
2.1. Experiment
TiO2 was synthesized using a sol-gel process. The sol solution was prepared using
hydrolysis and a condensation Ti(O-iC3H7)4 alkoxide. A uniform TiO2 coating layer on
the surface of the χ-Al2O3 layer was obtained using two different mixtures we call sol
B1 and sol B2. Sols B1 and B2 consisted of TTIP, DEA and EtOH with a molar ratio
of 1:1:34 and 1:2:34, respectively. Titanium tetraisopropoxide (TTIP) and ethyl alcohol
(EtOH) with a purity of 99.8% were provided by Wako Pure Chemical Industries Co.,
Ltd. Diethylamine (DEA) purchased from the Kishida Chemical Company (Japan) was
used in the preparation of the sol solution. χ-Al2O3 fibers having a diameter of about 0.1
mm and a surface area of 0.015 m2/g were provided by Alus Co., Ltd. (Japan). Al2O3
fibers were soaked for 60 minutes in the sol solution. The best samples were annealed at
470 0C for 3 hours to obtain crystalline TiO2 in the anatase form [4].
The crystalline structure of the TiO2 layer was determined by X-ray diffraction
(XRD, Siemens D5000). Surface morphology and crystal size was measured by scanning
using electron microscopy SEM (Hitachi S-4800). The band gap was calculated from
the results of absorption spectra measured by a Jasco V670 system. Photocatalytic
experiments were conducted in a 1 m×1 m×1 m sealed test chamber. The light sources
were 20 W UV lamps with wavelengths of 254 nm, 365 nm and a 10 W visible light
lamp. Photocatalysis materials placed 30cm from the light source were synthesized
TiO2:N/Al2O3, 35 cm×35 cm in size. A pollution gas in the chamber was moved through
the material several times by convection fan. The concentration of CO and NO were
determined using a colorimetric method (Shimadzu UV-Vis 2450).
2.2. Results and Discussion
The XRD patterns ofTiO2/Al2O3 dopedN are illustrated in Figure 1. The spectrum
peaks at 2θ angles 250, 370, 480, 540 and 630, respectively, correspond to planes ,
, , and of the anatase phase. Two diffraction peaks at positions
380 and 450 belong to χ-Al2O3. This result shows that the sample heated at 470 0C for 3
hours exhibits only an anatase phase and no diffraction peak relating to a rutile or brookite
phase was observed.
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Ma Thi Anh Thu, Nguyen Manh Nghia and Nguyen Thi Hue
SEM images of two samples showed that the particle size of B1 and B2 samples
were 30 nm, and 15 nm, respectively. In both samples, the TiO2 particles were quite
uniform and no cloud phenomenon was seen. The influence of amine concentration
in different samples on particle size was considered. Chemical reactions related to the
formation of TiO2 nanocrystals can be described as a two-step process: hydrolysis and
condensation [6]. The reaction mechanism is written as follows:
≡ Ti−OR+ HOH/H2NR′ →≡ Ti−OH/HNR′ + ROH (1)
≡ Ti−OH/HNR′ +R′NH/HO− Ti ≡→ Ti−O(N)− Ti ≡ + HOH/H2NR′ (2a)
≡ Ti−OH/HNR′ +RO− Ti ≡→≡ Ti−O(N)− Ti ≡ + ROH/R′OR (2b)
Figure 1. X-ray diffraction patterns of TiO2:N=Al2O3
with sol ratio 1:1:34 (a) and 1:2:34 (b)
Figure 2. SEM images of TiO2:N=Al2O3 with sol ratio 1:1:34 (a) and 1:2:34 (b)
Hydrolysis reaction (Equation 1) occurs when the hydroxyl group in diethanolamine
(H2NR′) undergoes nucleophilic substitution on the metallic center leading to the
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Fabrication and study on structure, photocatalysis of TiO2: N/Al2O3 material...
exchange of alkyl groups in the titanium alkoxides (Ti− OR). Following a condensation
reaction, which involves the formation of ≡ Ti − O(N) − Ti ≡, the byproduct is water
or a condensed 2a amino, alcohol or ether 2b. The rate of hydrolysis and condensation
is inversely proportional to the amount of ligand added. This means that the hydrolysis
rate will determine the particle properties. The rate of hydrolysis in solution with a molar
ratio of Ti(O− iC3H7)4 : NH(C2H4OH)2 (1:1) is faster than that of the solution using a
molar ratio of Ti(O − iC3H7)4 : NH(C2H4OH)2 (1: 2). This is the main reason for the
difference in TiO2 particle size in two samples.
Figure 3. Absorption spectra of Degussa P25 (a), sample B1 (b) and B2 (c)
To examine the changes of the electronic band structure of TiO2:N/Al2O3
materials, we studied the absorption spectra of the synthesized samples. Figure 3
is the absorption spectrum of Degussa P25, TiO2:N/Al2O3 with the molar ratio of
Ti(O-iC3H7)4 : NH(C2H4OH)2 of 1:1 and 1:2, respectively. From the results of the
absorption spectra, we determined the band gap of Degussa P25 powder to be 3.3 eV
and that of the samples B1 and B2 to 3.0 eV. Thus, the doped nitrogen atom causes the
band gap of TiO2/Al2O3 anatase to become smaller than that of P25 Degussa commercial
TiO2 and it increases the ability of the photocatalyst under visible radiation.
We assessed the ability of the catalyst by carrying out a decomposition experiment
of CO and NO. Figure 4 is the result of the decay of CO by materials under different
lighting conditions. Under UV light with the wavelength of 254 nm, both B1 and
B2 samples showed good catalytic activity, and the carbon dioxide with 5 ppm initial
concentration was almost completely decomposed after 30 minutes. Potential degradation
of the two samples differed when light wavelength was increased to 365 nm. Particularly,
the B1 sample could convert CO almost completely in the test box after 100 minutes
irradiation while the B2 sample needed just 60 minutes to do that. A special feature of
this catalytic result is that both samples can decompose CO when exposed to visible
radiation. The time needed to convert the total amount of CO in the test was 180 minutes
and 150 minutes when using B1 and B2 samples, respectively.
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Ma Thi Anh Thu, Nguyen Manh Nghia and Nguyen Thi Hue
(B1) (B2)
Figure 4. Results of the decomposition of CO
in B1 and B2 samples under different conditions
(B1) (B2)
Figure 5. Results of the decomposition ofNO
in B1 and B2 samples under different conditions
In similar experiments with a carbon dioxide photocatalyst,TiO2:N/Al2O3 samples
also showed a photocatalytic decomposition of NO in the test box. Using ultraviolet
radiation with a wavelength of 254 nm, an initial 5 ppm concentration of NO was
significantly reduced after 30 minutes when treated by samples B1 and B2 as shown in
Figure 5. Under natural light conditions, the reaction times for the decay of NO were 210
and 180 minutes when using samples B1 and sample B2, respectively. In both experiments
involving the decomposition of CO and NO, sample B2 (particle size 15 nm) displayed a
higher catalytic efficiency than that of sample B1 (particle size 30 nm). This is mainly due
to particle size changes. The increase in surface area as well as the decrease in particle
size lead to the phenomenon that the gas molecules can be exposed more efficiently to
a catalyst material, a capillary in a medium capillary, and thus increase photocatalyst
efficiency.
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Fabrication and study on structure, photocatalysis of TiO2: N/Al2O3 material...
3. Conclusion
We succeeded in synthesizing a nanomaterial covering Al2O3. From the XRD
results, TiO2:N/Al2O3 particles exhibited an anatase phase structure and there was
no evidence of a rutile or brooket phase. The molar ratio between Ti(O-iC3H7)4 and
NH(C2H4OH)2 in the initial solution was the key factor in the reaction rate and thus
it would decide the particle size of TiO2 crystalline. Compared to the Degussa P25
commercial TiO2, TiO2:N/Al2O3 extended the radiation absorption to the visible range.
This made the TiO2: N/Al2O3 capable of decomposing CO and NO even in natural light
conditions. The difference in performance degradation between sample B1 and sample
B2 was due to the difference in particle size: particle size reduction increased the surface
area, which increased the catalytic performance.
Acknowledgements. This work was financially supported by a grant from the
KC.08.26/06-10 program of the Ministry of Sciences and Technologies.
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