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PII: S0272-8842(16)31720-5
DOI: http://dx.doi.org/10.1016/j.ceramint.2016.09.194
Reference: CERI13854
To appear in: Ceramics International
Received date: 3 August 2016
Revised date: 26 September 2016
Accepted date: 27 September 2016
Cite this article as: M. Thamima, Y. Andou and S. Karuppuchamy, Microwave
Assisted Synthesis of Perovskite Structured BaTiO3 Nanospheres via Peroxo
Route for photocatalytic Applications, Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2016.09.194
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Microwave Assisted Synthesis of Perovskite Structured BaTiO3 Nanospheres via Peroxo
a
Department of Energy Science, Alagappa University, Karaikudi-630 003,Tamilnadu, India
b
Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, 2-4
Hibikino, Kitakyushu, Fukuoka 808-0196, Japan
skchamy@gmail.com
skchamy@alagappauniversity.ac.in
*
Corresponding author. Department of Energy Science, Alagappa University, Karaikudi-630 003,
Tamilnadu, India
Abstract
techniques such as X-ray diffraction analysis, Fourier transform infrared, Micro Raman,
Scanning electron microscope with energy dispersive analysis and ultraviolet-visible diffuse
reflectance spectroscopic techniques. Photocatalytic dye degradation study was carried out
using newly synthesized BaTiO3 catalyst. The synthesized sphere shaped barium titanate
nanopowders effectively degrade the various dyes such as Methylene Blue (MB), Malachite
Green (MG) and Alizarin Red S (ARS) under UV light irradiation. The band gap energy of
synthesized BaTiO3 was calculated by UV-DRS spectra using kubelka-Munk equation. The
higher dye decomposition efficiency of nearly 100% was successfully achieved by BaTiO3
1. Introduction
decompose dye effluents and eradicate microorganisms. Titanium dioxide nanomaterials have
been extensively used in photocatalytic degradation process. Hence, TiO2 nanomaterials are
materials show very little catalytic activity under visible light, therefore, it is necessary to
develop alternate efficient photocatalyst. The barium titanate (BaTiO3) material has attracted
much attention because of their potential applications in various fields. The established
BaTiO3 photocatalyst was used to perform a dye decomposition study and it works
properties such as high permittivity etc. [18]. Hence, BaTiO3 nanomaterial has shown
interesting attention owing to its unique ferroelectric, magnetic, high dielectric and
capacitors, sensors, electronic applications, actuators [19], coatings for hospitals, thermistors,
perovskite structure and the general formula of perovskite is ABX3. In this perovskite
structure, ‘A’ indicates the larger cation occupied by the sites of A, and ‘B’ indicates smaller
cation occupied by the sites of B. Perovskite families exhibit excellent physical properties
such as dielectric, ferroelectric, piezoelectric, pyroelectric behaviour and also it has plentiful
industrial applications [20]. Some of the examples of perovskite compounds are BaTiO3,
CaTiO3, PbZrO3, LiTiO3, PbTiO3, ZnTiO3, NiTiO3, PbLaZrTiO3 etc., which are mainly used
In recent years, the barium titanate has considered as an interesting material for
nanopowder at low temperature by a single-step wet chemical peroxo route. The developed
barium titanate nanomaterial was subjected to microwave irradiation for about 10, 20 and 30
min and denoted as BT10, BT20 and BT30, respectively. The synthesized materials were
analysed using advanced characterization techniques such as XRD, HR-SEM, FT-IR, Raman
and UV-DRS. The photocatalytic performance of BaTiO3 was studied using methylene blue
(MB), malachite green (MG) and alizarin red S (ARS) dyes. The decomposed dye solutions
typical reaction, the stoichiometric ratio of Ba(C2H3O2)2 and TiOSO4 salts were grounded
separately using mortar and pestle for 30 minutes. First, Ba(C2H3O2)2 was diluted using 50
ml of double distilled (DD) water under constant stirring for 1h. 0.1 M H2O2 solution was
added into TiOSO4 powder and it was diluted using 50 ml of DD water under constant
stirring until it forms a peroxo complex. After 1 h stirring, the two separate solutions were
mixed together to form a red-orange coloured solution and 5 ml of NaOH solution was added
for avoiding the formation of BaCO3. The colloidal pale yellow coloured precipitate was
obtained at the bottom of the beaker after completion of the reaction and the resultant
precipitate was heated at 95 oC for 30 min. The collected precipitate was washed with double
distilled water and ethanol and finally it was subjected to microwave irradiation at 400W for
10 min, 20 min and 30 min. The obtained powders are denoted as BT10, BT20 and BT30.
The photocatalytic dye degradation study was carried out using BaTiO3 powder and three
different dyes such as Methylene Blue (MB), Malachite Green (MG) and Alizarin Red S
(ARS).
The following analytical techniques were used to confirm the formation of barium
Scanning electron microscopy (SEM) with energy dispersive analysis (EDX), Fourier
transform infrared spectroscopy (FT-IR), Micro-Raman, UV-vis and UV-DRS were used.
Philips X’Pert PRO SUPER X-ray diffractometer equipped with monochromatized CuKα
radiation was used to analyse the crystallinity, lattice structure and phase of the synthesized
powders. Surface morphology of the samples was observed using X-650 scanning electron
The photocatalytic performance of the BaTiO3 was investigated using various dyes
such as methylene blue, malachite green and alizarin red S under UV light irradiation. The
photocatalytic experiment was carried out using the following procedure. 100 mg of the
BaTiO3 powder (BT10) was added into 10 ppm dye solution. In order to investigate the
influence of catalytic behaviour of BaTiO3, various dyes and 100 mg of BaTiO3 powder
were added in 100 ml of 10 mg/L MB, MG and ARS dye solution, respectively. Prior to the
experiment, the dye and catalyst mixture was sonicated for 10 min and kept in the dark for 1
h to obtain the adsorption/desorption stability between dye and BaTiO3 nanocrystals. Then,
the mixture (catalyst with dye solution) was transferred into a 250 ml Borosil cylindrical jar.
Finally, the UV light (254 nm) was irradiated using 6W Hg lamp. The dye solution was
removed from the cylindrical jar after every 15 min of irradiation time and then the
absorption spectrum was measured by Ultraviolet–Visible spectrophotometer. The percentage
of dye degradation efficiency can be calculated using the following formula as:
the final concentration considering (MB or MG or ARS) dye absorption after completion the
The prepared dye solution with catalyst was subjected to UV light (6W Hg lamp)
irradiation and consequently electron-hole pairs may be produced in the photocatalyst. At the
surface of the BaTiO3, the hydroxyl ions (OH-) and super oxides (O2-) could be generated
.
from air (containing oxygen and moisture). Then, it may generate hydroxyl radicals (OH )
.
and oxide radicals (O2 ) and ultimately these radicals to form CO2 and H2O by an efficient
interaction with the harmful organic substances [30-31]. Plausible photocatalytic reaction
3.1. XRD
Fig.1. shows the XRD patterns of the as-synthesized microwave irradiated well
crystallized products. The XRD show peaks correspond to hexagonal BaTiO3 nanoparticles
and secondary phases (Ba2TiO4). All the diffraction peaks are indexed well with JCPDS card
no. 82-1175 which is corresponding to the P63/mmc space group. The X-ray diffraction
patterns confirmed the presence of BaTiO3 crystallites (Fig.1). The successful formation of
The FT-IR spectra of synthesized BaTiO3 nanocrystallines was recorded using FT-IR
spectrophotometer in the wave number range of 4000-400 cm-1. Fig. 2 shows FT-IR spectra
The FT-IR spectra display the bands randomly at 642, 813, 985, 1071, 1197, 1275, 1394,
1428, 1566, 1645, 1764 and 1856 cm-1. There is no broad band appears in the range of 3000-
3500 cm-1, which clearly shows that there is no moisture content in the synthesized sample.
The peaks at 1645 cm-1 may be assigned to the small amount of humidity or water. The band
appears between the ranges of 509-680 cm-1 indicates the presence of Ti-O stretching bond
[32]. The two characteristic bands appear at 1566 and 1428 cm-1 range, which are
Peaks at 1071 cm-1 may be assigned to Ti-O-Ba bond. The absorption peak appears in the
range of 1733 cm-1 in the literature [34] which is here shifted to 1764 cm-1, and it indicates
the C=O stretching vibration of carboxylic group. The absorption bands at 1394, 1071, and
985 cm-1 can be considered as C-H bending modes of vibrations. The absorption peaks at 800
cm-1 is related to M-O bands, therefore the band at 813 cm-1 may be assigned to Ba-O or Ti-O
bond [35].
Fig. 3 shows the Raman spectra of BaTiO3 nanocrystals grown under microwave
irradiation. Besides, all phonons of the hexagonal P63/mmc symmetry (confirmed by XRD)
represented as three active Raman shifts, which are 2A1(TO) + E(LO) modes. The obtained
Raman peaks are in the range of 163, 516, and 702 cm-1. All the three spectra (Fig. 3) have
similar shapes, but the peak in 3(c), shows (BT30) high intensity at 163 cm-1 and the peaks at
516, 163 cm-1 corresponds to TO modes of A1 symmetry of BaTiO3 nanocrystal. The low
intensity peak at 516 cm-1 should be assigned to the coupling of TO modes associated with
hexagonal phase. The peak at 184 cm-1 should be assigned to the decoupling of TO modes
and it was reported [36] in our previous study [30-31]. Raman spectrum exhibited band at
163 cm-1 suggests that decoupling of TO modes i.e. A1(TO) phonons. The Raman shift at 720
cm-1 suggests that E(LO) modes [37] but in our study, the peak appears in the range of 702
by SEM. Figure 4(a) and 4(b) shows the typical SEM morphological features of nanosized
BaTiO3 materials. Fig. 4(a) represents the 10 min microwave irradiated BaTiO3 (BT10)
sample and Fig. 4(b) represents the 30 min microwave irradiated BaTiO3 nanomaterials
(BT30). The smooth surface morphology of the BaTiO3 was observed in the synthesized
BaTiO3 samples. The SEM photograph depicts the hexagonal shape like morphology of
BaTiO3 and were clearly matches with XRD pattern. The average particle size of BaTiO3
analysis (EDX). The diagram of Ba, Ti and O elements are shown in Fig. 5(a) and 5(b) and it
confirms the formation of BaTiO3. There is no other elemental impurity found from EDX.
The atomic % and the weight % of elements are given in Table 1 and 2. The EDX spectra of
the BaTiO3 show the existence of Ba, Ti and O elements in the range of 11.95, 21.39 and
22.02 at%, respectively. Table 1 and Table 2 shows the existence of Ba, Ti and O elements at
The band gap of BaTiO3 material was calculated using Kubelka–Munk formula from UV–
where, R is the reflection coefficient. Figure 6 shows the absorption spectrum of the barium
titanate nanocrystalline materials. The optical absorption spectrum was studied for the
microwave irradiated BaTiO3 samples in the wavelength range of 250 nm–2500 nm. The
earlier studies demonstrated that the band edge emission range of 400–500 nm is due to blue
shift emission and the emission bands in the range of 500–700 nm is due to red-shift emission
[38]. In the present study, the synthesized samples (BT10, BT20 and BT30) exhibited the
electron–hole recombination bands in the range of 520 nm (UV region) which is due to the
The band gap of BaTiO3 samples was evaluated using UV-DRS spectra. Band gap
was plotted against energy Vs calculated Kubelka-Munk values. Fig. 7 (a), (b) and (c) shows
the band gap value for BT10, BT20 and BT30 samples, respectively. BT10 has a lower band
gap of 2.32 eV compared to BT20 and BT30 which are 2.71 and 3.01 eV, respectively. A
lower band gap energy material (BT10) is promising for higher photocatalytic activity.
4. Photocatalytic Applications
The photocatalytic activity of the synthesized BT10, BT20 and BT30 photocatalysts were
Malachite Green (MG) and Alizarin Red S (ARS) under UV light illumination. The
photocatalytic decomposition study was carried out in 10 mg/L of each MB, MG and ARS dye
solutions using 100 mg of already prepared photocatalyst of BT10, BT20 and BT30. The dark
absorption test was also carried out. The concentration of photocatalyst plays an essential role in
the photocatalytic decomposition study. The BT10 photocatalyst shows higher decomposition
efficiency among the three synthesized samples due to the presence of sphere shape BaTiO3
nanomaterials and lower band gap. The B10 powder may have many active sites and ultimately
In order to examine the photocatalytic activity of synthesized BaTiO3, MB dye was used
for this study. The MB dye was completely decomposed within 240 min under UV light
irradiation. The decomposition efficiencies of 85%, 79% and 68% was achieved for BT10, BT20
and BT30 photocatalyst, respectively, while MB dye was used as a medium (Fig. 8a). The
present study clearly demonstrates that the BT10 sample has a greater decomposition efficiency
photocatalysts using MG dye under UV light illumination. The MG dye was completely
decomposed within 60 min. BT10 material shows 100% decomposition efficiency. BT20 and
BT30 exhibit 85% and 80% degradation efficiency, respectively (Fig. 8 b). BT30 sample shows
higher dye adsorption capacity, which was examined in the dark test. The MG dye solution with
BT30 sample was subjected to sonication for 10 min and then this solution was kept in dark
condition about 1 h. The green colour dye solution turned into a colourless solution i.e., MG dye
molecules entirely absorbed by the surface of the BT30 material. Again, the colourless solution
was subjected to UV light irradiation. Then MG dye colour was returned and after that, the
photocatalytic study was performed for 60 min under UV light. After 60 min of UV light
illumination, BT30 sample completely decomposed the MG dye. In this case, BT10 have a
higher decomposition efficiency than BT20 and BT30 (BT10 > BT20 > BT30).
ARS dye. BT10 catalyst shows higher decomposition efficiency of 100% within 60 min, BT20
shows about 84% of degradation efficiency in 120 min and BT30 shows 81% of degradation
efficiency in 180 min. The present study also shows that BT10 has a highest decomposition
efficiency than BT20 and BT30 (BT10 > BT20 > BT30).
Photocatalytic performance of the synthesized materials (BT10, BT20 and BT30) was
successfully examined using various dyes such as MB, MG and ARS. It has been found that
BT10 photocatalyst exhibits the excellent photocatalytic activity compared to BT20 and BT30,
due to the presence of sphere shaped BaTiO3 nanomaterials and lower band gap which was
calculated by UV-DRS spectra. The BT10 powders may have highest active site and ultimately
Figure 9(a), 9(b) and 9(c) show the UV–Vis spectra of MB dye in the presence of 100
mg of (a) BT10 (b) BT20 and (c) BT30 under the irradiation of UV light. The UV–Vis
spectra of MB dye was measured at different time intervals. The MB dye exhibited maximum
absorption bands at 665 and 290 nm wavelengths. The reaction time increases with the
decrease of the MB dye absorption. Similarly, MG dye decomposition was evaluated using
UV-Vis spectroscopy at various time intervals. The typical absorption peak of the MG dye
appears at 230, 320 and 620 nm wavelengths which are shown in Fig. 10(a). The
decomposition of the dye was increasing while increasing the UV light illumination time.
Similarly, the ARS dye decomposition was evaluated using UV-Vis spectroscopy at various
time intervals. The typical absorption peak of the ARS dye appears at 260, 330 and 480 nm
wavelengths which are shown in Fig. 10(b). The ARS dye absorption band intensity
decreases with increasing the reaction time intervals, i.e. the dye decomposition is directly
proportional to the UV light illumination time. The present investigation clearly evinces that
the developed barium titanate photocatalyst is capable of degrading the MB, MG and ARS
dye effectively.
Kinetic investigations were carried out to study the photocatalytic decomposition of the
methylene blue (MB), malachite green (MG) and alizarin red S (ARS) dye. The photocatalytic
degradation of MB, MG and ARS were found to follow first-order kinetics. The kinetic equation
where, Ci is the initial concentration of the dye solution, Ct is the dye solution concentration at ‘t’
time, k is the rate constant (first-order). The kinetics of the MB, MG and ARS dye decomposition
with barium titanate sample (BT10, BT20, and BT30 samples) is shown in Fig. 11(a), 11(b) and
11(c). The higher photocatalytic degradation efficiency was found in BT10 sample: similarly,
higher rate constant values were obtained for BT10 sample. Figure 11(a) shows the kinetic values
for samples BT10, BT20, and BT30 for degradation of MB dye and the values are 0.006120 min-1,
0.006041 min-1 and 0.004247 min-1, respectively. Figure 11(b) shows the kinetic values for BT10,
BT20, and BT30 samples and the kinetic values for MG dye degradation are 0.01953 min-1,
0.01316 min-1 and 0.01105 min-1, respectively (Fig.11b). Similarly, Figure 11(c) shows the kinetic
values for BT10, BT20, and BT30 for ARS dye degradation and the values are about 0.005352
min-1, 0.004557 min-1 and 0.002156 min-1, respectively. It is clear that the rate constant of BT10
was greater than that of BT20 and BT30 which were calculated from kinetic study and this was
5. Conclusions
In summary, the whole synthetic procedure is carried out using a domestic microwave
oven, which opens up a new route to scale up the preparation of BaTiO3 nanoparticles. The
structural, optical and morphological characterization was carried out for the synthesized BaTiO 3
nanomaterials. The photocatalytic dye degradation studies and kinetic studies were carried using
developed BaTiO3 nanomaterials. The highest decomposition efficiency of 100 % was achieved
using 10 min microwave irradiated BaTiO3 (BT10) nanomaterials. There is no characteristic new
band was observed in the UV-visible spectroscopic study of MB, MG and ARS dyes, reveals that
the dyes were directly decayed into harmless CO2 and water. The band gap energy of synthesized
BT10, BT20 and BT30 photocatalyst were found to be 2.32 eV, 2.71 eV and 3.01 eV respectively,
which are calculated by UV-DRS spectra using Kubelka-Munk equation. BT10 photocatalyst have
lower band gap energy compared to BT20 and BT30; hence, it shows good photocatalytic activity
Acknowledgements
The authors are grateful to the Department of Physics and Chemistry, Alagappa
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Fig. 1 XRD patterns of Prepared BaTiO3 samples (a) BT10 (b) BT20 and (c) BT30
Fig. 2 FT-IR spectrum of synthesized BaTiO3 samples (a) BT10 (b) BT20 and (c) BT30
Fig. 3 Raman spectra of microwave irradiated BaTiO3 Nanomaterials (a) BT10 (b) BT20 and
(c) BT30
Fig. 4 SEM images of microwave irradiated for 10 min and 30 min BaTiO 3 nanomaterials (a)
BT10 at 10 m (b) BT10 at 1m, (c) BT30 at 10 m and (d) BT30 at 1m
Fig. 5 EDX spectra of microwave irradiated for 10 min and 30 min BaTiO3 nanomaterials (a)
BT10 (b) BT30
Fig. 6 UV-vis DRS Absorbance spectra of microwave irradiated for 10, 20 and 30 min
BaTiO3.
Fig. 7 UV–vis DRS spectra of the Kubelka–Munk plot with corresponding band gap energy
of BT10 (b) BT20 and (c) BT30 samples
Fig. 8 Photocatalytic degradation of (a) Methylene blue dye (b) Malachite green dye and (c)
Alizarin Red S dye
Fig. 9 UV-vis spectra of Methylene blue dye with 0.1 g of BaTiO3 (a) BT10 (b) BT20 and (c)
BT30
Fig. 10 UV-vis spectra of (a) MG dye and (b) ARS dye
Fig. 11 Kinetic studies of (a) MB dye (b) MG dye and (c) ARS dye.
Table1. EDX spectra of Barium titanate (BT10) nanomaterials
CK 11.86 21.39
OK 16.11 22.02
Na K 11.21 15.51
SK 09.21 09.13
Ba L 41.60 11.95
Ti L 10.03 21.39
Table2. EDX spectra of Barium titanate (BT20) nanomaterials
OK 17.84 26.45
Na K 04.27 04.58
SK 05.79 04.45
Ba L 41.37 07.42
Ti L 11.73 21.39
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Scheme 1