Sepiolite was used as support for TiO2 catalysts
in the oxidative removals of rhodamine B. The
support has layered structure with fibrous
morphology. TiO2 was distributed on the sepiolite
through the suspension and calculation route.
TiO2/sepiolite was an excellent catalyst for the
photodegradation of rhodamine B in the presence of
H2O2 or air. Under the same experimental
conditions, H2O2 was more oxidative than air in the
discoloration of rhodamine B. The catalytic activity
was related to the amount of TiO2 loadings and
oxidant nature. An increased amount of TiO2 led to a
decreased degradation efficiency of rhodamine B.
The highest conversion of rhodamine B was
observed on 6.0 wt% TiO2/sepiolite with the
degradation efficiency of 99 % using either H2O2 or
air as oxidant.
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Vietnam Journal of Chemistry, International Edition, 55(2): 183-187, 2017
DOI: 10.15625/2525-2321.2017-00441
183
Catalytic activity of TiO2/sepiolites in the degradation
of rhodamine B aqueous solution
Nguyen Tien Thao
1*
, Doan Thi Huong Ly
1
, Dinh Minh Hoan
1
, Han Thi Phuong Nga
1,2
1
Faculty of Chemistry, VNU University of Science – Vietnam National University, Hanoi
2
Faculty of Environment, Vietnam National University of Agriculture
Received 7 July 2016; Accepted for publication 11 April 2017
Abstract
TiO2/sepiolite catalysts were prepared by suspension of titanium dioxide and support in solvent accompanying by
calcination. The characterization of the obtained powder has been examined by some physical means including XRD,
SEM, FT-IR, and UV-vis. The sepiolite support possesses fibrous structure. X-ray diffraction analysis pointed out that
the TiO2 particles are firmly distributed on fibrous sepiolite matrix. All TiO2/sepiolite samples were tested for the
degradation of rhodamine B and showed a high catalytic activity. The experimental data showed that the degradation
efficiency of rhodamine B is correlated with the amount of TiO2 loadings and oxidant behavior. At room temperature,
the conversion of rhodamine B reaches to 99-100 % over 6.0 wt% TiO2/sepiolite catalyst.
Keywords. TiO2, rhodamine B, sepiolite, degradation, photocatalysis.
1. ITRODUCTION
The development of economy and industry in
Vietnam also leads to some environmental issues
during the last decades. A large quantity of organic
contaminants in wastewater was exhausted into
environments [1, 2]. Many of them are highly
chemically stable, low biodegradable, and
potentially harmful to the human society. As Law on
Environmental Protection came ỉnto effect from
January 01, 2015 in Vietnam, all toxic contaminants
in exhausted wastewater must be treated before
releasing water into rivers, fields, etc. Organic dyes
and colored compounds are the source of
considerable water consumption and contamination.
Thus, the complete oxidation of these dyes in their
aqueous solutions offers an opportunity of direct
removal of these chemicals or their transformation
into non-toxic products [2, 3]. However, efficiency
of the classical oxidation processes for their removal
from wastewater is still limited. For this reason, new
advanced oxidation techniques are quite promising.
They use active catalysts activated by sunlight
irradiation for the dye degradation under ambient
conditions [2-4]. Among heterogeneous
photocatalysts used, TiO2 is reported as an effective
semiconductor catalyst for removing stable organic
compounds [3-5]. However, its catalytic activity
sometimes varies with light frequency, phase,
particle domain, dispersion... [4, 5]. Thus,
distribution of TiO2 on matrix leads to an increased
dispersion of active centers and improves catalytic
activity. Among various inorganic materials
reported, sepiolite a clay mineral having a unique
structure related to its functional properties and
adsorbability [6, 7]. Many works have reported the
potential adsorption ability of dyes on this clay [8-
10]. This adsorptive property is an advantage to
exploit its catalytic activity if this material is
consisted of active components such as ZnO, FeOx,
and TiO2.
The purpose of the present study is to prepare
TiO2 on fibrous sepiolite carrier as catalysts for the
oxidation of rhodamine B.
2. EXPERIMENTAL
2.1. Catalyst preparation and characterization
Sepiolite was purchased from Fluka Chemical
Company and used without further purification.
TiO2 was purchased from Wako Company. A certain
amount of TiO2 was added into 25 mL of absolute
ethanol under magnetic stirring at room temperature.
The suspension was stirred for 10 minutes prior to
adding a weighted quantity of dried sepiolite. The
mixture was further stirred at room temperature for 3
hours and then evaporated at 70-75
o
C for 15 hours
VJC, 55(2), 2017 Nguyen Tien Thao et al.
184
to the yield white powder. The solid was then
calcined at 400
o
C for 2 hours to give TiO2/sepiolite
samples.
Powder X-ray diffraction (XRD) patterns were
recorded on a D8 Avance-Bruker instrument using
CuKα radiation (λ = 1.59 Å). Fourier transform
infrared (FT-IR) spectra were obtained in 4000-400
cm
-1
range on a FT/IR spectrometer (DX-Perkin
Elmer, USA). The scanning electron microscopy
(SEM) microphotographs were obtained with a
JEOS JSM-5410 LV. UV–Vis spectra were collected
with UV-Visible spectrophotometer.
2.2 Degradation of rhodamine B
In photocatalytic experiments, 75 mL solution of
20 ppm of rhodamine B dye (RhB) and 0.45 grams
of catalyst were added in to a beaker under magnetic
stirring at room temperature. Then, either 75 mL
solution of H2O2 (30%) was dropwised into the
beaker or 5.0 mL/min flowrate of air was bubbled
into the reaction mixture 2-5 mL of dye samples
were taken out at a regular interval (20 min) from
the solution test, filtered and their absorbance was
recorded at 553 nm using a CARY 100 UV-vis
spectrophotometer (Shimadzu). The degradation
level is estimated by the following equation:
100
[RhB]
RhB][[RhB]
nDegradatio
init ial
finalinit ial
3. RESULTS AND DISCUSSION
3.1 Catalyst Characterization
All TiO2/sepiolite samples with different
loadings were prepared and their XRD patterns were
represented in figure 1. As seen in figure 1, the
reflection signals at 2-theta of 20.6, 23.8, 26.7, 28.0,
35.6, 37.9, 39.9, 43.8
o
are indexed to the sepiolite
phase (Joint Committee on Powder Diffraction
Standards (JCPDS) Card No. 00-013-0558) [6, 7, 9].
Some weaker signals at 2-theta of 25.5, 37.8, 55.1
o
are essentially assigned to the TiO2 anatase (CPJS
00-021-1272). These peaks are rather broadening,
implying the formation of nanocrystalline titanium
dioxide loaded on the support [4, 5, 11].
20 25 30 35 40 45 50 55 60
2-Theta (
o
)
2 wt.%TiO2/Sepiolte
6%TiO2/Sepiolte
15 wt.%TiO2/Sepiolte
*
*
*
Sepiolite
Figure 1: XRD patterns for TiO2/sepliolite catalysts
Morphology and microstructure of the raw
sepiolite and TiO2/support are observed using
scanning electron microscope and their micrographs
are displayed in Fig. 2. The solid is consisted of a
stick-like aggregation made up of lots of fibers and
the length of sticks is approximately 1μm. The
diameter of sticks is about 80 nm [12, 13]. No
remarkable changes in the shape and size of Mg-O-
Si sepiolite fibers were observed for the TiO2
loading samples (Fig. 2B).
Figure 2: SEM images of sepiolite (A) and sample 15.0 wt% TiO2/sepiolite (B)
A B
VJC, 55(2), 2017 Catalytic activity of TiO2/sepiolites in
185
40080012001600200024002800320036004000
Wavenumber (cm
-1
)
Sepiolite
2wt%TiO2/Sepiolite
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
200 300 400 500 600 700 800
Wavelength (nm)
A
b
so
rb
a
n
c
e
2 wt.%TiO2/Sepiolite
TiO2
Figure 3: IR spectra (left) and UV-spectra (right) of TiO2 and TiO2/sepiolite samples
FT-IR spectra of raw sepiolite and the
TiO2/support are illustrated in Fig. 3A. The weak
bands at 3610 and 3415 cm
-1
for the three samples
are assigned to the stretching vibrations of hydroxyl
groups in the octahedral Mg sheet and external
surface [8, 12, 13]. The band at 1650 cm
−1
is due to
the bending vibration of O-H bond of chemisorbed
water on the surface of the solids. The bands around
1026 and 472 cm
-1
which originate from stretching
of Si-O in the Si-O-Si groups of the tetrahedral sheet
still exist, indicating that the basic structure of
sepiolite is well preserved [12, 13]. Fig. 3A also
indicates no significant difference between the
spectra of the TiO2/clay before and after suspension
of TiO2.
Figure 3B presents the UV-Vis diffuse
reflectance spectra of TiO2/sepiolite. It is observed
that two samples show a similar wavelength of the
adsorption edge at 392 nm (Eg ≈ 3.20 eV), in line
with the theoretical value of TiO2 photocatalyts [5,
14, 15]. Thus, no chemical interaction between
titania and sepiolite was observed. The results
suggest that the TiO2/sepiolites have a suitable band
gap for photocatalytic reactions [16].
3.2. Degradation of rhodamine B
The degradation of rhodamine B was
investigated in water at room temperature,
laboratory lamp-light with air flow rate or 30% H2O2
solution as oxidant. For a comparison a blank test
was carried out under the same conditions and a
small amount of rhodamine B was converted,
confirming the stability of organic dye [10]. Figure
4A shows that TiO2 pure oxide was also tested for
the removal oxidation of rhodamine B with air. It is
not supervising to see a gradually increased
degradation degree of rhodamine B with reaction
time since TiO2 is a typical photocatalyst. Figure 4B
displayed the temporal changes in UV-vis spectra of
the rhodamine B in the solution with reaction time.
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10
Time (h)
D
e
g
r
a
d
a
ti
o
n
P
e
r
c
e
n
t,
%
6wt%TiO2/Sepiolite 15wt%TiO2/Sepiolite
8wt%TiO2/Sepiolite TiO2 (Pure)
Bank test (No Catalyst)
A
TiO2 Catalyst
300 350 400 450 500 550 600
Wavelength (nm)
0h
2h
4h
6h
8h
10h
B
Figure 4: Catalytic activity of TiO2/sepiolite samples (A) and UV-vis absorption spectra of rhodamine B
during visible light irradiation over TiO2 pure catalysts (20 ppm of rhodamine B, 0.30 grams of catalyst,
room temperature)
VJC, 55(2), 2017 Nguyen Tien Thao et al.
186
A gradual decrease in the intensity of the strong
absorption band with the peak maximum at 553 nm
is observed during the photocatalytic degradation of
RhB white no wavelength shift of the band at 553
nm, implying the de-ethylation process of rhodamine
B over the catalyst (Fig. 4B) [4, 5, 17, 18]. However,
the degradation efficiency of rhodamine B sharply
goes up as TiO2 particles were dispersed on sepiolite
support. Indeed, the three TiO2/sepiolite catalysts
exhibit rather high photocatalytic activity as
compared with that of TiO2 pure experiment (Fig. 4).
Figure 4A shows that the degradation level
reaches nearby 100 % after 4-8 hours on time. In
order to expedite degradation process, air flowrate
was replaced by H2O2 oxidant. The oxidation of
rhodamine B aqueous solutions with H2O2 was
carried out over TiO2/sepiolite catalyst under
ambient conditions. The catalytic activity of
rhodamine B discoloration is represented in Figure
5. All catalyst samples show good activity in the
oxidation of rhodamine B by H2O2. The
discoloration reaction occurs more quickly and the
degradation efficiency of rhodamine B increases
after initiating reaction as seen in Fig. 5 [2, 18-20].
Evidently, the degradation efficiency of rhodamine
B goes linearly up during 50 minute-reaction period
and then gradually approaches about 100 %.
80
82
84
86
88
90
92
94
96
98
100
20 30 40 50 60 70 80 90 100 110 120
Reaction time (min)
D
e
g
r
a
d
a
ti
o
n
P
e
r
c
e
n
t,
%
6 wt%TiO2/Sepiolite
8 wt% TiO2/Sepiolite
4 wt%TiO2/Sepiolite
10 wt% TiO2/Sepiolite
Figure 5: Catalytic activity of TiO2/sepiolite
samples in the degradation of rhodamine B in
the presence of H2O2 at room temperature, 0.3
grams of catalyst, 20 ppm RhB
Figure 5 also reveals the comparative activity
among catalyst samples. As seen in Fig. 5. The
catalytic activity can be arranged in order of 6.0
wt% TiO2/sepiolite ≥ 8.0 wt% TiO2/sepiolite > 4.0
wt% TiO2/Sepiolite > TiO2. A higher photocatalytic
activity for TiO2/sepiolite is explained by the high
dispersion of TiO2 on the sepiolite surface, which
provides more available active sites for the
photocatalytic reaction. Furthermore, sepiolite was
known as a good adsorbent and thus the catalyst
surface may be the accumulation of rhodamine B
molecules [7-10]. As a result, rhodamine B
molecules have more chances to reach active sites
and are therefore decolorized into intermediates [17-
19]. However, a higher TiO2 loading may lead to
form large crystallite titania clusters which cover the
sepiolite surface and finally decrease the
photocatalytic activity. This explained a lower
catalytic activity on 8.0 wt% TiO2/sepiolite [3, 15].
4. CONCLUSION
Sepiolite was used as support for TiO2 catalysts
in the oxidative removals of rhodamine B. The
support has layered structure with fibrous
morphology. TiO2 was distributed on the sepiolite
through the suspension and calculation route.
TiO2/sepiolite was an excellent catalyst for the
photodegradation of rhodamine B in the presence of
H2O2 or air. Under the same experimental
conditions, H2O2 was more oxidative than air in the
discoloration of rhodamine B. The catalytic activity
was related to the amount of TiO2 loadings and
oxidant nature. An increased amount of TiO2 led to a
decreased degradation efficiency of rhodamine B.
The highest conversion of rhodamine B was
observed on 6.0 wt% TiO2/sepiolite with the
degradation efficiency of 99 % using either H2O2 or
air as oxidant.
Acknowledgment. This research is funded by
Vietnam National Foundation for Science and
Technology Development (NAFOSTED) under grant
number 104.05-2014.01.
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Corresponding author: Nguyen Tien Thao
Faculty of Chemistry, Vietnam National University Hanoi
19 Le Thanh Tong Str., Hoan Kiem District, Hanoi, Viet Nam
E-mail: ntthao@vnu.edu.vn/nguyentienthao@gmail.com; Tel.: +84.043.8253503.
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