Article

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Nanoscience and Nanotechnology
All rights reserved Vol. 16, 7635–7641, 2016
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Synthesis of Geikielite (MgTiO3 ) Nanoparticles via

Sol–Gel Method and Studies on Their
Structural and Optical Properties
R. Rajesh Kanna, N. R. Dhineshbabu, P. Paramasivam, V. Rajendran∗ , and R. Yuvakkumar
Centre for Nanoscience and Technology, K. S. Rangasamy College of Technology, Tiruchengode 637215, Tamil Nadu, India

The geikielite (MgTiO3 ) ceramic nanoparticles with different compositions were synthesized by sol–
gel method (termed as MT00, MT37, MT55, MT73, and MT100). The structural properties and
average crystallite size were analysed. The results of Fourier transform infrared spectra for geikielite
nanoparticles showed the presence of functional groups of –O–Ti–O–Mg–O–. The specific surface
area of prepared nanoparticles surface area analyzer, which varied from 99 to 142 m2 g−1 for dif-
ferent compositions. The geikielite nanoparticles were transparent in the visible spectra region and
revealed a sharp absorption edges at different wavelengths between 363 and 376 nm. The energy
bandgap values of the nanostructured geikielites were investigated from the observed wavelength
(i.e., from 3.38 to 3.53 eV). From the above observation, it can be concluded that the geikielite
nanoparticles are the potential candidate for technological applications like dye synthesis solar cells
and textiles for production.
Keywords: Geikielite Nanoparticles, Sol–Gel Process, Optical Bandgap.

1. INTRODUCTION geikielite nanoparticles using different synthesis methods,

In recent years, nanomaterials with different structure,
morphology, and properties are developed for technolog-
ical applications such as microwave engineering, opti-
cal waveguide, superconductor, filter, and resonators with
cost-effective methods.1–7 The ceramic nanomaterials, i.e.,
PbTiO3 , SrTiO3 , BaTiO3 , FeTiO3 , CaTiO3 , and MgTiO3
are used in a wide range of technical applications such
as dielectric, pyroelectric, ferroelectric, piezoelectric, and
optoelectronic.8–13 Besides, the non-carbonaceous resistiv-
ity of MgTiO3 (geikielite) shows that it normally arises
in mantle derivative rocks that have rhombohedral crystal
structure with low dielectric constant and excellent optical
properties.13
14
Geikielite is an important material because of its mor-
phology and its structure, which is used in different
applications such as solar cells, fuel cells, and electro-
chemical capacitors.15
16 It is a lead-free ceramic material
having characteristics similar to BaTiO3 , and BiNaTiO3
causes lesser atmosphere degradation and is less toxic
to humans.17
18 Attempts have been made to prepare
∗
Author to whom correspondence should be addressed.
such as solid-state reaction, thermal decomposition, and
mechanochemical methods.19
20 Nevertheless, these meth-
ods have few drawbacks such as long processing time, high
temperature, contamination through impurities, and non-
uniform particle size. One can overcome these issues by
using wet chemical method, which is cost effective, also.14
Basically, TiO2 containing perovskite acts as a covering
layer of a second perovskite, which improves its optical
and electronic properties.21
In this study, different concentrations of geikielite
nanoparticles were prepared separately by wet chemical
method. Then, the properties of MgO, TiO2 , and MgTiO3
nanoparticles were studied through different characteri-
zation methods. The optical properties of the prepared
ceramic materials were explored to evaluate their use in
different energy applications such as capacitor and optical
waveguide.
2. EXPERIMENTAL DETAILS
2.1. Materials
In this study, chemicals such as magnesium nitrate
(Mg (NO3 2 · 6H2 O, 99%), titanium isopropoxide

J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 7 1533-4880/2016/16/7635/007 doi:10.1166/jnn.2016.11114 7635

Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies Kanna et al.

(Ti[OCH(CH3 2 ]4 , 97%), ammonia hydroxide (NH4 OH, Table I. Preparation of different synthesized nanoparticles.
99%), ethanol (EtOH, 99.9%), all from Merck, and double- Sample MgO:TiO2 Mg (NO3 )2 Ti [OCH(CH3 )2 ]4 Reducing agent
distilled water were used without further purification. code weight ratio (g) (mL) NH4 OH (mL)

MT00 0–100 0.00 20 10

2.2. Preparation of Geikielite (MgTiO3 ) Nanoparticles MT37 30–70 2.15 14 10
MgTiO3 nanoparticles were synthesized by wet chemical MT55 50–50 3.58 10 10
method. In this process, Mg(NO3 2 and Ti[OCH(CH3 2 ]4 MT73 70–30 5.02 06 10
were used as source materials. Initially, both were dis- MT100 100–0 7.16 00 10
solved in deionized water and EtOH under stirring con-
dition. Then, Ti[OCH(CH3 2 ]4 solution was gently mixed a current rating (30 mA) in the scan range from 10 to
with Mg(NO3 2 solution at room temperature. NH4 OH was 80 . Fourier transform infrared spectra of the nanoparti-
added drop-wise in the prepared solution while stirring for cles were recorded (Spectrum 100; Perkin Elmer, USA)
12 h at ambient temperature. The formed gel was washed using the spectral range of 4000–400 cm−1 using KBr pel-
three times with deionized water and once with EtOH. The let method with a consistent mixture of sample and KBr at
obtained precipitate was dried in a hot-air oven at 120  C the ratio of 1:100. The specific surface area (SSA) of the
for 7 h. Then, the obtained white powder was calcinated nanoparticles was obtained through Brunauer–Emmett–
at 400  C for 3 h. The preparation of MgTiO3 nanopar- Teller (BET) analysis (Autosorb AS-1MP; Quantachrome,
ticle is shown in Figure 1. Using the earlier-mentioned USA) under N2 atmosphere. The geometrical relationship
procedure, MgTiO3 nanoparticles were prepared with five between particle diameter and surface area was used to
concentrations (MgO:TiO2 , namely 0:100, 30:70, 50:50, evaluate the particle size of the prepared sample using the
70:30, and 100:0. equation22
Hereafter, the different concentrations of the prepared 6000
D= (1)
MgTiO3 nanoparticles are termed as MT00, MT37, MT55, s
MT73, and MT100. The composition of the MgTiO3 where s is SSA, D the particle diameter (in nm), and  the-
nanoparticles is given in Table I. oretical density of the material. The surface morphology
of the nanoparticles was analyzed using scanning electron
2.3. Characterization microscope equipped with energy-dispersive spectroscopy
The structural analysis of the nanoparticles was carried (SEM-EDS; JSM-6390LV; JEOL, Japan). The particle size
out using X-ray diffractometer (X’Pert PRO; PAN Ana- and morphologies was performed through transmission
lytical, the Netherlands), using CuK as radiation source electron microscopy along with a selected area electron
( = 1.54060 Å) with a constant voltage (40 kV) and diffraction (SAED) patternTEM; JEM-2100F;JEOL) oper-
ated at 200 kV.
The diffuse reflectance spectrum of the nanoparti-
cles was obtained using UV-2450 spectrophotometer
(Shimadzu, USA). The absorption spectra were recorded
using UV-VIS absorption spectrometer in the range from
200 to 800 nm. The direct and indirect bandgap energy
values of transition metal oxide were determined using the
Tauc equation23 which was related to the photon energy
and absorbance as:

hv ∝ hv − Egap n (2)

hc
E= (3)

where  is the absorbance, h the Planck constant, v the
frequency, Egap the optical bandgap energy,  the wave-
length, E the energy, c speed of light, and n the constant
related to the different types of electronic transitions.
All the prepared powder samples were characterized
using the earlier-mentioned techniques.

3. RESULTS AND DISCUSSION

The X-ray diffraction (XRD) patterns of different metal
Figure 1. Synthesis process of MgTiO3 . oxide nanoparticles (i.e., MT00, MT37, MT55, MT73,

7636 J. Nanosci. Nanotechnol. 16, 7635–7641, 2016

Kanna et al. Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies

and MT100) are shown in Figure 2. In all the pre- Table II. XRD and SEM detail of prepared nanoparticles.
pared nanoparticles, the peaks observed at 2 value differ Sample Crystallite JCPDS Surface Primary particle
from each other. The diffraction peaks of the pure and code size (nm) file no. morphology size (nm)
composite nanoparticles are matched with their respec- MT00 8 39 21–1272 spherical 13
tive JCPDS files, which are listed in Table II. From the MT37 17 1 06–0494 spherical 18
observed results, it is found that the combination of both MT55 12 17 06–0494 spherical 14
cubic (MT100) and anatase (MT00) phases existed as MT73 10 5 06–0494 spherical 13
MT100 16 09 45–0946 spherical 15
MT37, MT55, and MT73 composites14 at same temper-
ature (400  C). The mixer of MgO and TiO2 nanoparti-
cles as a crystalline phase is existed in MT37, MT55 and
MT73 (Fig. 2) which is related in earlier studies.24–27 The low-wavenumber of wide bands is visible in the range of
observed results indicate that the all (MT37, MT55 and 400–900 cm−1 .14
26
MT73) diffraction peaks might be guided to the rhombo- In MT37, the formation of a broad band which is related
hedral structure as referred in JCPDS No. 06-0494.27 The to the characteristic of observed pure titania. The less
average crystallite size of all samples is given in Table II. intense of titania to magnesia ratio increase which is con-
The FTIR spectra of the pure and composite nanopar- siderable in the high-energy bands due to the vibration
ticles are shown in Figure 3. The spectra of MT55 com- hydroxyl groups.14 On the other hand, a set of vibrating
posite are discussed followed by the other samples. The stretch bands (449–590 cm−1  can be seen at the middle
peak observed at 1639 cm−1 is attributed to OH bend- compositions of Ti (Fig. 3). These peaks are ascribed to the
ing vibration band, from the remaining water molecule. formation of metal-oxygen bonds of Ti–O–Mg–O (MT37,
The strong symmetric and sharp asymmetric C–H flex- MT55 and MT73) within the structure, and are in good
ion bonds appear at 1448 and 1384 cm−1 , respectively. agreement with XRD data. The wide vibration band of
The set of bands observed at 482 and 426 cm−1 are due MT73 are observed from 44922 to 820 cm−1 14 (for MgO)
to the bending modes of –O–Ti–O–Mg–O–. It is evi- at 400  C.
dent that titania is irradiated in infrared light, hence, the

Figure 2. XRD of prepared MT00, MT37, MT55, MT73 and MT100 Figure 3. FT-IR Spectra of prepared MT00, MT37, MT55, MT73 and
nanoparticles. MT100 nanoparticles.

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Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies Kanna et al.

Table III. BET analysis of prepared nanoparticles. band related to pure titania when the sample is heated the
Sample Specific surface Total pore Average pore C–H bonds disappears rapidly.27 The content of magne-
code area (m2 g−1 ) volume (ccg−1 ) diameter (nm) sia increases when the C–H flexion bonds are deformed
at 1386 cm−1 , producing water molecules at 1639 cm−1 in
MT00 149 1 0 0740 1 989
MT37 112 5 0 0559 1 985
the form of bending vibration, and the set of band between
MT55 99 93 0 0493 1 976 400 and 900 cm−1 (426, 560, 677, and 838 cm−1 ) indicates
MT73 142 4 0 0705 1 928 the occurrence of Mg–O vibration at MT100.28 Hence, the
MT100 198 6 0 0998 2 010 individual solid ion (Ti and Mg) networks are vibrated and
the spectral band is observed at lower energies due to the
ion weights.
The main difference between rich-end titania and rich- The observation of SSA is listed in Table III. It is found
end magnesia related to MT55 can be explained as follows: that MT100 nanoparticles have high SSA compared to
the titania content increases where OH stretching vibra- the other nanoparticles such as MT37, MT55, and MT73.
tion modes fade away and the shape of a broad strong The SSA of the pure nanoparticle TiO2 (MT00)29 and

Figure 4. SEM Image of the prepared MT100, MT37, MT55, MT73 and MT00 nanoparticles.

7638 J. Nanosci. Nanotechnol. 16, 7635–7641, 2016

Kanna et al. Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies

MgO (MT100) nanoparticle is 149.1 and 198.6 m2 g−1 ,
respectively. However, the SSA of composite nanoparti-
cles (MT37, MT55, and MT73) is less than that of the
pure nanoparticles as listed in Table III. Hence, The above
large variation of SSA and the average pore diameters as a
function of TiO2 :MgO ratio shows that the textural prop-
erties of mixed oxides depend essentially on the relative
concentration of their components. Figure 4 show that the
MT00, MT37, MT55, MT73, and MT100 nanoparticles
are compact and spherical. The primary particle size and
morphology are also obtained from TEM image, as shown
in Figure 5. It is observed that all nanoparticles have same
morphology and size, which is also given in Table II.
The insert of the SAED pattern on Figure 5 shows the
synthesized of all nanoparticles (MT100, MT37, MT55,
MT73, and MT00). This pattern shows the diffraction pat-
tern from an assembly of nanocrystallites which is evident
from XRD.
UV spectrometer is measured to the optical absorp-
tion of all nanoparticles for bandgap energy (Eg ) calcula-
tion and extrapolated from the wavelength axis, as shown
in Figure 6. This absorption edge is found so that the
type of transition and bandgap value of the all synthe-
sized nanoparticles can be determined. The absorption val-
ues of all synthesized nanoparticles are 382 (MT00), 371
(MT37), 363 (MT55), 376 (MT73), and 255 (MT100)
nm, respectively (Fig. 6(a)). The calculation of bandgap
for pure TiO2 (MT00) nanoparticles is 3.30 eV and the
bandgap values for pure MgO (MT100) and TiO2 –MgO
(MT37, MT55, MT73) composite nanoparticles estimated

Figure 5. TEM Image of the prepared MT100, MT37, MT55, MT73 and MT00 nanoparticles insert of SAED pattern.

J. Nanosci. Nanotechnol. 16, 7635–7641, 2016 7639

Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies Kanna et al.

Figure 6. UV Spectrum of prepared nanoparticles.

by the Tauc equation are given in Table IV. Figure 6(b) that the combination of TiO2 (MT00) and MgO (MT100)
shows the direct bandgap of transition plot [(Ephot 2 vs. nanoparticles leads to an increase in bandgap energy value
Ephot ] and the indirect bandgap transition plot (1/2 vs. by increasing concentration of TiO2 . The obtained mixture
Ephot , as shown in Figure 6(c). The direct transition graph of both nanoparticles (MT55) shows the bandgap value to
for MT00, MT37, MT55, MT73, and MT100 samples be 3.53 eV, as calculated from the UV absorption spec-
shows the bandgap energy values to be 3.30, 3.45, 3.53, tra. Generally, the combination of an insulator material
3.38, and 5.11 eV, respectively, whereas the indirect transi- (MgO and Al2 O3 ) with TiO2 to enhance their photocat-
tion graph shows the bandgap energy values as 3.22, 3.39, alytic performance as reported earlier30
31 due to the reason
3.47, 3.34, and 4.86 eV, respectively. of MgO layer act as a barrier for recombination of charges
The direct and indirect bandgap of the TiO2 -MgO on TiO2 .32
(MT73, MT37 and MT55) composite nanoparticles cal- In the previous discussion, we have seen that there is
cined at 400  C varies from 3.38 to 3.53 eV as well as 3.34 a deviation in the direct and indirect bandgap transition.
to 3.47 eV respectively as shown in Figures 6(b) and (c). Specifically, the indirect bandgap transition occurs at high
In general, the bandgap energy is indirectly proportional to energy level and varies between electron and holes pair
the absorption value of nanoparticles; that is, if the absorp- momentum, whereas the direct bandgap transition occurs
tion value is increased, then the bandgap energy decreases at the strong absorption and emission between valence
and vice versa. From these observed results, it is evident and conduction bands. Thus, the direct bandgap transition
materials, particularly nanoparticles, are used for applica-
tions such as photovoltaic device and solar panels.33
Table IV. Optical properties of prepared nanoparticles.
The refractive index depends on the absorption and
Sample Absorption Direct band Indirect band Refractive density of the prepared nanoparticles. Figure 6(d) shows
code (nm) gap (eV) gap (eV) index (n) the refractive index values of prepared nanoparticles as
MT00 382 3 30 3 22 2 34 2.34 (MT00), 2.31 (MT37), 2.29 (MT55), 2.32 (MT73),
MT37 371 3 45 3 39 2 31 and 2.02 (MT100) eV, which are obtained through the
MT55 363 3 53 3 47 2 29 bandgap energy values. The suitable absorption value of
MT73 376 3 38 3 34 2 32 MT55 shows good index value when compared with other
MT100 255 5 11 4 86 2 02
compositions of MgTiO3 .

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Kanna et al. Synthesis of Geikielite (MgTiO3 ) Nanoparticles via Sol–Gel Method and Studies
4. CONCLUSION
The geikielite (MgTiO3  nanoparticles were successfully
synthesized using sol–gel method. The structural prop-
erties of the prepared samples were determined using
XRD with an average crystallite size of about 12.17 nm.
The spherical morphology of geikielite nanoparticles was
determined. The SSA of geikielite nanoparticles (MT55)
was found to be 99 m2 g−1 . The geikielite (MT55) nanopar-
ticles were found to be transparent in the visible spec-
tra region, which shows a sharp absorption at 363 nm.
The energy bandgap value of the geikielite nanoparticles
is 3.53 eV (MT55) when compared to other compositions.
The obtained high optical bandgap energy of the nanopar-
ticles may be used in applications such as solar panels,
textile for production and photovoltaic devices.
Acknowledgment: The authors acknowledge the
financial support provided by Defence Research
and Development Organisation (DRDO), New Delhi
(ERIPR/ER/0905103/M/01/1279).
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Received: 13 February 2015. Accepted: 20 March 2015.
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