Journal of Saudi Chemical Society (2015) 19, 549556

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Nanocrystalline ZnO doped lanthanide oxide: An

ecient photocatalyst for the degradation of
malachite green dye under visible light irradiation
G.A. Suganya Josephine, Saranya Ramachandran, A. Sivasamy

Chemical Engineering Area CSIR-Central Leather Research Institute, Adyar, Chennai 600020, India
Received 28 February 2015; revised 20 May 2015; accepted 22 May 2015
Available online 6 June 2015

KEYWORDS
AOP;
Environmental remediation;
Photocatalysis;
Wastewater treatment

Abstract Visible light induced semiconductor photocatalysis has received a great attention in recent
years due to the contamination of water bodies. In the present study, we have reported the photo
catalytic degradation of a toxic organic dye, malachite green using a ZnO doped Dy2O3 photo catalyst under visible light irradiation. The nanocrystalline photocatalyst was prepared by a precipitation method employing the respective nitrates and sodium carbonate as precursors and were
characterized by FT-IR, XRD, UVVis DRS, FE-SEM and AFM analysis. The experimental results
proved that the prepared photo catalysts were crystalline, nanosized and highly active in the visible
region. UVVis DRS results suggested that the band gap was 3.1 eV for the prepared photo catalyst.
The photodegradation efciency of malachite green was analysed by various experimental parameters namely pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo rst order kinetics and was continuously
monitored by UVVisible spectrophotometer. The degradation of malachite green was above
99% within 1 h of visible light irradiation employing the doped photocatalyst, whereas pristine metal
oxide possessed only 67% and pristine lanthanide oxide possessed activity which was only due to
photolysis. A plausible mechanism for the generation of OH radicals and the pathway for MG
dye degradation has been proposed in this study. The experimental results clearly show that
nanocrystalline semiconductor doped lanthanide oxides are highly active under visible light
irradiations and may nd wider applications in environmental remediation technologies.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
* Corresponding author. Fax: +91 044 24911589, +91 044 24912150.
E-mail address: arumugamsivasamy@yahoo.co.in (A. Sivasamy).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

Environmental remediation technology is nowadays an emerging eld towards the eradication of pollutants from waste water.
Efuents from pharmaceutical, paint, tanneries and textile
industries discharge unwanted toxins and contaminants like
dyes, detergents and pigments into natural water bodies, thus
creating a hazard to mankind [1,2]. International surveys and

http://dx.doi.org/10.1016/j.jscs.2015.05.011
1319-6103 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

550
reports worldwide show a large increase in the extent of diseases
and health problems caused by these toxic substances which are
released from different industrial activities [3]. Hence, various
research groups focus on the development of different methods
available for the removal of these contaminants from water and
waste water. Literature survey reveals various physical and
chemical methods for the removal of organic dyes and pigments
from these efuents, which includes adsorption by carbonaceous material, solvent extraction and chemical oxidation
[4,5]. These methods often suffer from many disadvantages, like
the use of solvents for regeneration of spent adsorbent which is
against the principles of green chemistry, discharge of secondary waste generated in the case of activated carbon adsorption etc. Hence, to overcome all these demerits, advanced
oxidation process (AOP) has been attracted globally for the
degradation of organics through the intersession of photo
energy, employing a suitable semiconductor photocatalyst.
The efcacy of the catalyst for the treatment of efuents loaded
with different dyes is a critical task. Hence, our research is
focused on the treatment of organics through photocatalysis
reaction pathway. Metal oxides, for example ZnO, TiO2,
WO3, SnO2 etc. are often employed as semiconductor materials
as they full the criterion for an eligible photocatalyst [69].
Since, they poses the approximate band gap energy required
for excitation of the electron from the valance band to the conduction band by the absorption of photons they lead to further
photocatalytic degradation reactions. When we consider the
solar energy spectrum, it comprises a maximum of visible
(45%) and infra-red radiation compared to a smaller portion
of ultra-violet (5%) rays [10]. Though, UV light is energy intensive but very less in availability, hence the visible region of solar
spectrum is exploited to make the photocatalytic process viable
and cost efcient. Therefore, research towards the synthesis of a
better visible active photocatalyst is obtained by the modication of the semiconductor band gap. This could be attained
by doping of metals, non-metals and rare earth materials, by
semiconductor coupling, preparation of mixed metal oxides
[1116], core-shell nanomaterials and coating of metal oxides
on substrates like CNT, SiO2 and Al2O3 etc., [17]. Very recently
synthesis of nanocrystalline ZnO doped Dy2O3 was carried out
by our research group, and interestingly the material possessed
excellent visible light photocatalytic activity [18]. The material
was successfully synthesized by a simple precipitation technique
and the efciency was tested for the degradation of a model pollutant Orange G dye (azo dye) under visible light irradiation.
The doping percentage of semiconductor metal oxide plays a
major role in the visible photocatalytic activities. 50% of doping
was found to be the optimum concentration of dopant for
enhanced visible photocatalytic activity. Therefore, the present
study focused on the synthesis and characterization of
nanocrystalline ZnO doped Dy2O3 for the visible light photocatalytic degradation of a non-azo dye malachite green (MG).
The preliminary and kinetic studies were conducted and the
results are reported in detail.
2. Materials and methods
2.1. Materials
Zinc nitrate hexahydrate (98%, Zn(NO3)26H2O) and dysprosium nitrate (99.9%, Dy(NO3)6H2O) were purchased from

G.A. Suganya Josephine et al.

SigmaAldrich, India. malachite green Oxalate and Na2CO3
were supplied by S.D. Fine Chem., Mumbai, India.
2.1.1. Preparation of the doped photocatalyst
Nanocrystalline semiconductor doped dysprosium oxide was
prepared by a simple and efcient precipitation technique as
reported earlier [18]. The semiconductor metal nitrate (zinc
nitrate) and the dysprosium nitrate were taken in an equimolar
ratio. The solutions of nitrates and sodium carbonate were
prepared in doubly distilled water. 0.1 M of dysprosium nitrate
was taken in a beaker and stirred continuously when 0.1 M of
sodium carbonate was added drop-wise. Then, 0.1 M of zinc
nitrate was added to the solution followed by 0.1 M sodium
carbonate. After complete addition the precipitated mixture
was stirred for 15 min. The precipitates thus obtained were
ltered, washed and calcined at 700 C for 2 h. The calcined
sample was nely ground and used as such for the photocatalytic reaction. The sample was named as MO doped LO.
For pristine MO (zinc oxide) and pristine LO (dysprosium
oxide) the same procedure was followed employing only the
zinc nitrate or dysprosium nitrate as precursors.
2.1.2. Preparation of MG dye
The dye solutions were prepared by dissolving the required
amount of MG dye in distilled water in the required pH. A
1000 ppm stock solution of the MG sample was prepared by
taking 100 mg of MG in 100 mL of distilled water. Then the
required concentrations were prepared by diluting accordingly.
2.2. Methods
2.2.1. Characterization techniques
The prepared photocatalysts were characterized by FT-IR,
XRD, UVVis DRS, FE-SEM, and AFM techniques. Metal
oxide stretching frequencies were determined by FT-IR measurement in a Perkin Elmer FT-IR spectrometer. The crystallinity of the prepared photocatalyst was characterized by
XRD analysis in a PAN analytical X-ray diffractometer,
Germany using a Cu Ka radiation (2h scan range between
10 and 70) with an accelerating voltage of 40 kV and an
emission current of 25 mA. The surface morphology and size
of particle were analysed by FE-SEM analysis in an FESEM instrument Model Supra 55 Carl Zeiss, Germany.
The surface roughness was also determined by an atomic force
microscopy technique (Model-NTEGRA PRIMA-NTMDT,
Ireland) by using the contact mode. The UVVis DRS analysis
was performed in a UV 2600, Shimadzu, Japan using a scan
speed of 200 nm/min.
2.2.2. Photo-reactor setup
The photocatalytic degradation of MG dye was performed in a
visible light emitting annular batch type photo reactor supplied
by the HEBER Scientic, INDIA. Wherein, a tungsten lament lamp was used as an irradiation source (500 W). The
lamp was surrounded by a water jacketed tube. The preliminary photocatalytic reactions were conducted with a sample
volume of 10 mL. The appropriate amount of catalyst and
MG dye (prepared in the required pH solution) were taken
in the glass tubes of the photoreactor and subjected to visible
light irradiation. The kinetic studies were studied in a 100 mL

Photocatalytic Dye Degradation by ZnO doped Lanthanide oxide under Visible Light Irradiation
volume of sample, with aliquots of sample withdrawn at the
prescribed time intervals and analyzed by UVVisible spectrometer. The percentage degradation of the MG dye was calculated by the absorption measurement and computed from
the following Eq. (1):
Degradation efficiency%

C0  Ce
 100
C0

where, C0 and Ce are the initial and nal concentrations of

MG dye in the aqueous phase
3. Results and discussion
3.1. FT-IR and UVVis DRS analysis of the photocatalyst
The FT-IR analysis of the prepared photocatalyst is shown in
(Fig. 1(i)), characteristic peaks appeared at 565.24 and
463.12 cm1 which correspond to the stretching vibrations of
Zn-O and Dy-O in the prepared photocatalyst. The peak at
3452 cm1 which corresponds to the OH stretching vibration
is observed due to the presence of absorbed moisture present in
the sample. The FT-IR analysis proves the presence of both

551

zinc and dysprosium as oxides in the prepared sample. The

UVVisible Diffuse reectance spectrum of the prepared catalyst is shown in Fig. 1(ii). A maximum absorbance was
observed around 400 nm and the peaks at 700800 nm correspond to the ff transitions present in lanthanide elements.
The band gap of the material was calculated using the equation
as give below:
A K hv  Eg 1=2=hv

where, v is the frequency, h is the planks constant and k equals

a constant. Band gap was calculated by plotting (Ahv)2 vs hv.
The results are shown in Fig. 1(iii). The tangent drawn to the x
axis gives the band gap of the material directly. It was found to
be 3.1 eV which coincides with the literature values. Also, the
literature cites the band gap of pristine ZnO and Dy2O3 to be
3.07 and 4.70 eV respectively [18].
3.2. Particle size and morphology
The particle size of the catalyst was determined by XRD and
FE-SEM analysis. The X-ray diffraction analysis showed the
peaks to be sharp and narrow which suggested the prepared

60

% T

565.24
463.12

40

20

0
4000

3500

3000

2500

2000

1500

1000

500

Wavelength cm -1

(i)
40

1.0

35
0.8

MO doped LO

MO doped LO

30

Abs

2
Ahv

0.6

0.4

25
20
15
10

0.2

5
0.0

3.1

0
100

200

300

400

500

600

Wavelengh (nm)

(ii)
Figure 1

700

800

900

hv (eV)

(iii)

(i) FT-IR spectrum (ii) UVVisible DRS spectrum and (iii) band gap plot ((Ahv)2 vs hv) of MO doped LO.

552

G.A. Suganya Josephine et al.

approximately 6070 nm. Fig. 2(iii) shows the FE-SEM images
of the prepared photocatalyst.

MO doped LO to be highly crystalline and nanosized

(Fig. 2(i)). XRD data were corroborated by the literature values (ZnO as JCPDS No. 36-1451 and Dy2O3 as JCPDS 01-0791722) [19], and it was found that the peaks due to the presence
of both zinc and dysprosium oxides were present in the MO
doped LO photocatalyst. The crystallite size was calculated
by drawing the WilliamsonHall plot (3), and the results
obtained were found to be similar to the literature values [18].
b Cosh k

k
4e Sinh
D

3.3. Surface roughness analysis

The MO doped LO photocatalyst was evaluated for its surface
properties by atomic force microscopy. The prepared photocatalyst was nanosized and possessed a high surface roughness
(53.28 nm) and the surface was found to be highly porous with
a large number of peaks and troughs on it, which supports the
fact that the organic molecules could easily sit on the surface
and thereby proceeds through the degradation process. The
image is shown in Fig. 2(iv).

kk
intercept

3.4. Photocatalytic studies under visible light irradiation

where, k is 0.94 (spherical), k the wavelength of radiation

(0.154 nm), h half the diffraction angle, b the full width at half
maximum, e the lattice strain and D the size of the crystallite.
A plot of bCosh vs 4Sinh was drawn as shown in Fig. 2(ii),
from the value of the intercept crystallite size would be calculated from Eq. (4). The size of the crystallite was found to be
66.33 nm. The FE-SEM images of the prepared photocatalyst
proved the nanocrystalline semiconductor doped lanthanide
oxide to exhibit spherical morphology with a particle size of

3.4.1. Preliminary studies

Studies were conducted to compare the photocatalytic efciencies of the prepared MO, LO and MO doped LO on the degradation of MG under visible light irradiation. 10 mg of the
appropriate catalyst in 10 mL of 10 ppm MG solution at neutral pH was taken as the test solution, a blank solution was
also tested to study the effect of photolysis (without catalyst

250
0.010

(222)

MO doped LO

MO doped LO
Linear Fit

(211)

Cos

(622)

100

(400)

150

(100)
(002) (440)
(101)

Intensity

200

0.005

50

Slope : 0.00246
Intercept : 0.002183

0
10

20

30

40

2 (degree)

50

60

70

0.000
1.0

1.2

(i)

(iii)

1.4

1.6

1.8

2.0

4Sin

(ii)

(iv)

Figure 2 (i) Shows the XRD pattern (ii) WH plot for the determination of crystallite size (iii) FE-SEM and (iv) AFM images of the
prepared MO doped LO photocatalyst.

Photocatalytic Dye Degradation by ZnO doped Lanthanide oxide under Visible Light Irradiation
10 mL of 10 ppm MG). The results are shown in Fig. 3(i)
which proves the higher activity of MO doped LO (<99%)
when compared to MO (60%) and LO (42%). However, without catalyst it showed 43% degradation which suggests the
activity of LO is only due to photolysis, the percentage of
degradation is even lesser which is because the solid LO sample
inside the solution would prevent the penetration of light
inside possibly decreasing the photo bleaching process. The
band gap of LO (4.76 eV) supports the obtained results [18].
As, it is an insulator material, it would not possess photocatalytic activity under visible light irradiation [20]. Hence, the
preliminary studies were conducted as a comparison between
pristine MO and MO doped LO. Experiments on the effect
of aqueous phase pH on the degradation of MG dye were conducted in order to determine the capability of the prepared
photocatalyst at various acidic and basic conditions. Hence,
dye degradation studies at pH values between pH 2 and pH
12 (10 mg of catalyst/10 ppm MG dye) were performed and
the results are shown in Fig. 3(ii). It clearly proves that the
catalyst shows maximum efciency at neutral pH with good
catalytic activities at all pH ranges when compared to pristine
MO. Also the photocatalytic activity is higher than pristine
MO. To determine the optimum amount of photocatalyst

100

Pristine
MO

60

Without
Catalyst

90

% Degradation

80

% Degradation

required to degrade a known concentration of dye solution,

the initial amounts of the photocatalyst were varied from 3
to 20 mg for 10 ppm of MG dye solution at neutral pH.
The results shown in Fig. 3(iii) prove that the activity of MO
doped LO is nearly 99% for all catalyst dosages; hence 3 mg
of catalyst/10 mL of dye solution has been xed as the optimum catalyst amount. Whereas, in the case of pristine MO
the degradation percentage increases as the catalyst
concentration increases, and varied from 80 to 90%. Hence,
8 mg/10 mL was xed as the catalyst dosage for pristine
MO. To investigate the ability of the xed amount of photocatalyst to degrade different initial concentrations of dye solutions, studies on the variation of MG dye concentration from 5
to 50 ppm were conducted. The results shown in Fig. 3(iv) suggest that as the dye concentration increases degradation
decreases in the case of pristine MO and the degradation is
nearly 65% for 50 ppm. But, in the case of the prepared MO
doped LO the degradation decrease is very less even for
50 ppm the percentage of degradation is nearly 98%. Hence,
the time taken for degradation is very less for lower concentrations of dye solution. Therefore, the kinetics of photodegradation could possibly suggest the degradation with respect to
time.

MO doped LO

100

553

Pristine
LO

40

MO
MO doped LO

80

70

60

20
50

10

12

pH of aqueous phase

(i)

(ii)
100

100
98

90

94

% Degradation

% Degradation

96

MO
MO doped LO

92
90
88
86
84

MO
MO doped LO

80

70

60

82
80

50
2

10

12

14

16

Amount of Catalyst (mg)

(iii)

18

20

22

10

20

30

40

50

Concentration of Dye (mg/L)

(iv)

Figure 3 (i) Shows the comparison of photocatalytic efciency of MO, LO, MO doped LO and without catalyst. (ii)(iv) shows the effect
of aqueous phase pH, catalyst dosage and initial dye concentration.

554

G.A. Suganya Josephine et al.

3.4.2. Kinetic studies

The kinetic studies on the photodegradation of MG dye were
conducted in 100 mL volume of dye solution and appropriate
catalyst concentration at neutral pH. For pristine MO and
MO doped LO the catalyst dosages were 80 mg/100 mL and
30 mg/100 mL respectively. Fig. 4(i) shows the comparison
of percentage degradation for pristine MO, MO doped LO
and without catalyst. It is clearly seen that within 30 min the
degradation efciency is 99.9% for MO doped LO and it took
more than 300 min to reach 90% degradation in the case of
pristine MO. The plot for without catalyst shows 60% degradation on visible irradiation for 300 min, which conrms that
the degradation that has occurred in the prepared MO doped
LO photocatalyst is only due to photocatalytic action and not
due to photo bleaching, but for pristine MO the% degradation
is contributed by both photolysis and catalytic action. Also,
after completion of the degradation process MO doped LO
photocatalyst retained the original white colour of the photocatalyst, whereas, pristine MO was light blue in colour which
shows the absorbed dye on the catalyst surface. Fig. 4(ii) and
(iii) shows the rate constant plot for both the prepared photocatalysts, they followed a pseudo rst order kinetics. The rate

constant for degradation of 100 ppm MG dye was found to be

higher (0.149 * 103 min1) for MO doped LO whereas for
pristine MO it was very less (0.035 * 103 min1). Hence, these
results prove the efcacy of the prepared MO doped LO
photocatalyst.
3.5. Mechanism
3.5.1. Mechanism for the generation of OH radicals by MO
doped LO under visible light irradiation
The characterization results suggested the prepared material to
be highly crystalline, nanosized with spherical morphology
possessing a higher surface roughness and porosity. Hence, a
large number of organic moieties could adsorb on the surface
of the photocatalyst for further reaction to take place. The visible light induced photocatalysis is initiated by the generation
of OH radicals in the reaction system. A plausible mechanism
is proposed for the photocatalytic activity of the prepared photocatalyst[18,21,22]. From the UVVis DRS results band gap
energy was found to be 3.1 eV hence, the material is capable
of being excited by visible light. Upon irradiation of visible
light on MO doped LO (ZnO doped Dy2O3), the electrons

100
90

% Degradation

80
70
60
50

Without catalyst
Pristine MO
MO doped LO

40
30
20
10
0
0

50

100

150

200

250

300

Time (min)

(i)
3.5

2.6

MO doped LO

3.0

Rate constant:0.142 x 10 min

R2: 1

-1

Pristine MO

2.2

ln(Co/Ce)

2.5

ln(Co/Ce)

2.4
-3

2.0
1.5

2.0
1.8

Rate constant: 0.035x 10-3 min-1

R2: 0.9825

1.6

1.0

1.4

0.5
1.2

10

15

20

25

20

40

60

Time (min)

Time (min)

(ii)

(iii)

80

100

Figure 4 (i) Shows the kinetics of 100 ppm MG dye of MO, MO doped LO and without catalyst, (ii) and (iii) plot of ln(Co/Ce) vs time for
MO doped LO and pristine MO.

Photocatalytic Dye Degradation by ZnO doped Lanthanide oxide under Visible Light Irradiation

555

(i)
O
-

O-

OH

OH

O
C+
N

Malachite Green oxalate

OH

OH

f urther degradation
O
H

+
H

water

NH

HN

NH

OH

carbon dioxide

OH

H2 N

NH 2

H2 N

NH

(ii)
Figure 5
dye.

(i) Mechanism of the photocatalyst for the generation of OH radicals and (ii) a plausible mechanism for the degradation of MG

from the valance band (VB) are excited to the conduction band
(CB) of the photocatalyst. This would lead to a charge separation in the catalyst. Due, to the presence of f orbitals in the prepared material, they trap the excited electrons in CB, thereby
preventing the recombination of electron-hole pair. Hence, this
facilitates the separated hole to react with the water molecule
present in the surrounding for the generation of OH radicals.
These OH radicals on further reaction with the organic moieties (in this case malachite green) would bring about the photocatalytic degradation of the organic materials to yield
carbon dioxide and water as the end products. But, in the case
of pristine ZnO, though the electron gets excited upon light

irradiation, the possibility of recombination of electrons and

holes is higher hence the generation of OH radicals is lesser.
For Dy2O3, the band gap is very high for the excitation to take
place, therefore cannot generate OH radicals. The schematic
representation of the mechanism is shown in Fig. 5(i).
3.5.2. Plausible mechanism of MG dye degradation
The mechanism of MG dye degradation is initiated by the
attack of OH radicals on the malachite green cation. First
the N-demethylation occurs on the attack of OH radicals, leading to the removal of all the four methyl groups present in MG
dye. As there is a continuous generation of OH radicals in the

556
reaction system, attack of OH radicals occurs spontaneously
on the organic moiety [23]. On further reaction, the byproducts may undergo continuous degradation due to OH radical attack to bring about a benzene ring removal [24] and ring
opening to completely mineralize the material to yield carbon
dioxide and water as the end by-products [25]. A schematic
representation is shown in Fig. 5(ii).
4. Conclusions
Nanocrystalline metal oxide doped lanthanide oxide was efciently synthesized by a simple precipitation method. The prepared photocatalyst was characterized by FT-IR, UVVis
DRS, XRD, FE-SEM and AFM techniques. The prepared
photocatalyst was compared with pristine MO to check the
efciency of the photocatalyst for the degradation of MG
dye molecules. The preliminary results clearly proved the efcacy of the MO doped LO photocatalyst to readily degrade
MG dye molecules in the aqueous phase. Only 3 mg/10 mL
of MO doped LO photocatalyst was required for the complete
degradation of MG dye molecules whereas more than twice the
amount (8 mg/mL) were required for pristine MO. Also MO
doped LO showed 98% of degradation for 50 ppm dye concentration but MO showed only 65%. The kinetic studies proved
that MO doped LO was very effective in degrading even
100 ppm dye solution with faster rate (30 min) than pristine
MO (300 min). The rate constant for dye degradation was four
times higher in the case of MO doped LO when compared to
pristine MO. Therefore, MO doped LO is an environmentally
benign photocatalyst, which could be extended for the degradation of organics in industrial efuents.
Acknowledgements
Authors would like to thank the Department of Science and
Technology (DST), New Delhi, India for providing a fellowship under INSPIRE and the facility provided by
INDUSMAGIC 12 FYP programme to carry out this work.
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