Materials Science in Semiconductor Processing 26 (2014) 218–224

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Cobalt-doped cerium oxide nanoparticles: Enhanced

photocatalytic activity under UV and visible light irradiation
Jayapalan Saranya a,b, Kugalur Shanmugam Ranjith a, Padmanaban Saravanan c,
Devanesan Mangalaraj d, Ramasamy Thangavelu Rajendra Kumar a,d,n
a
Advanced Materials and Devices Laboratory, Department of Physics, Bharathiar University, Coimbatore, Tamil Nadu 641046, India
b
Data Mining and Text Mining Laboratory, Department of Bioinformatics, Bharathiar University, Coimbatore, Tamil Nadu 641046, India
c
Defence Metallurgical Research Laboratory, Hyderabad, Andhra Pradesh 500058, India
d
Department of NanoScience and Technology, Bharathiar University, Coimbatore, Tamil Nadu 641046, India

a r t i c l e in f o abstract

Available online 17 May 2014 CeO2 nanoparticles (NPs) were synthesized by coprecipitation using cerium(III) nitrate
Keywords: hexahydrate as the precursor and ethanol as the solvent. Different concentration of cobalt-
Cerium oxide doped cerium oxide NPs (3mol % and 6 mol %) were prepared by adding various
Cobalt-doped cerium oxide concentrations of cobalt chloride to cerium nitrate. The as-synthesized NPs were
Photocatalytic activity characterized through X-ray diffraction (XRD) measurements, ultraviolet (UV)–visible
Methylene blue spectroscopy, Photoluminescence (PL) spectroscopy, and transmission electron micro-
scopy (TEM). XRD results reveal that the as-prepared CeO2 NPs had a face-centered cubic
structure with crystallite size in the range of 5–8 nm. TEM analyses showed that the CeO2
NPs and Co-doped CeO2 NPs had a homogenous size distribution (sizes were within
5–12 nm). Band-edge absorption of CeO2 NPs redshifted upon increasing the Co concen-
tration as compared to undoped CeO2 NPs. PL spectra reveal a peak shift of CeO2 emission
upon cobalt doping, which were due to an increase in oxygen defects localized between
the Ce4f and O2p energy levels (i.e., via formation of Ce3 þ states). Photocatalytic
degradation of methylene blue in aqueous solution under UV and visible (sunlight)
irradiation in the presence of pure CeO2 NPs and of Co-doped CeO2 NPs was investigated.
The efficiency of photocatalytic degradation of CeO2 NPs increased with the Co concen-
tration both under UV irradiation and under visible light. Co-doped CeO2 NPs (6 mol%)
showed degradation efficiencies of 98% and 89% at 420 min of exposure to UV irradiation
and to visible light, respectively.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction area, and high chemical stability. Because of these proper-

ties, they are promising candidates for applications in
Recent studies have shown that nanostructures based environmental remediation, in selective organic syntheses
on metal oxides and carbon, as well as metal oxide–carbon of fine chemicals, and in water splitting technologies for
nanocomposites and core–shell nanostructures, have high clean hydrogen energy production [1–4]. Ceria-based
electron conductivity, high mobility, large specific surface nanostructures have attracted much interest because of
their unique chemical and physical properties. The unique
n
structures of cerium oxide (CeO2) nanoparticles (NPs) have
Corresponding author at: Bharathiar University, Department of
become increasingly popular because of their broad
Nanoscience and Technology, School of Physical Sciences, Coimbatore,
Tamil Nadu 641 046, India. Tel.: þ91 422422222; fax: þ 91 2422387. applicability to various areas such as microelectronics [5],
E-mail address: rtrkumar@buc.edu.in (R.T. Rajendra Kumar). optoelectronics [6], fuel cell technologies [7], gas sensors

http://dx.doi.org/10.1016/j.mssp.2014.03.054
1369-8001/& 2014 Elsevier Ltd. All rights reserved.
 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224 219

[8], solid-state electrolytes [9], and photocatalysis [10]. 2.2. Characterization

CeO2 has a band gap of 3.2 eV and is thus an absorbent for
ultraviolet (UV) radiation; it is used in UV-induced cataly- The phase and crystalline structures of the as-prepared
tic reactors, UV protective sunglass lenses, and sunscreen samples were studied on a Philips X’pert Pro Advance
cosmetics [11,12]. In recent years, numerous techniques powder X-ray diffractometer (Cu Kα radiation; λ ¼
have been proposed for the controlled synthesis of nano- 1.5418 Å). The crystallite size of the nanopowders, dXRD,
sized CeO2, such as chemical reduction, combustion synth- was calculated through a Williamson–Hall (W–H) plot
esis, sonochemical synthesis, sol–gel synthesis, and self- [25]. The morphology of the as-prepared CeO2 NPs was
assembly processes [13–15]. CeO2 nanostructures doping studied by using a Tecnai F-12 transmission electron
with various materials have drawn much interest because microscope operated at an acceleration voltage of 15 kV.
of their magnetically induced optical properties [16–18]. Energy dispersive X-ray analysis (EDAX) was performed on
CeO2 nanostructures doped with transition-metal ions a Bruker Qntax spectrum analyzer. UV–visible (UV–vis)
exhibit dilute magnetic oxide behavior because of the absorption spectra of both pure CeO2 NPs and Co-doped
route by which they utilize charge and spin degrees of CeO2 NPs were recorded at a wavelength range of
freedom of their electrons, which may be useful in 200–800 nm at room temperature by using a JASCO
electronic devices [19]. Very few studies have focused on V530 UV–vis spectrophotometer. Photoluminescence (PL)
dopant-assisted enhancement of physical properties spectroscopy at an excitation wavelength of 350 nm
of CeO2 nanostructures for environmental remediation. at room temperature was performed on a Fluorolog-3
Diffusion of photogenerated excitons to the catalyst sur- luminescence spectrometer (JASCO-FP-6600).
face is vital for enhancing the photocatalytic activity.
Diffusion of photogenerated charge carriers may be 2.3. Photocatalytic experiments
improved by doping the CeO2 lattice with 3d transition
metals [20]. Yue et al. [21] investigated the photocatalytic The photocatalytic behavior of both Co-free and
properties of CeO2 NPs doped with transition-metal ions Co-doped CeO2 NPs was examined by studying the photo-
such as Fe, Mn, Ti, and Co. They found that Co-doped CeO2 catalytic decomposition efficiency of methylene blue (MB)
NPs have higher photocatalytic efficiency compared with dye. Photocatalytic degradation of 15 ppm of MB was
other CeO2 NPs doped with transition-metal ions. Sabari carried out under UV irradiation with 30 W power and
Arul et al. [22] reported that Co doping influences the 365 nm wavelength and under visible irradiation (sun-
morphology of CeO2 nanostructures, thereby increasing light,  900 lm/m2) on a normal sunny day between
the surface area and enhancing their photocatalytic activ- 8.00 a.m. and 4.00 p.m. Catalyst (0.1 g) was added to
ity under UV irradiation. To date, few studies have been 100 mL of aqueous MB solution, and the solution was
done on the photocatalytic activity of nanoceria under stirred in the dark for 30 min to attain absorption–deso-
visible-light irradiation. The photocatalytic activity of rption equilibrium between the catalyst and the dye. After
N-doped CeO2 [23] and of Au-supported CeO2 nanostruc- 30 min of equilibrium, the samples were irradiated under
tures [24] under visible irradiation were studied. In the the respective sources. After irradiation, the solution was
present work, we report on the influence of Co dopant centrifuged and filtered to remove the dispersed catalyst
concentration on the structural, optical, and photocatalytic particles. A 2 ml of test sample was taken at 60 min
properties of CeO2 NPs. We show that there is no sub- intervals, and the concentration of MB in solution was
stantial change in size and shape of the CeO2 NPs upon determined by using a UV–vis spectrophotometer. The
increasing the Co dopant concentration. The photocatalytic efficiency of degradation (η) was calculated through Eq.
activity of pure and Co-doped CeO2 NPs under UV irradia- (1):
tion and under sunlight were investigated.
A0  At
η¼  100 ð1Þ
A0
2. Materials and methods
where A0 is the absorption maximum at time t ¼ 0, and At
2.1. Synthesis of undoped and Co-doped CeO2 NPs is the absorption maximum after complete degradation
of MB.
CeO2 NPs were prepared by a coprecipitation method.
Ce(NO3)3  6H2O (2 mol) was dissolved in 100 mL of etha- 3. Results and discussion
nol, and the resulting mixture was heated with stirring up
to 50 1C. After 30 min of stirring, 10 mL of 30% of ammonia 3.1. Crystalline structure of the prepared NPs
solution was added to the reaction mixture. A pale-yellow
dispersion was thus obtained. This growth solution was Fig. 1 shows the X-ray diffraction (XRD) patterns of
heated with stirring at 50 1C for 4 hrs. Subsequently, the undoped CeO2, 3% Co-doped CeO2, and 6% Co-doped CeO2,
precipitate was collected, centrifuged and washed thrice as well as standard data for bulk CeO2. The XRD pattern of
with water and with ethanol, dried at 60 1C, and then undoped CeO2 has diffraction peaks at 2θ ¼ 28.721, 33.331,
annealed at 200 1C for 2 hrs. Co-doped CeO2 NPs were 47.591, 56.41, and 58.91, which correspond to the (111), (200),
prepared by adding cobalt chloride at 0.06 and 0.12 moles (220), (311), and (222) planes, respectively. These results are
at different percentages for doping (mol %) to a 2 mol of Ce in good agreement with data for bulk CeO2 (JCPDS card no.
(NO3)3  6H2O solution, and the above procedure for synth- 43-1002). There was no evidence of the presence of the
esis and purification was repeated. Ce2O3 phase. Strong and broad crystal peaks in the XRD
220 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224

Fig. 2. Williamson–Hall plot of (a) pure CeO2, (b) 3% Co-doped CeO2, and
Fig. 1. X-ray diffraction pattern of (a) pure CeO2, (b) 3% Co-doped CeO2,
(c) 6% Co-doped CeO2 nanoparticles.
and (c) 6% Co-doped CeO2. (d) JCPDS data for bulk CeO2.

patterns indicate that the CeO2 particles were crystals with Table 1
sizes in the nanometer range. The average dXRD was calcu- Lattice constant (a) Å and crystallite size of undoped CeO2 NPs and of Co-
doped CeO2 NPs.
lated by using the W–H plot. The instrumental contribution
to line broadening in the diffraction peak was estimated. Co dopant concentration (%) Mean Lattice constant a (Å)
Correction for peak broadening (βhkl) corresponding to each crystallite size
peak of the ceria NPs was estimated through the equation (nm)

βhkl ¼ ½ðβhkl Þ2 measured  ðβÞ2 measured1=2 ð2Þ dXRD dTEM

where βhkl is the integral breadth of the reflection 2θ (in 0 7.97 6–12 5.379
radians), corrected for instrumental contribution. William- 3 7.07 5–10 5.372
son and Hall proposed a method of deconvolution for size 6 5.81 5–8 5.3513

and strain broadening. The diffraction angle 2θ is a function

of peak width, expressed in Eq. (3) [26] as:
(46%), CoO clusters formed (data not shown); therefore, 6%
βhkl ¼ ðKλ=Dv CosθÞ þ ð4ε tan θÞ ð3Þ
Co dopant was adopted as the maximum concentration of
Upon rearrangement, dopant.
βhkl cosθ ¼ ðKλ=Dv Þ þ ð4ε sin θÞ ð4Þ
3.2. Morphology of the prepared NPs
where K is the shape factor (0.9 for spheres); Dν is the
volume-weighted dXRD; and θ is the angle of reflection (in Images obtained by transmission electron microscopy
degrees). Plots of β cos θ versus 4 sin θ for undoped and Co- (TEM) show the morphology and size of the undoped, 3%
doped CeO2 NPs are shown in Fig. 2. The corresponding and 6% Co-doped CeO2 NPs (Fig. 3). The mean dXRD values
W–H plot is drawn only for preferentially oriented lattice and particle sizes of the Co-doped and undoped CeO2 NPs
planes, namely, (111), (200), (220), (311), (400), and (331). estimated by XRD and TEM, respectively, are as given in
The value of dXRD is the intercept of the line fitted against the Table 1. The dXRD values and size of Co-doped CeO2 NPs
plot. The estimated average dXRD values for undoped, 3% Co- were smaller than those of the pure CeO2 samples.
doped, and 6% Co-doped CeO2 NPs are 6.81, 5.79, and Selected area electron diffraction (SAED) patterns (inset
4.59 nm, respectively. The calculated lattice parameter a for of Fig. 3) of the CeO2 samples and the Co-doped CeO2
undoped CeO2 (0.5379 nm) is consistent with that of bulk samples are consistent with the cubic fluorite structure
CeO2 (0.5411 nm, JCPDS card no. 43-1002). The diffraction of bulk CeO2; their ring patterns correspond to the
peaks are consistent with the cubic fluorite structure of bulk (111), (200), (220), and (311) planes. Average particle size
CeO2 crystal (JCPDS card no. 43-1002). Lattice parameters for calculated from TEM characterization for both undoped
both doped and undoped samples were calculated. Lattice CeO2 and Co-doped CeO2 NPs were within the range
parameters of cubic CeO2 with various concentrations of 6–12 nm, in agreement with the XRD results. Fig. 4 shows
dopant were calculated (results are listed in Table 1). Upon the EDAX results for undoped CeO2 NPs, as well as for 3%
increasing the dopant concentration, lattice parameter and 6% Co-doped CeO2 NPs. Their chemical compositions
values tended to decrease because of replacement or were correlated with that of Ce, Co, and O. The inset in
because of defect formation due to Co ions in the CeO2 Fig. 4 shows the atomic ratios for each element in the
lattice. On further increasing the Co dopant concentration undoped NPs, as well as in 3% Co-doped CeO2 NPs and in
 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224 221

80
80 80
No of Particles
No of particles

No of particles
60
60 60

40 40 40

20 20 20

0 0 0
6 7 8 9 10 11 12 13 5 6 7 8 9 10 11 5 6 7 8 9 10 11
Particle size (nm) Particle size (nm) Particle size (nm)

Fig. 3. TEM images of (a) undoped CeO2, (b) 3% Co-doped CeO2, and (c) 6% Co-doped CeO2. Insets show their corresponding SAED patterns. Size-
distribution histograms of (d) undoped CeO2, (e) 3% Co-doped CeO2, and (f) 6% Co-doped CeO2.

cps / eV cps / eV cps / eV

4.5
10 Element Wt % At % Element Wt % At % Element Wt % At %
5 4.0
Ce 81.28 33.14 Ce 86.65 44.46 3.5 Ce 89.57 57.46
8
O 18.72 66.86 4 O 11.99 53.87 3.0 O 6.51 36.55
6 Co 1.37 1.67 2.5 Co 3.93 5.99
3
Co Co
O Ce O Ce Co 2.0 O Ce Co
4
Ce 2 Ce 1.5 Ce

1.0
2 1
0.5
0 0 0.0
0 2 4 6 8 10 12 14 16 18 2 4 6 8 10 12 14 16 18 20 2 4 6 8 10 12 14 16 18 20
keV keV keV

Fig. 4. EDAX spectra of (a) undoped CeO2 NPs, (b) 3% Co-doped CeO2 NPs, and (c) 6% Co-doped CeO2 NPs.

6% Co-doped CeO2 NPs. The presence of Co in the 3% and 340 nm, respectively. The optical band gap (EBG) was
6% Co-doped CeO2 NPs is indicated by the EDAX spectrum. calculated based on the absorption spectrum of the NPs
No evidence of Co is shown by the XRD spectrum, by using Eq. (5) [27]:
confirming Co doping of the CeO2 lattice. An increase in
1240
Co dopant concentration enhanced the presence of Co EBG ¼ ð5Þ
λAbsorpEdge
(weight %) in the EDAX spectrum.
where λ is the absorption edge of the respective
3.3. Optical properties of CeO2 NPs samples. The onset of the absorption edge for pure CeO2
NPs, 3% Co-doped NPs, and 6% Co-doped CeO2 NPs are at
3.3.1. UV–vis absorption study of CeO2 NPs 395, 403, and 436 nm, respectively. The corresponding
As a UV-blocking material, CeO2 has strong absorption band gaps based on the UV absorption peaks were found
characteristics in the UV range. The UV absorption peaks of to be 3.13, 3.07, and 2.84 eV, respectively. Absorption
undoped NPs, as well as of 3% Co-doped and 6% Co-doped spectra of the Co-doped CeO2 NPs are redshifted relative
CeO2 NPs, are presented in Fig. 5(a–c) as respectively. to that of the undoped CeO2 NPs. The lower EBG of Co-
Absorption peaks due to charge-transfer transitions from doped CeO2 (2.84 eV) compared with that of pure CeO2
O2  to Ce4 þ energy levels in CeO2 are at 325, 326, and (3.13 eV) is due to doping, as evidenced by their
222 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224

Fig. 5. UV–vis spectra of (a) undoped CeO2 NPs, (b) 3% Co-doped CeO2
NPs, and (c) 6% Co-doped CeO2 NPs. Fig. 6. Photoluminescence spectra of (a) undoped CeO2 NPs, (b) 3% Co-
doped CeO2 NPs, and (c) 6% Co-doped CeO2 NPs.

absorbance in the UV region. Yue et al. [21] reported that

doping CeO2 with Co could reduce the band gap of CeO2 to the catalytic activity under UV irradiation and under
more effectively than do other transition-metal dopants. visible light. The photocatalytic activity depends on the
Doping with Co ions creates oxygen vacancies and favors ability of the catalyst to separate the electron–hole pairs.
the formation of Ce3 þ from Ce4 þ . This increases the The rate of electron–hole pair separation and recombina-
amount of Ce3 þ states, resulting in the formation of tion is the most significant factor in photocatalytic activity.
localized energy states that are closer to the conduction When a photon of UV light strikes the catalyst surface,
band [26,28] and thereby decreasing the band gap. conduction-band electrons and valence-band holes sepa-
rate. The electrons then migrate to the catalyst surface,
3.3.2. PL studies of CeO2 NPs where they react with free radicals and undergo secondary
PL spectra (Fig. 6) of the CeO2 NPs and of the Co-doped reactions leading to degradation of the dye [34]. The
CeO2 NPs were obtained at an excitation wavelength of characteristic band for MB centered at 661 nm in the
350 nm. The PL emission around 400–500 nm is associated temporal UV–vis spectra weakened immediately upon UV
with charge transfer from the Ce4f energy level to the O2p irradiation, indicating degradation of the dye molecules.
level (valance band). Localization of the energy levels Fig. 8 shows the degradation curve for Co-doped CeO2 NPs
between the Ce4f and O2p bands due to defects could and for Co-free CeO2 NPs under UV irradiation and in the
lead to wider emission bands [29]. The PL emission of dark. The figure illustrates that the photocatalytic degrada-
undoped CeO2 at around 400–420 nm region is associated tion efficiency of undoped CeO2 NPs was 34.5% at 7 h of
with the charge transfer between Ce4f energy states [30], UV irradiation, which coincides with the efficiency of CeO2
and the blue green emission at  469 nm is attributed NPs reported by Magesh et al. [35]. The efficiencies of
to oxygen defects [31]. On doping with 3% Co, the emission photocatalytic degradation with 3% Co-doped NPs and with
peaks became redshifted because of the formation of 6% Co-doped CeO2 NPs under UV irradiation for 7 h
more oxygen defects and the conducive conditions for increased (87.1% and 98.7%, respectively). The degradation
Ce3 þ formation [32]. Formation of defect states from the efficiency increased with the increase in Co concentration.
Ce3 þ states localized slightly below the Ce4f conduction Fig. 9 depicts the photodegradation capability of undoped
band leads to a redshift of the band-edge emission. Upon and Co-doped CeO2 NPs under visible irradiation. The
further increasing the Co loading (6%), more oxygen undoped CeO2 NPs exhibited an efficiency of 34.7% under
defects form, and, in turn, reduce the optical emission. visible irradiation, which is similar to that under UV
This process leads to nonradiative recombination, as evi- irradiation. The degradation efficiency of 3% and 6% Co-
denced by the suppression of luminescence of 6% Co- doped CeO2 NPs under visible irradiation improved to 77.1%
doped CeO2 NPs [33]. and 88.9%, respectively which shows the higher photo
catalytic activity as compare to undoped CeO2 NPs. It is
3.4. Analysis of photocatalytic activity noteworthy that Co-doped CeO2 NPs showed a photocata-
lytic response under sunlight. Reduction of the band gap
The UV absorption maximum of MB in the absence of due to doping of CeO2 with Co resulted in improved
catalysts shows is at 662 nm. When CeO2 NPs were used as photocatalytic efficiency under UV illumination and under
photocatalyst under a UV lamp and under sunlight, the sunlight. Doping with Co might have increased the rate of
wavelength of maximum absorption (λ ¼ 662 nm) was charge transport and flow of photogenerated electrons and
observed to gradually decrease (Fig. 7a–f). This decrease holes to the NP surface, thereby increasing the photocata-
reveals that the degradation of aqueous MB was strictly due lytic efficiency.
 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224 223

Fig. 7. UV–vis spectra depicting dye degradation with respect to time in the presence of (a, d) undoped CeO2 NPs, (b, e) 3% Co-doped CeO2 NPs, and (c, f) 6%
Co-doped CeO2 NPs under UV and visible irradiation, respectively.

1.0 a 1.0
b
0.9 c 0.9

0.8 d 0.8

0.7 0.7
a

0.6 0.6
In C/C0

In C/Co

0.5 0.5
0.4 e 0.4
0.3
0.3 b
0.2
0.2
f c
0.1
0.1
0.0
0.0
0 50 100 150 200 250 300 350 400 450
0 50 100 150 200 250 300 350 400 450
Time (min)
Time (min)
Fig. 8. Photocatalytic degradation of MB in the presence of catalytic NPs
Fig. 9. Photocatalytic degradation of MB in the presence of Co-doped
under various conditions: (a) CeO2 NPs in the dark, (b) 3% Co-doped CeO2
CeO2 NPs under various conditions: (a) CeO2 NPs under visible irradia-
NPs in the dark, (c) 6% Co-doped CeO2 NPs in the dark, (d) CeO2 NPs
tion, (b) 3% Co-doped CeO2 NPs under visible irradiation, and (c) 6% Co-
under UV irradiation, (e) 3% Co-doped CeO2 NPs under UV irradiation,
doped CeO2 NPs under visible irradiation.
and (f) 6% Co-doped CeO2 NPs under UV irradiation.

4. Conclusion induced formation of oxygen vacancies. Experiments on

photocatalytic activity showed that Co-doped CeO2 had
Mono dispersed Co-doped CeO2 NPs were successfully higher capability for photocatalytic degradation of MB com-
prepared by a coprecipitation method. The sizes of the NPs pared with that of the pure CeO2 catalyst. Enhancement of
were in the range of 5–12 nm. The band gap of the NPs the photocatalytic degradation efficiency of CeO2 NPs upon
decreased with the increase in Co dopant concentration. Pl Co doping may be due to an increase in the charge transport
spectra showed that increasing the dopant concentration rate. The efficiency of Co-doped CeO2 NPs in catalytic
224 J. Saranya et al. / Materials Science in Semiconductor Processing 26 (2014) 218–224

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