Applied Physics A (2020) 126:52

https://doi.org/10.1007/s00339-019-3227-z

Synthesis and characterization of cerium oxide nanoparticles using

different solvents for electrochemical applications
K. Sakthiraj1 · B. Karthikeyan2 

Received: 14 October 2019 / Accepted: 10 December 2019 / Published online: 20 December 2019
© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
Cerium oxide nanoparticles were synthesized through sol–gel method using different solvents which include water, acetone,
ethanol and ethylene glycol. Cerium (III) nitrate hexahydrate and ammonium hydroxide were used as the precursors. The
influence of the solvent on the structural, optical and electrochemical properties was investigated using powder X-ray dif-
fraction, transmission electron microscope imaging, selected area electron diffraction (SAED), Fourier transform infra-
red spectroscopy (FTIR), UV–visible absorption spectroscopy, photoluminescence (PL) spectroscopy, cyclic voltammetry
(CV) measurement and galvanostatic charge–discharge analysis. A significant change in the properties of the samples was
observed in all the characterization techniques, and it was well discussed with the already reported data. Especially with the
help of electrochemical studies, it was found that ethylene glycol used as a solvent can easily activate the surface defects in
the crystal structure rather than other solvents. This may be due to the fact that the nanocrystalline cerium oxide contains
interchangeable oxidation states (­ Ce4+ and C­ e3+) resulting from the oxygen vacancy. The atmospheric molecular oxygen
can easily react with these surface oxygen vacancies and forms highly active atomic oxygen over the surface of the material
which enhances the electrochemical property of the material. The results of the present study provide a promising platform
for developing a cathode material for electrochemical applications.

1 Introduction as well as better cycling stability. Environment-friendly

Metal oxide nanoparticles are an important class of semicon-
ductors which can be used in a variety of applications like
storage media, electronics, solar power, catalysis, etc. [1].
They have attracted considerable attention by the researchers
for the synthesis, structure and properties of their applica-
tions. Among the rare earth oxides, cerium oxide ­(CeO2)
has been extensively studied and considered as a promising
material because of its high refractive index, good trans-
mission in the visible light region, excellent UV absorption
and high stability [2–4]. The cerium oxide nanoparticles
are highly interested in the field of electrochemistry as they
can act as electrode materials in power storage devices like
super-capacitors, because it provides a large energy density
* B. Karthikeyan
karthi.madhubalan@gmail.com;
karthikeyanb@mepcoeng.ac.in
1
Department of Physics, Kamaraj College of Engineering
and Technology, Madurai, Tamil Nadu 625 701, India
2
Department of Physics, Mepco Schlenk Engineering College,
Sivakasi, Tamil Nadu 626 005, India
power generation devices like solid oxide fuel cells (SOFCs)
require the good cathode material like cerium oxide nano-
material for electrochemical reduction of oxygen in the tem-
perature range of 500–700 °C.
Generally, cerium can exist in two oxidation states,
namely ­Ce3+ and C ­ e4+. Hence, in the bulk scale, ceria can
exist in two different oxide forms, C ­ e4+ state) and
­ eO2 (in C
3+
­Ce2O3 (in ­Ce state). In nanoscale, the cerium oxide lattice
has a cubic fluorite structure and both ­Ce3+ and ­Ce4+ can
coexist on its surface [5]. The reason for choosing cerium
oxide nanoparticle in the present study is the presence of
these two interchangeable oxidation states (­ Ce3+ and C­ e4+)
which is favourable for a redox material in an electrochemi-
cal reaction. The surface nature of the cerium (IV) oxide
nanoparticles has been studied by many researchers, and
it was found that oxygen vacancy can be present over the
surface of the ceria, which in turn can change the surface
charge distribution [5]. Creation and annihilation of oxygen
vacancies and alterations in cerium valence impart excep-
tional redox activity to cerium oxide nanoparticles, which
is further enhanced by the increased surface area and quan-
tum lattice alterations that occur at the nanoscale [6]. It is

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Page 2 of 10
noteworthy that because of these surface-functionalized
properties of nanoceria, it can be used in many applications
like biomedical [6], water treatment [7], antioxidant [8],
catalyst [9], sensor [10], etc.
It is widely known that the conventional route called the
sol–gel method is a useful and attractive technique for the
preparation of metal oxide nanoparticles [11]. The sol–gel
technique is employed in the present study for the synthesis
of cerium oxide nanocrystals. Another reason for choosing
this technique is that the surface properties of the materials
can be easily controlled during the sol–gel synthesis proce-
dure. It was found that the electrochemical behaviour of the
nanomaterials mainly depends on the size and shape of the
particles and the composition of the solvents influences the
growth rates and thereby properties of crystalline materials
[12]. The present study therefore deals with the effect of
organic solvents (acetone, ethanol and ethylene glycol) on
structural, optical and electrochemical properties of cerium
oxide nanocrystal. The influence of these solvents on the
structural, optical and electrochemical properties of cerium
oxide nanocrystal was investigated, and the results were dis-
cussed in detail in the following section. The main objective
of the work is to study the electrochemical behaviour of
ceria nanoparticles prepared using various solvents, in view
of the fact that the ceria nanoparticles may be considered as
the promising candidate as a cathode material for electro-
chemical applications.
2 Experimental procedure
2.1 Chemicals used
The raw materials used in the present study are cerium (III)
nitrate hexahydrate [Ce(NO3)3·6H2O, GR grade (99% pure),
Sigma-Aldrich], ammonium hydroxide (­ NH4OH 25%, ACS
reagent, Sigma-Aldrich), ethylene glycol (­ C2H6O2, Merck
Millipore), ethanol (­ C2H5OH, Analytical grade, Merck Mil-
lipore), acetone ­(C3H6O, Analytical grade, Merck Millipore)
and ultra-pure water.
2.2 Synthesis
In metal oxide synthesis, metal–oxygen–metal bond crea-
tion is an important stage. It requires oxygen for the oxy-
gen bridge formation. In aqueous synthesis method, oxygen
atoms are provided by water. However, in non-aqueous syn-
thesis, organic solvents cannot provide the required amount
of oxygen during the condensation reaction. Hence, a finite
amount of water has to be added during the synthesis proce-
dure. Hence, a mixture of 40% of water and 60% of organic
liquid was used as a solvent for all the non-aqueous synthesis
reactions.
13
K. Sakthiraj, B. Karthikeyan
0.1 M cerium nitrate (Ce (­ NO3)3·6H2O) was added to
75 ml of ultra-pure water by stirring for 30 min followed by
the addition of ammonia (5 drops per minute). The pH value
of the reaction was maintained as 3 using ammonia solution,
and the whole reaction was carried out at 60 °C. The result-
ing solution was turned into pale-pink-coloured sol which
was further stirred continuously for 3 h. Finally, the sol got
transformed into white-coloured sol. The sol was then aged
at room temperature for 5 days until it reached a gel state.
The resulting gel was then washed thoroughly with ethanol
and ultra-pure water to remove the impurities, if any. The
gel was dried at 100 °C for 10 h in air. The obtained powder
was ground using mortar and pestle and finally calcinated
at 550 °C for 3 h in air. The final sample is named as ‘CW’.
The above-mentioned experimental procedure was fol-
lowed to obtain organic solvent-assisted ceria nanoparticle.
In the forthcoming discussions, acetone-assisted, ethanol-
assisted and ethylene-glycol-assisted samples have been
designated as ‘CAC’, ‘CET’ and ‘CEG’, respectively. The
as-prepared ceria nanocrystals appear in a pale yellow colour
­ e3+ ions
instead of pure white colour due to the presence of C
4+
along with ­Ce ions.
2.3 Characterization
The phase structure and crystallite size of the samples were
determined by X-ray diffraction (XRD) pattern using a PAN-
alytical X’Pert Pro diffractometer with a Cu-Kα wavelength
of 1.5406 Å in the 2θ range from 20° to 80°. The particle
size, morphology and selected area electron diffraction pat-
tern (SAED) of the samples were obtained by using JEOL
2100 transmission electron microscope (TEM). The UV–Vis
absorption spectrum was recorded by using Shimadzu-UV
2450 spectrophotometer. The photoluminescence (PL) meas-
urements were carried out by using PerkinElmer-LS 45 spec-
trofluorometer. The Fourier transform infrared spectroscopy
(FTIR) spectra of the samples were recorded in the range of
400–4000 cm−1 using a Shimadzu FTIR spectrometer.
2.4 Electrode preparation
The mild steel (type 304L, low-carbon steel) was carefully
polished followed by ultrasonication in water for 5 min.
Then, the steel plate was rinsed with acetone and water for
more number of times to remove the impurities. The well-
cleaned electrodes were then dried in an oven. After dry-
ing, 2 mg of CW sample (­ CeO2 prepared using water as
a solvent) was mixed with 100 µl of ethylene glycol as a
solvent. Then, 30 µl of the solution was then poured over the
surface (1 cm × 1 cm) of the mild steel plate, and the plate
or electrode was dried at 100 °C for 5 h. The thickness of
the sample coated over the steel plate is calculated using the
gravimetric method, and its value is around 1.4 µm for all the
Synthesis and characterization of cerium oxide nanoparticles using different solvents for…
samples. The final product is named as CW-coated electrode.
The same procedure was followed for the electrode prepara-
tion using other samples (CAC, CET and CEG).
2.5 Electrochemical measurements
All the electrochemical measurements of the as-synthesized
­CeO2 nanocrystals were performed using the electrochemi-
cal workstation CHI660C (three-electrode system). The
mild steel modified by the as-prepared samples was used
as the working electrode. Ag/AgCl and platinum wire were
used as the reference electrode and the counter electrode,
respectively. The electrochemical reaction was performed in
0.5 M KOH solution. All the CVs were measured between
0 and − 1 V at different scan rates of 25, 50, 75, 100 and
200 mV s−1. Galvanostatic charge–discharge measurements
were also carried out at the current density 0.7 A g−1 in the
potential range 0 to − 1 V.
3 Results and discussion
3.1 Structural characterization
The powder X-ray diffraction (XRD) patterns of the as-syn-
thesized ceria with different solvents (water, acetone, etha-
nol and ethylene glycol) are shown in Fig. 1. All the sam-
ples show the existence of diffraction peaks at (111), (200),
(220), (311), (222), (400), (331) and (420). These peaks are
well indexed with the face-centred cubic fluorite structure of
ceria (JCPDS card: 34-0394). Using Williamson–Hall equa-
tions, a plot is drawn with 4 sinθ along the x-axis and β cosθ
along the y-axis for as-prepared ceria nanoparticles as shown
Fig. 1  XRD pattern of ­ CeO2 nanocrystals prepared with different
organic solvents’ assistance: (a) water, (b) acetone, (c) ethanol, (d)
ethylene glycol and (e) JCPDS card: 34-0394
Page 3 of 10  52
in Fig. 2. From the linear fit of the data, the crystallite size
was estimated from the y-intercept, and the strain ε, from
the slope of the fit.
The average crystallite size (d) of the as-prepared samples
has also been calculated by using the Debye–Scherrer equa-
tion as follows:
k𝜆
d= , (1)
𝛽 cos 𝜃
where k is the shape factor, λ is the wavelength of X-ray
used, β is full width half maximum and θ is the Bragg’s
angle.
The lattice constant (a) of the as-prepared samples is cal-
culated using the following equation:
√
a = 3 × d111 , (2)
where a is the lattice parameter of the ceria structure and
d111 is the interplanar distance between the crystallographic
plane (111) in the ceria structure. The obtained lattice con-
stant and the average crystallite size of the as-prepared sam-
ples are listed in Table 1.
The particle size calculated for all the samples by using
two different methods (Scherrer’s formula and William-
son–Hall plot) shows a notable coincidence. The lattice
constants obtained in the present study are also found to be
coinciding well with the already reported value 5.41134 Å
(JCPDS card number: 34-0394). However, there is a small
variation in the lattice constant depending on the type of
solvent used for synthesis. The sample prepared using ace-
tone shows smaller lattice constant and hence smaller lat-
tice volume. It is widely known that the lattice parameter
expansion is related to the increase in oxygen vacancy in the
ceria structure [13], which may be the reason for observing
Fig. 2  Williamson–Hall plot for the samples prepared with solvents:
(a) water, (b) acetone, (c) ethanol and (d) ethylene glycol
13
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Page 4 of 10 K. Sakthiraj, B. Karthikeyan

Table 1  Lattice parameters and average crystallite size of the ceria nanoparticles prepared using different organic solvents’ assistance
Sl. no. Solvent used to prepare ceria nanoparticles (hkl) d-spacing (Å) Average crystallite size (nm) Lattice Lattice strain ε
constant
Scherrer’s method Williamson– (Å)
Hall method

1 Water (111) 3.12691 11.99 ± 0.27 15.34 ± 0.01 5.4160 0.00142

2 Acetone + water mixture (111) 3.09609 12.53 ± 0.26 14.51 ± 0.07 5.3626 0.00155
3 Ethanol + water mixture (111) 3.10946 13.78 ± 0.19 17.06 ± 0.04 5.3857 0.00150
4 Ethylene glycol + water mixture (111) 3.12754 16.30 ± 0.19 10.16 ± 0.06 5.4171 0.00202

lattice expansion only in water and ethylene-glycol-assisted
samples.
3.2 Electron microscopy
The morphology and size of the as-prepared ceria materials
were analysed by the HRTEM images. Figure 3a, b shows
the HRTEM images of the ceria prepared using water as a
solvent, and Fig. 3c–e displays the TEM images of ceria
nanocrystals prepared using the organic solvents such as
acetone, ethanol and ethylene glycol, respectively. The inset
in Fig. 3b, e shows the selected area electron diffraction
(SAED) pattern which clearly exposes the nanocrystalline
nature of the as-prepared samples. From the TEM images,
it is clear that the particles are well distributed in CET and
CEG samples compared to CW and CAC samples. Clear
lattice fringes are observed in Fig. 3b, and the interplanar
spacing of 0.31 nm is consistent with the (111) plane of
cubic fluorite structure of ceria. The particle size of the CW
sample measured in Fig. 3b gives 11.47 nm, which agrees
well with the average crystallite size calculated using the
Debye–Scherrer formula. Similarly, the average size of the
particles for other samples CAC, CET and CEG is found to
be 14, 15 and 18 nm using the respective HRTEM images.

Fig. 3  HRTEM images of the C ­ eO2 nanocrystals prepared using organic solvents: a, b water, c acetone, d ethanol and e ethylene glycol. Inset of
the figures b and e shows the SAED pattern of the corresponding sample

13
Synthesis and characterization of cerium oxide nanoparticles using different solvents for…
3.3 Fourier transform infrared spectroscopy (FTIR)
The FTIR spectra of all the samples are shown in Fig. 4. The
IR spectroscopy characterizes the presence of OH group on
the surface of the sample by its stretching frequencies at
3400 and 3509 cm−1. These peaks are highly visible only
in CW and CAC samples. Ethanol- and ethylene-glycol-
assisted samples (CET and CEG) show only a lesser amount
of water molecules adsorbed on the surface of the sample.
The absorption peak at 2362 cm−1 in the CAC sample may
be due to atmospheric ­CO2 adsorbed by the surface of the
sample [13]. All the samples contain a group of bands
around 1630 cm−1, which is due to the bending vibration of
water molecules [3, 5]. In the case of CW and CEG samples,
the peak at 1343 cm−1 shows the existence of molecular oxy-
gen absorbed on the surface of the nanocrystal. The peaks
observed at 674 cm−1 and 545 cm−1 are attributed to the
antisymmetric Ce–O–Ce stretching vibration of the surface
bridging oxide, which is observed in all the samples with a
­ eO2 nanocrystals prepared using the solvents: a water, b acetone, c ethanol and d ethylene glycol
Fig. 4  FTIR spectra of the C
Page 5 of 10  52
very small change in intensity. The intense peak detected at
471 cm−1 is related to the vibrational mode of the F
­ 2g sym-
metry in the cubic fluorite structure.
3.4 UV–Vis spectroscopy
The UV–visible absorption spectrum of samples CW, CAC,
CET and CEG is shown in Fig. 5. It is observed from the fig-
ure that the UV–Vis absorption spectrum of CET (ethanol-
assisted sample) is about 10 times higher than others. The
reason for observing such high absorbance may be due to
the fact that ethanol has more reducing strength than other
organic solvents and water. All the samples show a strong
absorption band in the ultraviolet region. This absorption
band may be due to the charge transfer between the 2p level
of ­O2− and 4f levels of ­Ce4+. The cerium oxide nanoparti-
cles prepared using water (CW) and ethanol (CET) show the
strong absorption band around 360 nm (3.4 eV). In the case
of the other two samples (CAC and CEG), the absorption
13
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Page 6 of 10
Fig. 5  UV–Vis absorption spectra of the ­CeO2 nanocrystals prepared using the solvents: a water, b acetone, c ethanol and d ethylene glycol
band appears around 386 nm (3.2 eV) and its tail is extended
up to the visible region. In addition to this main peak, the
samples CW and CAC exhibit an additional peak around
292 nm, which may be due to the charge transfer from ­O2− to
the ­Ce3+ [14]. As evident from the result, nanoceria contains
both ­Ce3+ and C­ e4+ oxidation states and the C
­ e3+ concentra-
tion is more in CW and CAC samples.
3.5 PL spectroscopy
The room-temperature photoluminescence (PL) spectra of
the as-prepared ceria nanocrystal are shown in Fig. 6. The
samples were excited with two different excitation wave-
lengths 360 nm and 380 nm. It is clear from the figure that
different excitation energies are penetrating into the samples
at different depths and hence it can be confirmed that defect
levels arise in the band gap region. The emission spectra of
the samples show that the observed peak values are nearly
identical, but the peak intensities of the peaks are different.
13
K. Sakthiraj, B. Karthikeyan
There are two main emission peaks at 408 nm and 488 nm
when the excitation wavelength is 360 nm. In the case of an
excitation wavelength of 380 nm, the situation is slightly
different; the samples show additional peaks at 421, 446,
460, 487, 519 and 542 nm. These peaks are attributed to
the charge transfer between the different defect levels to the
O-2p band because oxygen vacancy-related defect states are
present just below the Ce-4f level. The violet and blue emis-
sions in between 400 and 490 nm confirm the presence of
­Ce3+ phases like ­Ce2O3 and ­Ce6O11 in the structure [15–17].
Particularly, Choudhury et al. [18] reported that the emis-
sion peaks at 441, 461 and 487 nm are due to the ‘F centres’
present in the ceria, which means that the electron pair is
trapped in the oxygen vacancy site. Green colour emission
centred at 519 nm may arise from the oxygen vacancy pre-
sent in the samples [19]. The intensity of the peak at 519 nm
for the excitation wavelength 380 nm is also correspond-
ing to the oxygen vacancy. It is known that the atmospheric
molecular oxygen can easily react with these surface oxygen
Synthesis and characterization of cerium oxide nanoparticles using different solvents for…
Fig. 6  Room-temperature PL emission spectra of the ­CeO2 nanocrystals prepared using the solvents: a water, b acetone, c ethanol and d ethylene
glycol, for two different excitation wavelengths
vacancies and form highly active atomic oxygen over the
surface of the material. Thus, the PL measurement reveals
that the oxygen vacancies lead to the emissions observed in
different wavelength regions.
3.6 Electrochemical studies
The electrochemical behaviour of the as-prepared samples
was examined using the cyclic voltammetry (CV), which is
shown in Fig. 7. CV curve for all the samples at different
scan rates (25, 50, 75, 100 and 200 mV s−1) in the potential
window 0 to − 1 V reveals the electrochemical performance
of all the electrodes. It is observed that except for the bare
electrode, the peak current value increases with increasing
scan rate, which shows the stability of the electrode.
The specific capacitance (Cs) of the nanoparticle-coated
electrodes was calculated using the following relation:
I×t
Cs = , (3)
m×V
where I is the discharge current (in A g−1), t is the discharge
time (in s), m is the mass of the active material (in g) and V
is the potential window (in V). The variation of the specific
capacitance value of the samples versus scan rate is shown
in Fig. 8. From the graph, one can notice that the variation
of specific capacitance is different for all the samples. The
maximum specific capacitance of 83 F g−1 at a scan rate
25 mVs−1 is observed for CEG sample-coated electrode. It
is interesting to correlate this result with the result obtained
from the PL spectrum of the CEG sample which revealed
the existence of ­Ce3+ ions in the sample.
Page 7 of 10  52
It is obvious that the electrochemical property of the
nanoceria can be enhanced further due to the shifting
between the oxidation states of ceria ­(Ce3+ and ­Ce4+). The
FTIR analysis in the present study showed that the ‘CW’ and
‘CEG’ samples only contain the molecular oxygen over their
surface. This is the reason for the high specific capacitance
observed in these samples. Similarly, the lattice contraction
is observed in ‘CAC’ and ‘CET’ samples due to the lack of
oxygen vacancy in the structure and hence it may lead to
the decrease in specific capacitance value of the electrode.
A plot of specific peak current versus square root of
scan rate (Randles–Sevcik plot) is shown in Fig. 9 for all
the as-synthesized samples. From the figure, ceria-coated
electrodes follow the Randles–Sevcik equation [20] and it
shows the linear dependence of specific peak current on the
square root of scan rate. It can be concluded that diffusion-
controlled kinetic occurs towards the electrode surface [20,
21]. However, the plot corresponding to the bare electrode
deviates from linearity at higher scan rates. The reason for
this deviation is the predominance of non-Faradaic current
[22].
To analyse the charge storage capacity of the ceria-coated
electrodes, Galvanostatic charge–discharge analysis has been
performed at the current density 0.7 A g−1. Figure 10 shows
the charge–discharge plots with potential window 0 to − 1 V.
The shape of the curve for all the samples except CAC was
triangular symmetric in nature. The symmetry got deviated
in the case of CAC sample-coated electrode which clearly
indicates that the Faradaic current component is enhanced
only in the case of acetone-assisted C ­ eO2 nanoparticle-
coated mild steel, in accordance with the results of cyclic
13
52 
Page 8 of 10 K. Sakthiraj, B. Karthikeyan

Fig. 7  Cyclic voltammogram of the as-prepared ceria-coated electrode with different scan rates: a plain/bare, b CW-coated, c CAC-coated, d
CET-coated and e CEG-coated electrodes

Fig. 8  Variation of the specific capacitance value of the as-prepared Fig. 9  Specific peak current versus square root of scan rate (Randles–
samples versus scan rate Sevcik plot) for all the samples

13
Synthesis and characterization of cerium oxide nanoparticles using different solvents for…
Fig. 10  Galvanostatic charge–discharge for the as-prepared samples
Fig. 11  Cyclic stability of the samples at the current density
0.7 A g−1
voltammetry. It is worthy to mention here that UV–Vis anal-
ysis also showed that the CAC sample contains more amount
of ­Ce3+ ions in their structure, which may be the reason for
observing such a high Faradaic current component in the
respective sample. Figure 11 shows the cyclic stability of all
the electrodes at the current density 0.7 A g−1. The discharge
capacitance values have been reached minimum only after
500 cycles for all the samples. Capacitance retention for the
samples CW, CAC, CET and CEG is 65%, 68%, 73% and
76%, respectively.
4 Conclusion
Cerium (IV) oxide nanocrystals were successfully synthe-
sized by the sol–gel method. Four different types of solvents
(water, acetone, ethanol and ethylene glycol) were used in
Page 9 of 10  52
this study. The influence of the solvents on various proper-
ties such as structural, optical and electrochemical properties
was investigated using various characterization techniques.
Nanocrystalline nature of the as-prepared samples was con-
firmed from the SAED pattern. TEM images showed that
the particle distribution is uniform in CET and CEG sam-
ples. It was observed that nanoceria contains both C ­ e3+ and
4+ 3+
­Ce oxidation states and the ­Ce concentration is more in
CW and CAC samples. The cyclic voltammograms of the
as-prepared ceria-modified electrode showed that the peak
current in the electrode increases with an increase in the
scan rate. The highest specific capacitance of 83 F g−1 was
observed in CEG sample at a scan rate of 25 mV s−1. This
may be due to the presence of molecular oxygen over the
surface of the sample. Galvanostatic charge–discharge curve
revealed that the Faradaic current component is maximum
in the acetone-assisted sample. The results attribute that the
valance transition of C­ e4+ to ­Ce3+ resulting from the oxygen
vacancy was responsible for the electrochemical behaviour
in cerium (IV) oxide nanocrystal. From the present study, it
can be concluded that ethylene glycol is an efficient solvent
to induce an electrochemical reaction in ceria nanocrystal.
As mentioned earlier, the results of the present study may
provide a promising platform for developing a cathode mate-
rial for electrochemical applications.
Acknowledgements  The authors acknowledge the Sophisticated
Analytical Instrumentation Facility (SAIF) of IIT-Madras, India, for
HRTEM analysis. The authors would like to thank the respective col-
lege management members, the Principal and Head of the Department
for their constant support towards the research.
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