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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 15463–15477
www.elsevier.com/locate/ceramint

Synthesis of TiO2
MgO mixed metal oxide nanoparticles via a sol
gel
method and studies on their optical properties
Nisha Bayal, P. Jeevanandamn
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India

Received 1 April 2014; received in revised form 28 June 2014; accepted 28 June 2014
Available online 5 July 2014

Abstract

TiO2
MgO mixed metal oxide nanoparticles with variable MgO content were prepared by a simple sol
gel method. The nanoparticles were
characterized by power X-ray diffraction, field emission scanning electron microscopy coupled with energy dispersive X-ray analysis,
transmission electron microscopy and UV
visible diffuse reflectance spectroscopy. X-ray diffraction results indicate that the presence of MgO
prevents the complete transformation of anatase to rutile in the TiO2
MgO mixed metal oxide nanoparticles prepared using lower MgO content
even at 900 1C. The presence of MgO in TiO2
MgO nanoparticles suppresses the crystal growth of TiO2 leading to a blue-shift of its band gap.
The TiO2
MgO samples prepared using higher MgO content and calcined at 700 1C and 900 1C lead to mixed metal oxide nanoparticles with
high band gap ( 4.3 eV) due to the formation of MgTiO3.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Optical properties; Mixed metal oxide nanoparticles; Semiconductor nanoparticles; Sol
gel method

1. Introduction
TiO2 nanoparticles have been extensively investigated since
they exhibit interesting optical, electronic and photochemical
properties [1,2]. A number of applications such as photovoltaic
cells, electrochromic materials, photocatalysis and waste water
treatment have become possible using TiO2 nanoparticles
[3–7]. TiO2 is a semiconductor with wide band gap (3.2 eV),
high refractive index, mechanical strength and chemical
stability [8]. Due to this, TiO2 nanoparticles are being used
in pigments, protective coatings, ceramics, catalysis and
antiphoto-corrosion applications [9–12]. TiO2 nanoparticles
possess good absorption in the UV region due to which they
are in high demand as UV blockers and they play an important
role in cosmetics and biomedicine [13–17]. TiO2 is present in
three distinct allotropic phases (anatase, rutile, and brookite)
[18]. Anatase and rutile have been widely investigated for
photocatalysis and photoelectrochemical applications [19,20].
n
Corresponding author. Tel.: þ91 1332 285444; fax: þ 91 1332 273560.
E-mail address: jeevafcy@iitr.ac.in (P. Jeevanandam).
Anatase is more active than rutile since the Fermi level in
anatase is higher than that of rutile by about 0.1 eV. Anatase
also plays an important role in the charge injection process in
photochemical solar cells with high conversion efficiency
[21,22].
Nanocrystalline MgO is an interesting functional material
due to its low heat capacity, chemical inertness, optical
transparency and high thermal stability [23]. MgO nanoparti-
cles are useful in high temperature resistant insulating materi-
als, fuel-oil additives, liquid crystals, electroluminescence
display panels and fluorescence tubes [24–28]. Due to its high
surface area, nanocrystalline MgO is used as an efficient
adsorbent for numerous toxic chemicals (e.g. organopho-
sphorus compounds) and acid gases [29–32]. Researchers
have reported bactericidal activity of MgO nanoparticles and
their halogen adducts [33–35] and MgO nanoparticles act as
catalyst/support in various organic reactions [36–42].
Combining an insulator material (e.g. MgO and Al2O3) with
TiO2 can enhance its photocatalytic performance [43,44]. TiO2
surface modified with MgO or SiO2 shows good degradation
activity for cationic surfactants [43]. For example, Bandara et al.

http://dx.doi.org/10.1016/j.ceramint.2014.06.122
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
15464 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477
have reported that TiO2 coated with MgO enhances the photo-
degradation of eosin by three fold [44]. They have also reported
that the degradation efficiency of TiO2
MgO for chlorophenol is
enhanced four times compared to that of pure TiO2 nanoparticles
[45]. The reason behind the enhanced activity of TiO2
MgO
compared to pure TiO2 is that the MgO layer acts as a barrier for
charge recombination. Liu et al. have investigated the photoreduc-
tion of CO2 with water vapor using TiO2
MgO as a hybrid
adsorbent-photocatalyst [46]. Mguni et al. have demonstrated the
catalytic activity of TiO2
MgO mixed metal oxide nanoparticles
for transesterification of soyabean oil [47]. Dye sensitized solar
cells (DSSCs) based on TiO2 are alternative to silicon due to their
low cost and high efficiency [48,49]. Enhanced efficiency in solar
cells has been achieved by coating a layer of MgO on TiO2. The
MgO layer retards the recombination of electrons and holes and
since MgO is more basic than TiO2, the carboxylic groups of the
organic dyes easily adsorb on the surface thus improving the
efficiency of the dye sensitized solar cells [50,51].
The reported synthetic methods for the preparation of
TiO2
MgO nanoparticles include aerosol method, flame
pyrolysis, a sol–gel method and precipitation-decomposition
[45,52–55]. Wen et al. have synthesized TiO2
MgO mixed
metal oxide nanoparticles via the sol–gel method under helium
atmosphere and the synthesis requires about 40 h [54]. Lopez
et al. have reported that the TiO2
MgO nanoparticles
synthesized by a sol–gel process are a mixture of anatase,
karooite (MgTi2O5), geikielite (MgTiO3) and quadilite
(Mg2TiO4) [55]. Shrestha et al. used an autoclave to attain
supercritical conditions [52]. Kraleva et al. have reported the
synthesis of TiO2
ZrO2 and TiAlZr mixed oxides [56,57].
Mixed TiO2
ZrO2 oxides (3–37 mol% of ZrO2) have been
prepared by the sol–gel method followed by calcination at
different temperatures (e.g. 550 1C, 700 1C). The authors
report that the thermal stability of anatase TiO2 increases in
the presence of 3 to 13 mol% of ZrO2 [56]. The anatase to
rutile transformation is retarded above 700 1C. At 37 mol% of
ZrO2 and calcination at 700 1C, srilankite (Ti0.63Zr0.37Ox) is
obtained. TiAlZr mixed oxide nanoparticles have been synthe-
sized using the sol–gel method and they have been used as
supports for hydrodesulfurization catalysts containing 12 wt%
molybdenum [57]. In the synthesized mixed metal oxides,
there was no formation of a new oxide phase. In the present
study, TiO2
MgO mixed metal oxide nanoparticles have been
synthesized using the sol–gel method. The present method is
relatively simple compared to other reported methods and it
does not require special conditions and leads to homogeneous
TiO2
MgO nanoparticles with good purity. After thorough
characterization, optical properties of the nanoparticles were
investigated.
2. Experimental
The chemicals used were titanium isopropoxide (Sigma-
Aldrichs), magnesium turnings (Sigma-Aldrichs), glacial
acetic acid (Rankem), methanol (Rankem) and Millipores
water. The chemicals were of analytical grade and were used
Table 1
Concentration of reagents used during the synthesis of TiO2
MgO
nanoparticles.
Sl. no. [Ti4 þ : Mg2 þ ]
1. 1:0
2. 1:0.1
3. 1:0.25
4. 1:0.5
5. 1:1
6. 1:2
without further purification. More synthetic details are as
follows.
The concentration of the reagents (titanium isopropoxide
and magnesium methoxide) used during the sol–gel synthesis
of TiO2
MgO nanoparticles are given in Table 1. First,
4.5 mL of titanium isopropoxide was taken in a 250 mL
beaker. Then, 9 mL of glacial acetic acid was added followed
by the addition of 100 mL water dropwise. A transparent sol
was obtained within 15 min. Then, magnesium methoxide
slurry, prepared according to a reported procedure [58], was
added to the above sol with continuous stirring. A light yellow
colored sol was obtained after 5 h. The sol was kept in an oven
at 80 1C for gelation and the gel obtained was then dried at
100 1C to get a powder. The as prepared sample powders were
grounded and subjected to calcination at 500 1C, 700 1C and
900 1C to get TiO2
MgO mixed metal oxide nanoparticles.
X-ray diffraction patterns were recorded with the help of a
Bruker AXS-D8 diffractometer using CuKα radiation
(λ ¼ 1.5406 Å). FE-SEM images and the elemental analysis
were carried out with the help of a FEI Quanta 200F scanning
electron microscope equipped with an energy-dispersive
spectroscopy (EDS) facility operating at an accelerating
voltage of 20 kV. TEM images of the mixed metal oxide
nanoparticles were obtained using a FEI TECNAI G2 trans-
mission electron microscope operating at an accelerating
voltage of 200 kV. Diffuse reflectance spectra were recorded
with the help of a Shimadzu UV-3600 UV–vis–NIR spectro-
photometer using BaSO4 as the reference. Photoluminescence
(PL) spectra were recorded at room temperature with the
help of a Shimadzu RF 3501-PC photoluminescence spectro-
meter. The excitation source was Xe lamp and the excitation
wavelength was 320 nm. For the PL measurements, the
powder samples were well dispersed in methanol by sonication
and the spectra were recorded for the suspensions.
3. Results and discussion
Fig. 1a shows the powder X-ray diffraction patterns of as
prepared TiO2
MgO nanoparticles prepared using different
concentrations of magnesium methoxide and titanium isoprop-
oxide. The XRD patterns indicate the formation of anatase
(JCPDs File no. 84-1286). Fig. 1b shows the XRD patterns
of the TiO2
MgO samples calcined at 500 1C. The XRD
patterns of TiO2
MgO mixed metal oxide nanoparticles prepared
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15465

* anatase
MgO
$

(101)
MgTiO3

(004)

(200)

(105)

(204)
Intensity (arb. units)

Intensity (arb. unit)

4+ 2+
[Ti : Mg ]= 1:0 * * * * * * *
4+ 2+
4+ 2+ [Ti :Mg ] =1:0
[Ti : Mg ]= 1:0.1
4+ 2+
4+ 2+
$ [Ti :Mg ] =1:0.1
[Ti : Mg ]= 1:0.25
4+ 2+
4+ 2+
[Ti :Mg ] =1:0.25
[Ti : Mg ]= 1:0.5 4+ 2+
4+ 2+ [Ti :Mg ] =1:0.5
[Ti : Mg ]= 1:1
4+ 2+
[Ti :Mg ] =1:1
4+ 2+
[Ti : Mg ]= 1:2 4+ 2+
[Ti :Mg ] =1:2

20 40 60 80 20 40 60 80
2θ 2θ

#
* anatase
* rutile * anatase
#
# rutile
^ brookite MgTiO3
MgTiO3
#
Intensity (arb. units)

# * Intensity (arb. units)

*^^^ * ^*^ ^ #
* * *^
#
^ *
4+ 2+
[Ti : Mg ] =1:0 # # #
4+ 2+
[Ti : Mg ] =1:0.1 # ## #
4+ 2+ *
[Ti : Mg ] =1:0.25 4+
[Ti : Mg ]= 1:0
2+

4+ 2+
[Ti : Mg ] =1:0.5 * * ** * 4+ 2+
[Ti : Mg ]= 1:0.1
* 4+ 2+
[Ti : Mg ]= 1:0.25
4+ 2+
4+
[Ti : Mg ] =1:1
2+ [Ti : Mg ]= 1:0.5
4+ 2+
[Ti : Mg ]= 1:1
4+ 2+ 4+
[Ti : Mg ] =1:2 2+
[Ti : Mg ]= 1:2

20 40 60 80 20 40 60 80
2θ 2θ

Fig. 1. XRD patterns of TiO2
MgO samples: (a) as prepared, (b) after calcination at 500 1C, (c) after calcination at 700 1C and (d) after calcination at 900 1C.

Table 2
Crystallite size and band gap values of metal oxides in TiO2
MgO nanoparticles calcined at different temperatures.

[Ti4 þ : Mg2 þ ] 500 1C 700 1C 900 1C

Crystallite size (nm) Band gap (eV) Crystallite size (nm) Band gap (eV) Crystallite size (nm) Band gap (eV)
a a r a r
MgO TiO2 MgTiO3 TiO2 TiO2 MgTiO3 TiO2 TiO2 MgTiO3

1:0 – 9.5 – 3.29 35.1 58.9 – 3.03, 3.74 – 67.6 – 2.98

1:0.1 – 5.6 – 3.31 20.9 25.8 – 3.06 36.2 58.6 – 2.93, 3.45
1:0.25 – 6.9 – 3.35 19 22 – 3.25 34.5 52.7 – 2.53
1:0.5 7.8 6.9 – 3.33 12.3 10.2 – 3.11 32.3 46.9 – 2.97, 3.30
1:1 7.6 4.5 – 3.42 – – 23.8 4.31 – – 29.4 4.18
1:2 11.15 – – 3.65 – – 27.7 4.32 – – 34.5 4.30

a- anatase, r- rutile.

using higher magnesium content (e.g. [Ti4 þ :Mg2 þ ]¼ 1:2, 1:1 and also the fact that MgO is well dispersed on TiO2. One can
1:0.5) show peaks both due to anatase TiO2 and MgO. notice two additional peaks at 2θ ¼ 33.051 and 56.751 in the
However, the XRD patterns of TiO2
MgO nanoparticles TiO2
MgO nanoparticles prepared using higher magnesium
prepared using lower concentration of magnesium methoxide content ([Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1) which can be indexed to
([Ti4 þ :Mg2 þ ]¼ 1:0.25 and 1:0.1) show peaks due to only MgTiO3 (JCPDS File no. 79-0831). Fig. 1c shows the XRD
anatase. The reason for the absence of MgO peaks in these patterns of TiO2
MgO mixed metal oxide nanoparticles
samples is attributed to the presence of low MgO content and calcined at 700 1C. The samples prepared using higher
15466 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477

magnesium content ([Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1) show peaks
only due to MgTiO3. In the TiO2
MgO samples prepared
using lower magnesium content ([Ti4 þ :Mg2 þ ]¼ 1:0.25 and
1:0.1), the XRD peaks due to anatase are intense.
On further increase in the calcination temperature to 900 1C,
complete transformation of anatase to rutile occurs in the case
of pure TiO2 (Fig. 1d). In the XRD patterns of TiO2
MgO
nanoparticles, prepared using higher magnesium content
([Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1), the XRD peaks are attributed
to MgTiO3. In the samples prepared using lower MgO content
([Ti4 þ :Mg2 þ ] ¼ 1:0.5, 1:0.25 and 1:0.1) and after calcination
at 900 1C, the XRD patterns indicate the presence of both

[Ti4+:Mg2+]= 1: 2 [Ti4+:Mg2+]= 1: 1

[Ti4+:Mg2+]= 1: 0.5 [Ti4+:Mg2+]= 1: 0.25

[Ti4+:Mg2+]= 1: 0.1

Fig. 2. FE-SEM images of TiO2
MgO nanoparticles synthesized using different [Ti4 þ :Mg2 þ ] molar ratios followed by calcination at 700 1C.
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15467

anatase and rutile. The peaks due to anatase are more
prominent compared to that of rutile in the sample prepared
using [Ti4 þ :Mg2 þ ]¼ 1:0.5. From the XRD results on
TiO2
MgO mixed metal oxide nanoparticles, it can be
concluded that the presence of MgO prevents the complete
transformation of anatase to rutile in the mixed metal oxide
nanoparticles prepared using lower magnesium oxide content
([Ti4 þ :Mg2 þ ] ¼ 1:0.5, 1:0.25 and 1:0.1) even at 900 1C.
The crystallite size of MgO and TiO2 in the TiO2
MgO
nanoparticles was calculated using Debye Scherrer formula
and the results are shown in Table 2. In general, the crystallite
size of pure TiO2 is higher than that in the TiO2
MgO mixed

[Ti4+:Mg2+]= 1: 2 [Ti4+:Mg2+]= 1: 1

[Ti4+:Mg2+]= 1: 0.5 [Ti4+:Mg2+]= 1: 0.25

[Ti4+:Mg2+]= 1: 0.1

Fig. 3. FE-SEM images of TiO2
MgO nanoparticles synthesized using different [Ti4 þ :Mg2 þ ] molar ratios followed by calcination at 900 1C.
15468 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477
metal oxide nanoparticles. The crystallite size of TiO2 in the
mixed metal oxide nanoparticles calcined at 500 1C is in the
range 4.5 to 6.9 nm. Increasing the calcination temperature to
700 1C leads to an increase in the crystallite size. For anatase
phase, it varies from 12.3 nm to 20.9 nm whereas for rutile
phase, it varies from 10.2 nm to 25.8 nm. After calcination at
900 1C, the crystallite size of anatase phase varies from
32.3 nm to 36.2 nm and the crystallite size for the rutile phase
varies from 46.9 nm to 58.6 nm. It has been reported in the
literature that pure anatase nanoparticles with a diameter of
6–30 nm are stable; as the particle size exceeds 30 nm, anatase
transforms to rutile [59]. It is well known that rutile is thermo-
dynamically more stable than anatase and surface energy plays
a key role in the phase transformation [60].
The FE-SEM images of as prepared TiO2
MgO samples
showed agglomerates of small spherical particles. The
FE-SEM micrographs of TiO2
MgO mixed metal oxide
nanoparticles calcined at 500 1C also showed spherical parti-
cles. The FE-SEM micrographs of TiO2
MgO nanoparticles
calcined at 700 1C are shown in Fig. 2. The samples prepared
using [Ti4 þ :Mg2 þ ]¼ 1:2 and 1:1 display dumb-bell shaped
particles. The FE-SEM images of TiO2
MgO nanoparticles
prepared using [Ti4 þ :Mg2 þ ] ¼ 1:0.5, 1:0.25 and 1:0.1 show
two types of particles. First ones are the clusters of small
spherical particles and the second ones are the large agglo-
merated irregular particles. The presence of two types
of particles in the SEM images is attributed to the presence
of rutile and anatase together. The FE-SEM images of
TiO2
MgO samples after calcination at 900 1C are shown
in Fig. 3. The samples show large, irregular and highly
agglomerated particles. The Ti/Mg atomic percent ratios, as
observed by EDX analysis in the TiO2
MgO samples, have
been summarized in Table 3. In general, the observed Ti/Mg
ratio is close to that of titanium isopropoxide and magnesium
methoxide used during the synthesis. In the TiO2
MgO
sample, prepared using [Ti4 þ :Mg2 þ ]¼ 1:2, the elemental
distribution was inhomogeneous. The sample synthesized
using [Ti4 þ :Mg2 þ ]¼ 1:1 showed the best homogeneity com-
pared to all the other TiO2
MgO samples.
TEM measurements were carried out for the TiO2
MgO
samples calcined at two different temperatures (500 1C and
900 1C) and the results are shown in Figs. 4 and 5, respec-
tively. The TEM images of TiO2
MgO nanoparticles and
pure TiO2 nanoparticles after calcination at 500 1C indicate
Table 3
EDX analysis data for TiO2
MgO mixed metal oxide nanoparticles.
[Ti4 þ : Mg2 þ ] ratio used to prepare the Observed Ti/Mg ratio
mixed metal oxide nanoparticles
Calcination temperature¼ 500 1C
1:0.1 11.14
1:0.25 4.46
1:0.5 2.30
1:1 1.02
1:2 0.78
that the particles (close to spherical) are in nanometer range.
The mean particle size for pure TiO2 nanoparticles is
13.57 3.4 nm. The mean particle size of TiO2
MgO nano-
particles varies from 6.67 1.7 nm ([Ti4 þ :Mg2 þ ]=1:2) to
11.07 2.3 nm ([Ti4 þ :Mg2 þ ]=1:0.1). The TEM micrographs
for the samples calcined at 900 1C show large particles with
irregular morphology (Fig. 5). Fig. 6 shows the electron
diffraction patterns of pure TiO2 and TiO2
MgO nanoparti-
cles after calcination at 500 1C. The SAED patterns show a
series of rings and the rings observed in pure TiO2 were
indexed to anatase. The rings in the SAED pattern
of TiO2
MgO prepared using higher MgO content (e.g.
[Ti4 þ :Mg2 þ ] ¼ 1:2) correspond to the reflections of MgTiO3.
The rings in the SAED patterns of TiO2
MgO samples
prepared using lower MgO content ([Ti4 þ :Mg2 þ ]¼ 1:0.5,
1:0.25 and 1:0.1) are attributed to anatase. The SAED results
are in good agreement with the results obtained from the XRD
measurements (Fig. 1b).
The optical properties of pure TiO2 and TiO2
MgO mixed
metal oxide nanoparticles were investigated using diffuse
reflectance spectroscopy (DRS). Figs. 7a, b and c show the
DRS spectra of TiO2
MgO nanoparticles calcined at 500 1C,
700 1C and 900 1C, respectively. The diffuse reflectance
spectra of pure TiO2 and all the TiO2
MgO nanoparticles
calcined at 500 1C show band gap absorption in the range
325
340 nm which is characteristic of anatase TiO2.
After calcination at 700 1C, the DRS spectra of TiO2
MgO
nanoparticles prepared using lower magnesium content ([Ti4 þ :
Mg2 þ ]¼ 1.0.5, 1:0.25 and 1:0.1) show absorption in the range
325
340 nm. The mixed metal oxide nanoparticles prepared
using higher magnesium content ([Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1)
absorb in the shorter wavelength region (270
290 nm) due to
the formation of MgTiO3.
The band gap (Eg) values for pure TiO2 and TiO2
MgO
nanoparticles were estimated using the Tauc equation for direct
band gap semiconductors using the diffuse reflectance data
[61]. By extrapolating the linear portion of the (αhν)2 versus
hν curves to the X-axis, the Eg values were estimated.
The estimated band gap for pure TiO2 nanoparticles is
3.29 eV and the band gap values for pure TiO2 and the
TiO2
MgO mixed metal oxide nanoparticles estimated using
the Tauc equation are given in Table 2. The band gap of the
TiO2
MgO mixed metal oxide nanoparticles calcined at
500 1C varies from 3.65 eV to 3.31 eV (Fig. 8) and the
Calcination temperature ¼700 1C Calcination temperature¼ 900 1C
8.20 9.40
3.70 4.00
1.96 1.45
1.07 0.89
0.65 0.58
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15469

[Ti4+:Mg2+]= 1: 0 [Ti4+:Mg2+]= 1: 2

[Ti4+:Mg2+]= 1: 1 [Ti4+:Mg2+]= 1: 0.5

[Ti4+:Mg2+]= 1: 0.25 [Ti4+:Mg2+]= 1: 0.1

Fig. 4. TEM images of TiO2
MgO nanoparticles synthesized using different [Ti4 þ :Mg2 þ ] molar ratios. The samples are calcined at 500 1C.
15470 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477

[Ti4+:Mg2+]= 1: 0 [Ti4+:Mg2+]= 1: 2

[Ti4+:Mg2+]= 1: 1 [Ti4+:Mg2+]= 1: 0.5

[Ti4+:Mg2+]= 1: 0.25 [Ti4+:Mg2+]= 1: 0.1

Fig. 5. TEM images of TiO2
MgO nanoparticles synthesized using different [Ti4 þ :Mg2 þ ] molar ratios. The samples are calcined at 900 1C.
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15471

Fig. 6. SAED patterns of TiO2–MgO nanoparticles calcined at 500 1C: (a) [Ti4 þ :Mg2 þ ]¼ 1:0, (b) [Ti4 þ :Mg2 þ ] ¼1:2, (c) [Ti4 þ :Mg2 þ ]¼ 1:1, (d) [Ti4 þ :Mg2 þ ]¼
1:0.5, (e) [Ti4 þ :Mg2 þ ]¼ 1:0.25 and (f) [Ti4 þ :Mg2 þ ]¼ 1:0.1.
15472 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477

% Reflectance (arb. unit)

% Reflectance (arb. units)

4+ 2+
[Ti :Mg ] =1:0
4+ 2+
[Ti :Mg ]=1:0 4+ 2+
[Ti :Mg ] =1:2
4+ 2+
[Ti :Mg ]=1:2 4+ 2+
4+ 2+ [Ti :Mg ] =1:1
[Ti :Mg ]=1:1
4+ 2+
4+ 2+
[Ti :Mg ]=1:0.5 [Ti :Mg ] =1:0.5
4+ 2+ 4+ 2+
[Ti :Mg ]=1:0.25 [Ti :Mg ] =1:0.25
4+ 2+ 4+ 2+
[Ti :Mg ]=1:0.1 [Ti :Mg ] =1:0.1

200 300 400 500 600 200 300 400 500 600
Wavelength (nm) Wavelength (nm)
% Reflectance (arb. units)

4+ 2+
[Ti :Mg ]=1:0
4+ 2+
[Ti :Mg ]=1:2
4+ 2+
[Ti :Mg ]=1:1
4+ 2+
[Ti :Mg ]=1:0.5
4+ 2+
[Ti :Mg ]=1:0.25
4+ 2+
[Ti :Mg ]=1:0.1

250 300 350 400 450 500

Wavelength (nm)

Fig. 7. Diffuse reflectance spectra of TiO2
MgO nanoparticles: (a) after calcination at 500 1C, (b) after calcination at 700 1C and (c) after calcination at 900 1C.

observed band gap is due to anatase, as indicated by the XRD 3.25 eV and 3.06 eV, respectively due to anatase. Fig. 10
results (Fig. 1b). The TiO2
MgO mixed metal oxide nano- displays the Tauc plots for TiO2
MgO mixed metal oxide
particles prepared using [Ti4 þ :Mg2 þ ]¼ 1:2 show the highest nanoparticles calcined at 900 1C. The samples prepared
band gap (3.65 eV) and the sample prepared using [Ti4 þ : using [Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1 show similar results as that
Mg2 þ ]¼ 1:0.1 possesses the lowest band gap (3.31 eV). The reported for the samples calcined at 700 1C. The samples
TEM results reveal that the particle size of the TiO2
MgO prepared using lower MgO content, i.e. [Ti4 þ :Mg2 þ ]¼ 1:0.5
mixed metal oxide nanoparticles prepared using [Ti4 þ : and 1:0.1 show two band gap absorptions. TiO2
MgO
Mg2 þ ]¼ 1:2 is smaller (  6.6 nm) compared to that of the ([Ti4 þ :Mg2 þ ] ¼ 1:0.5) possesses one absorption at 2.97 eV
sample prepared using [Ti4 þ :Mg2 þ ] ¼ 1:0.1 ( 11 nm). The and another one at 3.30 eV (see the inset of Fig. 10d) due
presence of MgO suppresses the crystal growth of TiO2 to rutile and anatase phases of TiO2, respectively. Similarly,
because MgO nucleates as a second phase and migrates to TiO2
MgO ([Ti4 þ :Mg2 þ ] ¼ 1:0.1) possesses band gap
the surface of TiO2 due to which higher MgO content leads to absorptions at 2.93 eV (rutile) and 3.45 eV (anatase). The
the formation of smaller particle size of TiO2. Thus higher DRS results are in good agreement with the results obtained
MgO content in the TiO2
MgO samples lead to blue-shift of from the XRD analysis.
band gap of TiO2. In the literature, blue-shift of the band gap of TiO2 when it is
The Tauc plots of TiO2
MgO samples after calcination at coupled with different insulators such as SiO2, Al2O3, In2O3,
700 1C are shown in Fig. 9. The samples prepared using higher etc. has been reported [50,63–65]. Kumar et al. have reported a
MgO content (e.g. [Ti4 þ :Mg2 þ ] ¼ 1:2 and 1:1) show high Eg band gap of 3.8 eV for TiO2
SiO2 [50]. Similarly, Lassaletta
( 4.3 eV). This is due to the formation of MgTiO3 as evident et al. have reported a band gap of 4.1 eV for TiO2
SiO2 [63].
from the XRD results (Fig. 1c). Santosh Kumar and co- Recently, Laha et al. have reported a band gap of 3.6 eV for
workers have reported a band gap of around 4.18 eV for TiO2
Al2O3 [64]. Poznyak et al. have reported a blue-shift of
MgTiO3 [62]. The TiO2
MgO samples prepared using lower the band gap of TiO2 in TiO2
In2O3 mixed metal oxide
magnesium content ([Ti4 þ :Mg2 þ ]¼ 1:0.5, 1:0.25 and 1:0.1) nanoparticles [65]. In the present study, the TiO2
MgO
and calcined at 700 1C possess band gap values of 3.11 eV, mixed metal oxide nanoparticles show a blue-shift of band
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15473

(αhυ)2 (a. u.)

(αhυ)2(a. u.)
3.29 eV
3.65 eV

2.50 2.75 3.00 3.25 3.50 3.75 4.00 3.00 3.25 3.50 3.75 4.00 4.25 4.50
hυ (eV) hυ (eV)
(αhν)2 (a.u)

(αhν)2 (a.u)

3.33 eV
3.42 eV

3.00 3.25 3.50 3.75 4.00 4.25 4.50 3.00 3.25 3.50 3.75 4.00
hυ (eV) hυ (eV)
(αhν)2 (a.u)

(αhν)2 (a.u)

3.35 eV 3.31 eV

3.00 3.25 3.50 3.75 4.00 3.00 3.25 3.50 3.75

hυ (eV) hυ (eV)

Fig. 8. Tauc plots of TiO2
MgO nanoparticles calcined at 500 1C: (a) [Ti4 þ :Mg2 þ ]¼ 1:0, (b) [Ti4 þ :Mg2 þ ]¼ 1:2, (c) [Ti4 þ :Mg2 þ ] ¼1:1, (d) [Ti4 þ :Mg2 þ ]¼
1:0.5, (e) [Ti4 þ :Mg2 þ ]¼ 1:0.25 and (f) [Ti4 þ :Mg2 þ ]¼ 1:0.1.

gap of TiO2 compared to that of pure TiO2 nanoparticles at
different calcination temperatures.
Fig. 11 shows the photoluminescence spectra of TiO2

MgO mixed metal oxide nanoparticles calcined at different
temperatures along with pure TiO2 nanoparticles. The PL
studies were carried out with an excitation wavelength of
320 nm using methanol as the solvent. The emission band
observed at 360 nm in all the samples is attributed to direct
band-to-band transition [66]. The visible emission bands in the
range of 400–500 nm are associated with excitons, surface
defects and oxygen vacancies. The emission band at 450 nm is
due to self trapped excitons and the band at 470 nm is
associated with oxygen defects [67]. The emission band at
494 nm is attributed to the charge transfer transition from Ti3 þ
to O2
in TiO6 octahedra. Alves de Castro et al. have reported
an emission band at 373 nm in TiO2
WO3 heterostructures
15474 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477

(αhν) (a. u.)

(αhυ) (a. u.)

2

2
3.03 eV 4.32 eV
3.74 eV

2 3 4 5 6 4.00 4.25 4.50 4.75

h υ (eV ) hυ (eV)

(αhν) (a.u)
(α hν) (a. u.)

2
2

3.11 eV
4.31 eV

4.00 4.25 4.50 2.50 2.75 3.00 3.25 3.50 3.75 4.00
hυ (eV) hυ (eV)
(αhν) (a.u.)
(αhν) (a.u)
2

3.06 eV
3.25 eV

2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50 2.50 2.75 3.00 3.25 3.50 3.75
hυ (eV) hυ (eV)

Fig. 9. Tauc plots of TiO2
MgO nanoparticles calcined at 700 1C: (a) [Ti4 þ :Mg2 þ ]¼ 1:0, (b) [Ti4 þ :Mg2 þ ]¼1:2, (c) [Ti4 þ :Mg2 þ ] ¼1:1, (d) [Ti4 þ :Mg2 þ ]¼
1:0.5, (e) [Ti4 þ :Mg2 þ ]¼1:0.25 and (f) [Ti4 þ :Mg2 þ ]¼ 1:0.1.

[68] and Hu et al. have reported an emission band for TiO2 at
393 nm in TiO2
SiO2 nanoparticles [69].
4. Conclusions
Synthesis of TiO2
MgO nanoparticles with different of
magnesium contents has been carried out using a simple sol–
gel method. The effects of calcination temperature and the
molar ratio of titanium to magnesium on the phase transforma-
tion of anatase to rutile have been investigated. The presence
of MgO prevents the complete transformation of anatase
to rutile even at 900 1C. Higher magnesium oxide content
facilitates the formation of spinel (MgTiO3). At lower MgO
content, both the anatase and rutile phases remain separate.
The optical properties of TiO2
MgO nanoparticles with
different compositions were investigated and it was found that
 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477 15475

(αhν) (a. u.)

(αhν) (a.u)
2
2

2.98 eV 4.30 eV

2 3 4 4.00 4. 25 4.5 0
h υ (eV) hυ (eV)

(αhν) (a.u)
(αhν) (a.u)

2
2

2.97 eV
4.18 eV

4.00 4.2 5 4. 50 2.5 3.0 3.5 4.0

hυ (eV) hυ (eV)

Fig. 10. Tauc plots of TiO2
MgO nanoparticles calcined at 900 1C: (a) [Ti4 þ :Mg2 þ ] ¼1:0, (b) [Ti4 þ :Mg2 þ ]¼ 1:2, (c) [Ti4 þ :Mg2 þ ] ¼1:1, (d) [Ti4 þ :Mg2 þ ]¼
1:0.5.

Fig. 11. Photoluminescence spectra of TiO2
MgO samples: (a) after calcination at 500 1C, (b) after calcination at 700 1C and (c) after calcination at 900 1C.
15476 N. Bayal, P. Jeevanandam / Ceramics International 40 (2014) 15463–15477
the TiO2 in the mixed metal oxide nanoparticles calcined
at different temperatures show a blue-shift of the band gap
compared to the pure TiO2 nanoparticles. The samples
prepared using higher MgO content (e.g. [Ti4 þ :Mg2 þ ]¼ 1:2
and 1:1) and calcined at high temperature (e.g. 700 1C and
900 1C) lead to mixed metal oxide nanoparticles with high
band gap (e.g.  4.3 eV) due to the formation of MgTiO3. The
perspective applications of the synthesized materials include
photocatalysis (e.g. reduction of CO2, degradation of CH3
CHO, dye degradation, etc), dye sensitized solar cells, nano-
fluids with high thermal conductivity, heavy metal ions
removal, textiles for decontamination and protection and
adsorption and oxidation of asphaltenes in fuels.
Acknowledgment
The award of research fellowship (JRF/SRF) to Ms. Nisha
Bayal by the Council of Scientific and Industrial Research,
Government of India is gratefully acknowledged. Thanks are
due to the Institute Instrumentation Centre, IIT Roorkee for
providing the facilities.
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