materials
Article
Structural, Optical, Magnetic and Electrochemical Properties of
CeXO2 (X: Fe, and Mn) Nanoparticles
Shalendra Kumar 1,2, * , Faheem Ahmed 1 , Nagih M. Shaalan 1,3 , Nishat Arshi 4 , Saurabh Dalela 5
and Keun H. Chae 6
Citation: Kumar, S.; Ahmed, F.;
Shaalan, N.M.; Arshi, N.; Dalela, S.;
Chae, K.H. Structural, Optical,
Magnetic and Electrochemical
Properties of CeXO2 (X: Fe, and Mn)
Nanoparticles. Materials 2023, 16,
2290. https://doi.org/10.3390/
ma16062290
Academic Editor: Alexander
N. Obraztsov
Received: 7 February 2023
Revised: 6 March 2023
Accepted: 8 March 2023
Published: 13 March 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2023, 16, 2290. https://doi.org/10.3390/ma16062290
1 Department of Physics, College of Science, King Faisal University, P.O. Box 400,
Hofuf 31982, Al-Ahsa, Saudi Arabia
2 Department of Physics, University of Petroleum & Energy Studies, Dehradun 248007, India
3 Physics Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
4 Department of Basic Sciences, Preparatory Year Deanship, King Faisal University, P.O. Box 400,
Hofuf 31982, Al-Ahsa, Saudi Arabia
5 Department of Pure & Applied Physics, University of Kota, Kota 324005, India
6 Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
* Correspondence: sjagdish@kfu.edu.sa
Abstract: CeXO2 (X: Fe, Mn) nanoparticles, synthesized using the coprecipitation route, were inves-
tigated for their structural, morphological, magnetic, and electrochemical properties using X-ray
diffraction (XRD), field emission transmission electron microscopy (FE-TEM), dc magnetization, and
cyclic voltammetry methods. The single-phase formation of CeO2 nanoparticles with FCC fluorite
structure was confirmed by the Rietveld refinement, indicating the successful incorporation of Fe
and Mn in the CeO2 matrix with the reduced dimensions and band gap values. The Raman analysis
supported the lowest band gap of Fe-doped CeO2 on account of oxygen non-stoichiometry. The
samples exhibited weak room temperature ferromagnetism, which was found to be enhanced in the
Fe doped CeO2 . The NEXAFS analysis supported the results by revealing the oxidation state of Fe
to be Fe2+ /Fe3+ in Fe-doped CeO2 nanoparticles. Further, the room temperature electrochemical
performance of CeXO2 (X: Fe, Mn) nanoparticles was measured with a scan rate of 10 mV s−1 using
1 M KCL electrolyte, which showed that the Ce0.95 Fe0.05 O2 electrode revealed excellent performance
with a specific capacitance of 945 F·g−1 for the application in energy storage devices.
Keywords: CeO2 ; XRD; UV-vis spectroscopy; ferromagnetism; NEXAFS; supercapacitors
1. Introduction
Supercapacitors have gained enormous attention due to their highly demanding ap-
plications in sustainable energy storage and harvesting [1–3]. Therefore, the development
of supercapacitors with enhanced performance is one of the main current research areas.
Scientists are widely working in search of new materials useful for the fabrication of im-
portant components of supercapacitors, such as electrodes. The key points to enhancing
the performance of the supercapacitor are to obtain high energy as well as high power
densities and a durable life with stable cycles. Ceria (CeO2 ) is one of the most extensively
probed potential candidates due to its fundamental chemical and physical properties [4,5].
However, the properties of CeO2 can be easily tailored simply by adding suitable dopant
ions into the host lattice for various technological applications such as spintronics [6–9],
electrode materials for supercapacitors [10–12], a solid oxide fuel cell [13], and antimicrobial
agents [4]. From this perspective, cerium oxide (CeO2 ) appears to be a potential candidate
due to its redox properties, which are associated with the reversible oxidation states of
cerium (Ce3+ /Ce4+ ). Reportedly, Rodrigues et al. have investigated the electrochemical
performance of CeO2, proving it a reversible redox electrochemical system due to the
coexistence of Ce4+ /Ce3+ states [14]. Other than dynamic electrochemistry, nanoceria has
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Materials 2023, 16, 2290 2 of 15

additional advantages, such as a high surface-to-volume ratio, oxygen vacancies, and a

tunable morphology. The oxygen non-stoichiometry gives rise to certain ionic defects
and vacancies, which significantly affect the electronic properties. The oxygen vacancies
can modify the conductivity via charge delocalization. Owing to its unique modifiable
electronic properties, CeO2 takes part in the electrochemical reactions in such a way as to fa-
cilitate the charge transport in electronic components [15–25]. In addition, CeO2 can display
synergistic effects when combined with other materials. Thereby, electrochemically active
CeO2 may be a suitable electrode material for the development of enhanced-performance
supercapacitors. However, despite its various advantages, CeO2 has a drawback that
restrains its usage in energy storage devices. CeO2 exhibits low electrical conductivity [26].
Additionally, the electrochemical properties and charge transport of CeO2 based elec-
trodes can be positively modified by doping with various transition metals. The addition of
a small fraction of transition metal ions in the CeO2 matrix has been found to modify vari-
ous properties, including the electrochemical activity of the resulting material [7,27,28]. The
transition metal doping reduces the crystallite size in CeO2, resulting in an enhancement
of the surface-to-volume ratio. Alongside, doping induces oxygen vacancies, which show
charge interplay around them, causing an enhancement in charge transport. Moreover, the
nature of transition metal ions greatly affects the morphology and electronic structure of
the material [19]. The specific capacitance of pure CeO2 has been reported to be 235 F/g,
which increased after doping with Co and Ni to be in the range ~ 500–600 F/g [14,29].
Similarly, Zr-doped CeO2 also showed a specific capacity of 448.1 F/g at a current density
of 1 A/g [30]. The device assembled using Zr-doped CeO2 displayed capacity retention
of 96.4% at larger cycles along with cyclic stability [31]. In addition to the nature of the
dopant ion, the synthesis method employed to prepare the material is equally significant.
For instance, Prasanna et al. used the combustion method, which favors electrochemical
activity by inducing anionic vacancies, to prepare porous nanoceria [32]. The resulting
product was found to have created oxygen vacancies on the surface of nanostructures ana-
lyzed by x-ray photoelectron spectroscopy. The induced oxygen vacancies, along with the
high surface area and adequate pore size, magnified the rate of ion diffusion, due to which
the material exhibited a specific capacitance of up to 134.6 F/g at 5 A/g with a retention
ratio of up to 92.5%. Likewise, Jeyaranjan et al. have investigated the electrochemical
properties of various morphologies (nanoparticles, nanorods, and nanocubes) of nanoceria
prepared using the hydrothermal method and reported a specific capacitance of 162.47 F/g
for nanorods [33]. It is perceivable that the chemical route methods are more favorable
to facilitate the electrochemical reaction by modifying the electronic structure of the ma-
terial. Herein, the structural, optical, magnetic, electronic structural, and electrochemical
properties of CeXO2 (X: Fe, Mn) nanoparticles have been reported.

2. Experimental
The undoped and CeXO2 (X: Fe, Mn) nanoparticles have been synthesized via the
co-precipitation route using the following raw materials: cerium (III) nitrate hexahydrate
(432.22 g/mol); manganese (II) nitrate hydrate (178.95 g/mol); iron (II) nitrate nonahydrate
(404.0 g/mol); and NH4 OH solution of highest purity (99.99%) of CDH. The cerium
nitrate hexahydrate was used to synthesize the undoped CeO2 , while the iron nitrate
nonahydrate and manganese nitrate hydrate were used for doping along with the cerium
nitrate hexahydrate. The precursors were weighed in stoichiometric amounts and added to
the deionized water to make 0.06 M of the solution with continuous stirring. The dropwise
ammonia solution was added until the pH of the solution reached 9 and was maintained
throughout the experiment. After 2.5 h, the stirring was stopped and the solution was
centrifuged to get the precipitate. The precipitates were washed with deionized water and
ethanol many times to wash out the impurities and then dried in a hot air oven at 80 ◦ C
for 24 h. After grinding, the fine powders were sintered at 500 ◦ C for 5 h. The product
was finally ground to characterize for various measurements, viz., XRD, TEM, UV-vis
spectroscopy, dc-magnetization, and electrochemical analysis.
Materials 2023, 16, 2290 3 of 15

Characterization Techniques
A Philips X-pert X-ray diffractometer was used to record the diffraction patterns using
Cu Kα (λ ~ 1.5418 Å). The FE-TEM (JEOL/JEM-2100F version) operated at 200 kV and
was used to capture the TEM micrographs and selected area electron diffraction (SAED)
pattern. The UV-vis spectroscopy measurements were obtained using Model LAMBDA
35, PerkinElmer (Waltham, MA, USA), and Raman spectra were recorded using a Raman
spectrometer (NRS-3100) of SINCO Instrument Co. The magnetic behavior of the samples
was studied using the quantum design physical properties measurement setup (PPMS). The
Corrtest-CS150 workstation was utilized for the electrochemical measurements of CeO2 ,
Ce0.95 Fe0.05 O2 , and Ce0.95 Mn0.05 O2 nanoparticles. All the electrochemical characterizations
were performed with a 1 M aqueous solution of KCL as an electrolyte in a conventional
three-electrode cell configuration. The working electrodes were designed by mixing 80%
active materials (CeO2 , Ce0.95 Fe0.05 O2 , and Ce0.95 Mn0.05 O2 nanoparticles), 10% carbon
black, and 10% polyvinylidene fluoride (PVDF). The weighted electrode materials were
homogeneously mixed using n-methyl-2 pyrrolidinone (NMP) as a solvent to form a slurry.
The slurry was pasted on the nickel foam substrate (~1.0 cm2 ) and then dried at 80 ◦ C in
the hot air oven for 12 h. All the electrodes were identical with respect to shape and size.
The Ag/AgCl and Pt wires were utilized as reference and counter electrodes, respectively.

3. Results and Discussion

3.1. XRD Analysis
The structural features of the nanoparticles have been investigated using X-ray diffrac-
tion patterns. Rietveld refinement of the patterns, performed using open-access Fullprof
software, is displayed in Figure 1a. The lattice parameters, peak shape parameters, back-
ground, atomic positions, and occupancies are carefully refined using the pseudo-Voigt
function. The experimentally observed and theoretically calculated patterns are represented
in black and red, respectively, whereas the difference between the two is represented at the
bottom by blue, green, and pink colored lines for undoped, Fe-doped, and Mn-doped CeO2
nanoparticles, respectively. Bragg’s positions are shown by the vertical orange-colored lines.
The values of reliability factors and χ2 obtained after refinement are mentioned in Table 1.
The value of χ2 is between 1.3–1.5, which is acceptable for the good quality of refinement.
The refined crystal structure showing 4 oxygen atoms bonded to 1 Ce atom and the 5%
fraction of dopant ions substituted in Ce are displayed along with the respective refined
XRD spectra. The indexing of the peaks associates the peak positions to the face-centered
cubic fluorite structure (space group: Fm3m) of CeO2, which corresponds to the JCPDS
number: 75–0158 [34]. The indexing shows that all the samples attain similar crystallite
structures, indicating effective incorporation of Fe2+ and Mn2+ in place of Ce4+ . However,
the strain is found to be increased in the doped compounds, giving a maximum value
for Fe-CeO2 . As a consequence, the size-strain plot (SSP) calculation is carried out using
equation [35], as shown below.
   ε 2
k
(dhkl β hkl cos θ )2 = d2hkl β hkl cos θ + (1)
D 2

Now, using the aforementioned equation, a plot is made with each diffraction peak’s
associated (d2 hkl βhkl cosθ) term along the X-axis and (dhkl βhkl cosθ)2 along the Y-axis,
as shown in Figure 1b. The intercept of the straight line provides the intrinsic strain
of the nanoparticles, and the slope gives the average size. We observed that the size
of the crystallites in all samples calculated using the size strain plot is comparable to
that determined using the Scherrer method [5]. Rietveld refinement further reveals a
shifting in the peak position towards a higher 2θ value, which indicates the decrease in
the lattice parameter as displayed in Figure 2a. Comparing the XRD diffraction peaks
(111) of undoped CeO2 and Fe- and Mn-doped CeO2 nanoparticles, it is evident that
the replacement of some Ce4+ (0.097 nm) ions by smaller radius Fe2+ (0.077 nm) ions and
 Materials 2023, 16, x FOR PEER REVIEW 4 of 17

Materials 2023, 16, 2290 Scherrer 4 of 15

SSP TEM Ce/X/O Ce/X/O
Method

0.02083/ 0.03336/
CeO2 20.4 26.6 21.6 1.5 8.40 5.13 9 7.361
0.04167 0.08165

Mn2+ (0.087 nm) ions results in an increase in FWHM0.0197885/ with a decrease

0.01956/ in the crystallite size
Ce0.95Fe0.05O2 14.2 10.1 47.2 1.4 7.14 7.37 14 6.901 0.001042/ 0.00177/
of the particles. The crystallite structure formed with0.04133 the smallest
0.04148 unit cell volume is in
the case of Fe-CeO2 nanoparticles, as displayed in Figure 2b. This
0.0197885/ also attains the smallest
0.01839/
Ce0.95 Mndensity
O
0.05
of the
31.2
2 40.5 compound,
35.4 1.3 6.9 7.053 (see
6.34 g/cm 13 Table
7.3501). Further,
0.001042/ Scherrer’s
0.00142/ formula is used to
0.04133 0.04133
calculate the crystallite sizes, which are shown in Figure 2c.

Materials 2023, 16, x FOR PEER REVIEW 5 of 17

(a)

(b)
Figure 1. (a). Rietveld refined X‐ray diffraction patterns of undoped and CeXO2 along with the re‐
Figure 1. (a). Rietveld
spective images refined X-ray diffraction
showing incorporation of Fe and Mn inpatterns
CeO2 matrix: of undoped
Experimental andare
data points CeXO2 along with the
shown in colour, the red line shows superimposed theoretically calculated curve, vertical orange
respective images showing incorporation of Fe and Mn in CeO 2 matrix:
colour lines show Bragg’s positions and blue/green/pink line at the bottom indicate Experimental
the difference data points
in respective fittings. (b) Size‐strain plots of undoped and CeXO2 (X: Fe, Mn) nanoparticles.
are shown in colour, the red line shows superimposed theoretically calculated curve, vertical orange
colour lines show Bragg’s positions and blue/green/pink
𝑘 line 𝜀at the bottom indicate the difference in
𝑑 𝛽 cos 𝜃 𝑑 𝛽 cos 𝜃 (1)
𝐷
respective fittings. (b) Size-strain plots of undoped and CeXO22 (X: Fe, Mn) nanoparticles.
Now, using the aforementioned equation, a plot is made with each diffraction peak’s
associated (d2hklβhkl cosθ) term along the X‐axis and (dhklβhklcosθ)2 along the Y‐axis, as
shown in Figure 1b. The intercept of the straight line provides the intrinsic strain of the
nanoparticles, and the slope gives the average size. We observed that the size of the crys‐
tallites in all samples calculated using the size strain plot is comparable to that determined
using the Scherrer method [5]. Rietveld refinement further reveals a shifting in the peak
position towards a higher 2θ value, which indicates the decrease in the lattice parameter
as displayed in Figure 2a. Comparing the XRD diffraction peaks (111) of undoped CeO2
and Fe‐ and Mn‐doped CeO2 nanoparticles, it is evident that the replacement of some
Ce4+(0.097 nm) ions by smaller radius Fe2+(0.077 nm) ions and Mn2+(0.087 nm) ions results
Materials 2023, 16, 2290 5 of 15

Table 1. The reliability factors, densities, and occupancies were obtained through Rietveld Refinement
of undoped and CeXO2 (X: Fe, Mn) nanoparticles. The crystallite sizes and particle sizes were
calculated using various methods.

Occupancy
Particle
Crystallite Size (nm) Size (nm) Density After
χ2 Initial
Rp (%) Rw p (%) Rexp (%) ρ Refinement
(g/cm3 )
Scherrer
SSP TEM Ce/X/O Ce/X/O
Method
0.02083/ 0.03336/
CeO2 20.4 26.6 21.6 1.5 8.40 5.13 9 7.361
0.04167 0.08165
Materials 2023, 16, x FOR PEER REVIEW 6 of 18
0.0197885/ 0.01956/
Ce0.95 Fe0.05 O2 14.2 10.1 47.2 1.4 7.14 7.37 14 6.901 0.001042/ 0.00177/
0.04133 0.04148
lite structure formed with the smallest unit cell volume is in0.0197885/
the case of Fe-CeO 2 nanopar-
0.01839/
Ce0.95 Mn0.05 O2 31.2 40.5 35.4 1.3 ticles, 6.34
as displayed 7.05 13 also attains
in Figure 2b. This 7.350the smallest
0.001042/ 0.00142/
density of the compound,
0.04133 0.04133
6.9 g/cm3 (see Table 1). Further, Scherrer’s formula is used to calculate the crystallite sizes,
which are shown in Figure 2c.

Figure 2. The variation of (a) lattice parameter; (b) unit cell volume; (c) crystallite size and (d) strain
Figure 2. The variation of (a) lattice parameter; (b) unit cell volume; (c) crystallite size and (d) strain
obtained for undoped and CeXO2 (X: Fe, Mn) nanoparticles.
obtained for undoped and CeXO2 (X: Fe, Mn) nanoparticles.
3.2. TEM Analysis
3.2. TEM Analysis The morphology of the nanoparticles is analyzed through TEM micrographs, as
demonstrated
The morphology of theinnanoparticles
Figure 3a–c. The spherical
is analyzed particles with aggregation
through can be seen in the
TEM micrographs, as
demonstrated in micrographs
Figure 3a–c. with unaffected
The spherical morphology
particles forwith
Fe3+ and Mn2+ion incorporation
aggregation can be seenin thein
CeO
the2

nanolattice. The particle sizes are calculated using open-access ImageJ software and are
micrographs withrepresented
unaffected morphology
through Fe3+ and Mn
for distribution
the fitted size
2+ ion incorporation in the CeO
histograms shown in the insets of respec-2
nanolattice. The tive
particle
Figuresizes are histograms
3a–c. The calculated using
show open-access
a narrow ImageJ
particle size software
distribution, anduni-
indicating are
represented through theinfitted
formity size distribution
the particle sizes. Mn-CeO histograms
2 nanoparticlesshown in smallest
have the the insets of respective
particle size of 13
nm as compared
Figure 3a–c. The histograms showto CeO 2. The indexing through selected area electron diffraction (SAED)
a narrow particle size distribution, indicating uniformity
ring patterns, shown in Figure 3a′–c′ confirms the face-centered cubic fluorite structure of
in the particle sizes. Mn-CeO2 nanoparticles have the smallest particle size of 13 nm as
all the samples. The indexed planes are marked along with the ring patterns and indicate
compared to CeOsmall-sized
2 . The indexing through
particles with selected
increased areafor
crystallinity electron
Fe and Mndiffraction (SAED)
cation doping ring
in the CeO 2

patterns, shown in Figure 3a 0 –c0 confirms the face-centered cubic fluorite structure of all
nanolattice. Further, the high-resolution transmission electron micrographs are displayed
the samples. Theinindexed
Figure 3a″–c″.
planesThe are
interplanar
marked spacing
along forwith
undopedthe CeO
ring2, patterns
Fe-, and Mn-doped CeO2
and indicate
nanoparticles is approximately 0.210, 0.230, and 0.210 nm, respectively, corresponding to
small-sized particles with increased crystallinity for Fe and Mn cation doping in the CeO2
the (200) plane of fluorite structure.
nanolattice. Further, the high-resolution transmission electron micrographs are displayed
in Figure 3a”–c”. The interplanar spacing for undoped CeO2 , Fe-, and Mn-doped CeO2
nanoparticles is approximately 0.210, 0.230, and 0.210 nm, respectively, corresponding to
the (200) plane of fluorite structure.
 Materials 2023, 16, x FOR PEER REVIEW 7 o
Materials 2023, 16, 2290 6 of 15

Figure 3. (a–c) Transmission Electron Micrographs of undoped and CeXO2 (X: Fe, Mn) nanoparticles; in-
Figure 3. (a,b,c) Transmission Electron Micrographs of undoped and CeXO2 (X: Fe, Mn) nanopa
set shows the histograms representing
cles; inset shows theparticle size distribution
histograms representingfitted withsize
particle Gauss (a0 –c0with
function; fitted
distribution ) shows
Gauss functi
the SAED patterns(a′,b′,c′) 00
and (a shows 00
–c ) highlights
the SAEDthe HRTEM
patterns and patterns of CeXO
(a″,b″,c″) 2 (X: Fe,
highlights theMn) nanoparticles.
HRTEM patterns of CeXO2 (X:
Mn) nanoparticles.
3.3. UV-Vis Absorption Spectra
Figure 4a displays the absorption spectra in the wavelength range of 400–800 nm.
The spectra show the maximum absorption at 400 nm, which decreases with the increase in
Materials 2023, 16, x FOR PEER REVIEW 8 of 18

Materials 2023, 16, 2290

3.3. UV-Vis Absorption Spectra 7 of 15
Figure 4a displays the absorption spectra in the wavelength range of 400–800 nm.
The spectra show the maximum absorption at 400 nm, which decreases with the increase
in wavelength.
wavelength. TheThe highest
highest absorption
absorption hasobtained
has been been obtained
for undoped for undoped
CeO2 . TheCeO 2. The elec-
electronic band
tronic band gap of nanoparticles is calculated with Tauc’s plots,
gap of nanoparticles is calculated with Tauc’s plots, which are displayed in Figure 4b–d for which are displayed in
Figure 4b–d for undoped CeO 2, Fe-CeO2, and Mn-CeO2, respectively. The band gap energy
undoped CeO2 , Fe-CeO2, and Mn-CeO2, respectively. The band gap energy of undoped CeO2
of undoped CeO
nanomaterials 2 nanomaterials (2.9 eV) is smaller in comparison to its bulk counterpart,
(2.9 eV) is smaller in comparison to its bulk counterpart, CeO2 (3.35 eV),
CeO 2 (3.35 eV), which may be the outcome of a shift in the 4f electronic
which may be the outcome of a shift in the 4f electronic states from Ce4+ (4f states from
0 ) to Ce Ce14+),
3+ (4f
(4f ) to indicates
0
which Ce (4f ), the
3+ 1 which indicates the
introduction introduction
of an extra electron of aninextra
the electron
4f orbitalinand
the decreases
4f orbital andthe
decreases the band gap energy of undoped CeO 2 nanomaterials.
band gap energy of undoped CeO2 nanomaterials. The highest band gap is found to be The highest band gap is
found to be 2.9 eV for the undoped CeO while the lowest
2.9 eV for the undoped CeO2, while the lowest band gap (eV) is exhibited by Fe-doped
2, band gap (eV) is exhibited by
Fe-doped CeO2 nanoparticles.
CeO2 nanoparticles. The loweringThe lowering
of the band of the
gapband
may gap may be associated
be associated with the with the
smallest
smallest ionic radii and oxidation state of Fe ions. When 2+ Fe
ionic radii and oxidation state of Fe ions. When Fe is doped in the CeO2 lattice, it 2+ is doped in the CeO2 lattice,

it substitutes
substitutes ininplace
placeofofthe
thehost
hostcation,
cation,Ce Ce 3+3+. . There
There is
is aa difference
difference between
between thethe oxidation
oxidation
states and ionic radii of Fe ions and Ce ions that leads to the creation of the defect states
in the lattice. These
These defect
defect states
states are very likely to be the oxygen vacancies in such cases
of diluted magnetic semiconductors. These These oxygen oxygen vacancies
vacancies create intermediate states
via exchange interactions with neighboring electrons, which reduces the band gap of the
material. Therefore,
Therefore, the the decrease in band gap energy in our doped nanoparticles may be
induced
induced by the development of localized impurity defect levels brought brought on on by Fe2+
by Fe 2+ and

Mn ion2+
2+ iondoping,
doping,which whichmanifests
manifestsin inoxygen
oxygenvacanciesvacanciesand andCe 3+
Ce defects.
3+ defects.

Figure 4. (a) UV-vis absorption curves for undoped and CeXO2 (X: Fe, Mn) nanoparticles; (b–d)
Figure 4. (a) UV-vis absorption curves for undoped and CeXO2 (X: Fe, Mn) nanoparticles; (b–d) Tauc’s
Tauc’s plots to determine the band gap of the respective samples.
plots to determine the band gap of the respective samples.
3.4.
3.4. Raman
Raman Spectroscopy
Spectroscopy
The
The influence
influence of
of the
the dopant
dopant ion
ion is
is investigated
investigated using
using the
the molecular
molecular vibrations
vibrations of
of the
the
Ce-O8 vibrational unit of the CeO matrix [37]. The substitution of TM in place of Ce
Ce-O8 vibrational unit of the CeO2 matrix [36]. The substitution of TM in place of Ce affects
2 af-
fects the symmetrical stretching of O-ions around Ce-ions, and the resulting vibrations
the symmetrical stretching of O-ions around Ce-ions, and the resulting vibrations have been
have been
detected detected
through through
Raman Raman
spectra, spectra, as represented
as represented in The
in Figure 5a–c. Figure 5a–c.show
spectra The spectra
the F2g
Raman active modes corresponding to CeO2 , which are sensitive to the molecular disorder
around Ce ions. The characteristic symmetrical breathing Raman active mode F2g of cubic
fluorite CeO2 is obtained at ~460 cm−1 , which corresponds to the oxygen ions around Ce4+
ions (O-Ce-O) [37]. This Raman peak for undoped CeO2 nanomaterials is caused by the
Materials 2023, 16, x FOR PEER REVIEW 9 of 17

Materials 2023, 16, 2290 8 of 15

ions around Ce4+ ions (O‐Ce‐O) [37]. This Raman peak for undoped CeO2 nanomaterials
is caused by the growth of oxygen vacancies at the Ce3+ site as a consequence of the change
3+ site as a consequence of the change of the valence
ofgrowth of oxygen
the valence state vacancies
of Ce4+ ions at totheCeCe3+ ions. In the present case, the bands are obtained at
Ce
−1
4+ ions to
−1 Ce 3+
~ 462 cm , 453 cm , and 455 cm for undoped,case,
state of ions. In
−1 the present the bands
Fe doped, andare obtainedCeO
Mn‐doped at ~462 cm−1 ,
2, respec‐
453 cm − 1 , and − 1
tively, which are455 cm to for
closer theundoped,
characteristic Fe doped, and Mn-doped
band indicative of theCeO 2 , respectively,
effective substitutionwhich
of
dopant ions in place of the host cation. However, a decrease in the Raman frequency isin
are closer to the characteristic band indicative of the effective substitution of dopant ions
place of
clearly the host indicating
observed, cation. However, a decrease
the occurrence of in the Raman
oxygen frequency is clearly
non‐stoichiometry observed,
with O/Ce < 2.
The reduction in oxygen content has been found by calculating the value of oxygen deficitin
indicating the occurrence of oxygen non-stoichiometry with O/Ce < 2. The reduction
oxygen
(δ) content
using the has δ
formula: been
= 2.66found
(1‐ωnby /ωbcalculating
), where ωn is thethevalue of oxygen
position deficitactive
of the Raman (δ) using
bands the
formula: δ = 2.66 (1 − ω n /ω b ), where ω n is
of the samples and ωb is the frequency of the bulk CeO2 (465 cm the position of the Raman
−1 active bands of
) [29]. The values of δ are the
samples and ω is the frequency of the bulk CeO (465 cm −1 ) [29]. The values of δ are
b 2
indicated in the respective Figure 5a–c, which reveal that even undoped CeO2 shows a
indicated
slight oxygen in the respective
deficiency. It isFigure 5a–c, which
noteworthy reveal
here that whenthatthe
even undoped
particle CeO2 shows
size reduces froma
slight oxygen deficiency. It is noteworthy here that when the particle size reduces from bulk
bulk to nm scale, noticeable changes take place in the host lattice, including size confine‐
to nm scale, noticeable changes take place in the host lattice, including size confinement
ment effects that may lead to oxygen non‐stoichiometry. Further, the substitution of Fe
effects that may lead to oxygen non-stoichiometry. Further, the substitution of Fe and Mn in
and Mn in place of Ce creates more oxygen non‐stoichiometry. The introduction of oxygen
place of Ce creates more oxygen non-stoichiometry. The introduction of oxygen vacancies
vacancies in the CeO2 nanolattice leads to a change in the oxidation states of Ce from +4
in the CeO nanolattice leads to a change in the oxidation states of Ce from +4 to +3, which
to +3, which2 is favorable for the redox properties and therefore influences the density of
is favorable for the redox properties and therefore influences the density of states, which
states, which further affects the important properties of the material.
further affects the important properties of the material.

(a–c)Raman
Figure5.5.(a–c)
Figure Ramanspectra
spectraofofundoped
undopedand
andCeXO
CeXO2 2
(X:Fe,
(X: Fe,Mn)
Mn)nanoparticles.
nanoparticles.

3.5. Magnetisation
3.5. Magnetisation
The magnetization behavior of CeO2 , Fe-CeO2 , and Mn-CeO2 nanoparticles has been
The using
studied magnetization behavior
VSM at room of CeO2, The
temperature. Fe‐CeO 2, and Mn‐CeO2 nanoparticles has been
hysteresis loops showing magnetization ver-
studied using VSM at room temperature. The hysteresis
sus magnetic field (M-H) are displayed in Figure 6a–c. The loops showinginsets
respective magnetization
show the ver‐
M-H
sus
curve at a low field and infer that all the samples demonstrate weak ferromagneticthe
magnetic field (M‐H) are displayed in Figure 6a–c. The respective insets show M‐H
ordering
at room temperature. The various magnetic parameters such as saturation magnetization
Materials 2023, 16, x FOR PEER REVIEW 10 of 17

Materials 2023, 16, 2290 9 of 15

curve at a low field and infer that all the samples demonstrate weak ferromagnetic ordering
at room temperature. The various magnetic parameters such as saturation magnetization
(MS),), remnant
(M magnetization (MR), and coercivity (HC) are calculated for the undoped and
S remnant magnetization (MR ), and coercivity (HC ) are calculated for the undoped and
X (Fe,
X (Fe, Mn)Mn) doped
doped CeOCeO22nanoparticles
nanoparticles(see(seeTable
Table2).2).
The undoped
The undoped CeO 2 has the lowest Ms
CeO 2 has the lowest
value ~1.5 × 10 −4 emu/g which changes after doping and shows the maximum value for Fe‐
− 4
Ms value ~1.5 × 10 emu/g which changes after doping and shows the maximum value
doped
for CeO2 nanoparticles.
Fe-doped Although
CeO2 nanoparticles. there have
Although therebeen
havenumerous theoretical
been numerous and experi‐
theoretical and
mental investigations on RTFM in these oxides [7,8], there is still great controversy
experimental investigations on RTFM in these oxides [7,8], there is still great controversy regard‐
ing the ferromagnetic
regarding ordering
the ferromagnetic in theseinoxides
ordering with rare
these oxides earth
with rareand
earthtransition metal cation
and transition metal
doping and its correlation to the formation of defects and oxygen vacancies.
cation doping and its correlation to the formation of defects and oxygen vacancies. con‐ The main The
ditioncondition
main in CeO2 forintheCeO observation of ferromagnetic behavior is its tendency towards oxygen
2 for the observation of ferromagnetic behavior is its tendency to-
non‐stoichiometry.
wards When transition
oxygen non-stoichiometry. Whenmetal ions aremetal
transition dopedionsinare
thedoped
CeO2 inlattice,
the CeOthey2 lattice,
create
defects such as oxygen vacancies, which interact with the neighboring
they create defects such as oxygen vacancies, which interact with the neighboring elec- electron [38]. The
oxygen
tron [38].vacancies
The oxygen entrap the electrons,
vacancies entrap thewhich undergo
electrons, whichexchange
undergointeractions and create
exchange interactions
bound
and magnetic
create boundpolarons
magnetic (BMP), which
polarons induce
(BMP), ferromagnetic
which ordering [39].
induce ferromagnetic ordering [39].

Figure 6.
Figure 6. (a–c)
(a–c) MH
MH hysteresis
hysteresisloops
loopsfor
forundoped
undopedCeO
CeO2 2and
andCe
Ce0.95 X0.05
0.95X 0.05O
O22(X:
(X:Fe,
Fe, Mn)
Mn) nanoparticles;
nanoparticles;
(a –c ) Fitting of M-H loops using Langevin function to find BMP and matrix contribution to
(a′–c′)
0 0 Fitting of M‐H loops using Langevin function to find BMP and matrix contribution the
to the
ferromagnetic behavior.
ferromagnetic behavior.
Materials 2023, 16, 2290 10 of 15

Table 2. List of parameters obtained from experimental M-H curve and fitting of the Langevin
equation to find BMP and matrix contribution to the ferromagnetic behavior.

Experimental Data Fitting Parameters Extracted from BMP Model

Ms (emu/g) Mr (emu/g) Hc (Oe) Mo (emu/g) meff (µB ) N (cm−3 ) χm (emu g Oe−1 )
CeO2 1.5 × 10−4 5.7 × 10−6 20.0 1.97 × 10−4 2.12 × 10−16 9.3 × 1011 5.8 × 10−9
Ce0.95 Fe0.05 O2 3.5 × 10−4 3.2 × 10−5 60.0 0.058 0.77 × 10−16 7.4 × 1014 2.076 × 10−7
Ce0.95 Mn0.05 O2 5.6 × 10−2 4.3 × 10−3 80.0 3.26 × 10−4 1.1 × 10−16 3.0 × 1014 6.02 × 10−9

In order to get more insights into the contribution of BMP to the ferromagnetic behavior
of the samples, the M-H loops are fitted with the Langevin function (L(x)). The Langevin
function has been employed as described in the literature [40–43]. The expression may
be written as M = Mo L(x) + χmH and is simplified as M = A[coth(B·H)-(B·H)−1 ] + C·H,
where A = Mo = N·ms (N being the number of BMPs per cm3 ), B = meff /KB T (KB being the
Boltzmann constant and T being the temperature of taking measurements), and C = χm
(χm ·H is the matrix contribution). The ms (~meff ) is the true spontaneous magnetic moment.
The values obtained for these parameters are indicated in Table 2. The value of Mo is
found to be highest for the Ce0.95 Fe0.05 O2 and lowest for pure CeO2 , even though the true
spontaneous magnetization (meff ) is observed to be in reverse order. A similar case has
been reported by Mohanty et al., indicating meff varying inversely from the spontaneous
magnetization, which has been attributed to the competing exchange interactions between
BMPs and the matrix [43]. Further, the values of N and χm are also found to be highest
for Ce0.95 Fe0.05 O2 . Thus, the values of Mo , N, and χm are observed to be lowest for
pure CeO2 and highest for Ce0.95 Fe0.05 O2 , indicating enhanced ferromagnetic behavior in
Ce0.95 Fe0.05 O2 , which confirms the formation of BMPs as a consequence of doping as well
as the contribution of the matrix. Since the dopant concentration is the same (5%) in both
the doped samples, the enhanced ferromagnetic ordering can not only be associated with
the dopant concentration; however, the nature of the elements, i.e., Fe and Mn, also plays
a part. Although individual Mn atoms have a higher magnetic moment than Fe, Mn is
likely to dwell in the matrix antiferromagnetically, which may be the possible reason for
the higher magnetic behavior induced in Fe doped CeO2 as compared to Mn doped CeO2 .
In addition, the oxidation state may significantly affect the exchange interactions as Mn is
possibly incorporated in the host matrix in the Mn2+ oxidation state (see Section 3.6) and Fe
is in Fe2+ /Fe3+ mixed valence states, which leaves Fe with more electrons and/or induces
a higher number of oxygen vacancies in the matrix. Thus, the doping of Fe in the CeO2
matrix enhances the ferromagnetic behavior of the host system.

3.6. Near Edge X-ray Absorption Fine Spectroscopy (NEXAFS)

The oxidation states of the ions are investigated using the NEXAFS spectra shown
in Figure 7a–d. Figure 7a displays the L3,2 edge spectra of Fe-doped CeO2 at ~ 705 and
709 eV together with the reference spectra of FeO, Fe2 O3 , and Fe3 O4 . The L3,2 spectra
arise due to the electronic transitions between the core levels of Fe 2p3/2 and 2p1/2 states
and outer Fe 3d states. These transitions result in the formation of holes that take part in
charge transfer processes [14]. The L3 edge of Fe-doped CeO2 shows no splitting and shows
more resemblance to that of Fe3 O4 , indicating that Fe is dissolved in mixed valence states
(Fe2+ /Fe3+ ). Similarly, Figure 7b displayed the L3,2 edge spectra of Mn-doped CeO2 along
with the reference spectra of MnO, MnO2 , and Mn2 O3 . The spectra of Mn-doped CeO2
resemble more closely those of MnO, which show the presence of Mn2+ states in the host
matrix. Thus, the various enhanced properties in Fe-doped CeO2 can be associated with the
mixed valence states of Fe, which are responsible for the reduced oxygen stoichiometry in
the lattice and the formation of oxygen vacancies. We conclude that the electronic structure
of CeO2 changes due to a change in the vacant number of 4f orbitals and hybridization with
the lattice oxygen, although TM does not show any secondary phases in the CeO2 lattice.
Materials 2023, 16, x FOR PEER REVIEW 12 of 17
Materials 2023, 16, 2290 11 of 15

Figure7.7.NEXAFS
Figure NEXAFSspectra
spectraofof (a)
(a) Fe
Fe L L3,2 edge of
3,2 edge of Ce
Ce0.95 Fe0.05
0.95Fe 0.05OO
2 2 nanoparticles;(b)
nanoparticles; (b)Mn
MnLL edge
3,23,2edge
Ce
Ce 0.95 Mn
0.95 Mn O2 nanoparticles;
O2 nanoparticles;
0.050.05 (c) M
(c) Ce Ce5,4M 5,4 edge
edge undoped
undoped and CeXO
and CeXO 2 (X: 2 (X:Mn)
Fe, Fe, nanoparticles,
Mn) nanoparticles,
and (d)and
O(d)
K edge of undoped
O K edge and CeXO
of undoped 2 (X: Fe,
and CeXO Mn)
2 (X: Fe, nanoparticles.
Mn) nanoparticles.

Figure7c7cdepicts
Figure depictsthethenormalized
normalizedM M5,45,4edge
edgeXASXASspectra
spectraofofCeO CeO 2 and
2 and TM-dopedCeO
TM‐doped CeO 2. 2 .
Thetwo
The twowhite
white lines
lines at at
878878eVeV and and896896
eV eVon theon the
M5,4M 5,4 -edge
‐ edge XASXAS of CeOof CeO 2 correspond
2 correspond to theto
the electron
electron transitions
transitions Ce 3dCe 3d5/2
5/2→4f →4f
7/2 (M 7/2 (M
5) and Ce5 )3d
and
3/2→4fCe5/2 3d(M3/24)→ 4f5/2
[44]. The (Mspectral
4 ) [44]. The
whitespectral
lines
Mwhite
5 and lines
M4 areM5approximately
and M4 are approximately
17.91 eV apart. 17.91 eV apart. Furthermore,
Furthermore, due to changes dueintospectral
changes
in spectral characteristics
characteristics caused by Fe caused and Mnby Fe and
doping in Mn
CeOdoping in CeOof
2, the position 2 , the
the Ce position of the
M5,4‐edges hasCe
M
been -edges has been seen to move somewhat towards lower
5,4seen to move somewhat towards lower energy. The post‐edge two satellites appear energy. The post-edge two
satellites
due to the appear
transitiondueoftothe
the4f transition
state in theof the 4f state inband;
conduction the conduction
therefore,band;these therefore,
peaks arethese
the
peaks are the distinctive peaks to show the contribution of 4f o states, and the strength of
distinctive peaks to show the contribution of 4fo states, and the strength of the satellite
the satellite
peaks is usedpeaks is usedthe
to measure to measure
quantitythe of quantity
the 4fo state.of the 4fo state.
When TM is When TM is introduced,
introduced, it forms
it forms oxygen vacancies and increases the fraction of Ce 3+ in comparison to undoped
oxygen vacancies and increases the fraction of Ce in comparison to undoped CeO2. Fig‐
3+
CeO
ure 7d2 .represents
Figure 7d represents
the O K edge thespectra
O K edge of spectra of theindicating
the samples, samples, indicating
transitions transitions
from O 1sfromto
O 1s to hybridized higher
hybridized higher energy states. energy states.
 Materials 2023, 16, x FOR PEER REVIEW 13 o
Materials 2023, 16, 2290 12 of 15

3.7. Electrochemical Study

3.7. Electrochemical Study
The CV measurements are performed to study the capacitance performance of C
The CV measurements
Ce0.95Mn0.05Oare 2, andperformed
Ce0.95Fe0.05toOstudy the capacitance
2 electrodes performance ofsystem
using the three‐electrode CeO2 , in 1 M K
Ce0.95 Mn0.05 O2 , and Ce0.95 FeThe
electrolyte. O2 electrodes
0.05 CV curves of CeO using the
2, Ce three-electrode
0.95Mn 0.05O2, and Cesystem
0.95Fe0.05O in2 nanoparticles,
1 M KCL as h
electrolyte. The CV curves
lighted of CeO
in Figure 2 , Cewere
8a–d, 0.95 Mn 0.05 O2 , and
measured Ce0.95 Fe0.05
at different O2 nanoparticles,
potential scan rates of as 10, 20, 50,
highlighted in Figure
100 mV 8a–d, were
s−1. The CVmeasured
measurement at different
was done potential scan rates
in the potential windowof 10, of20,−0.9
50, V and 0.
and 100 mV s−1 .ItThe CV measurement
is worth noticing that the was done in
features ofthe
the potential
CV curveswindow of −0.9 V
for all electrodes areand
analogous.
0.0 V. It is worth noticing
comparison thatofthethefeatures
CV profiles of theofCV CeOcurves
2, Ce0.95 forMn all
0.05electrodes
O2, and Ceare 0.95Feanalogous.
0.05O2 electrodes m

The comparison uredof theatCV a scan

profilesrateofofCeO 10 mV2 , Ce s−1 has
0.95 Mnbeen0.05 Odisplayed
2 , and Ce0.95 in Fe
Figure
0.05 O28d. One can notice f
electrodes
Figure 8d that the −
Ce1
measured at a scan rate of 10 mV s has been displayed in Figure 8d. One can noticecurve
0.95Fe 0.05 O 2 electrode has a higher area under the fromcompare
other electrodes. The specific capacitance (C
Figure 8d that the Ce0.95 Fe0.05 O2 electrode has a higher area under the curve compared of the C
S ) calculated using the CV profiles
Ce0.95
to other electrodes. Mn0.05
The O2, andcapacitance
specific Ce0.95Fe0.05O2(C electrodes
S ) calculated has been using shown
the CV in Figure
profiles 9a–c. The specific
of the
pacitance
CeO2 , Ce0.95 Mn0.05 O2 , and(CCe S) 0.95
values
Fe0.05 areO2determined
electrodes has using beenthe shown
following relation:
in Figure 9a–c. 𝑛𝐴
𝐶 The ∆𝑉 𝑚
nA
specific capacitance
where(CS )vvalues
denotes arethedetermined
scan rates (V/s), usingm the(g)following
is the mass relation: CS = material
of the active ∆V ×m×v ,deposited
where v denotesthe scan rates∆𝑉
theelectrode, 𝑉 represents
(V/s), m (g) is the themasspotentialof the window, and n = 1deposited
active material is used for the th
∆V (V ) represents
on the electrode,electrode cell. It is observed
the potential that the Cs values
window, and decrease
n = 1 iswithusedanfor increase in scan rates
the three-
mV s −1–100 mV s−1) from 205 Fּ g−1 to 120 Fּ g−1, 805 Fּ g−1 to 199 Fּ g−1, and 945 Fּ g−1 to
electrode cell. It is observed that the Cs values decrease with an increase in scan rates
(10 mV s−1 –100 mV Fּ g−1s−for
1 ) CeO
from2,205Ce0.95 g−10.05toO120
F·Mn 2, and g−0.95
F·Ce 1 , 805
Fe0.05FO ·g2,−respectively,
1 to 199 F·g−which 945 F·g−1the usual
1 , andindicates
− 1 formance of supercapacitors. Figure 9d describes
to 261 F·g for CeO2 , Ce0.95 Mn0.05 O2, and Ce0.95 Fe0.05 O2 , respectively, which indicates the comparison of thetheCs for diffe
electrodes and highlights that the Ce Fe
usual performance of supercapacitors. Figure 9d describes the comparison of the Cs for
0.95 0.05 O 2 electrode has the highest specific cap
tance value of 945 F∙g −1.
different electrodes and highlights that the Ce0.95 Fe0.05 O2 electrode has the highest specific
capacitance value of 945 F·g−1 .

Figure 8. CV plots of (a) CeO2 nanoparticles, (b) Ce0.95 Mn0.05 O2 nanoparticles, (c) Ce0.95 Fe0.05 O2
Figure 8. CV plots of (a) CeO2 nanoparticles, (b) Ce0.95Mn0.05O2 nanoparticles, (c) Ce0.95Fe0.05O2 n
nanoparticles with different scan rates (d) CV plots CeO2 , Ce0.95 Mn0.05 O2 , Ce0.95 Fe0.05 O2 nanoparti-
particles with different scan rates (d) CV plots CeO2, Ce0.95Mn0.05O2, Ce0.95Fe0.05O2 nanoparticles
cles at a scan rate of 10 rate
mV S −1 .
scan of 10mV S−1.
 Materials 2023, 16, x FOR PEER REVIEW 14 of 17

Materials 2023, 16, 2290 13 of 15

Figure 9. The specific capacitance of (a) CeO2 nanoparticles, (b) Ce0.95 Mn0.05 O2 nanoparticles,
Figure 9. The specific capacitance of (a) CeO2 nanoparticles, (b) Ce0.95Mn0.05O2 nanoparticles, (c)
(c) Ce0.95 Fe0.05 O2 nanoparticles with different scan rate (d) Variation in specific capacitance of CeO2 ,
Ce0.95Fe0.05O2 nanoparticles with different scan rate (d) Variation in specific capacitance of CeO2,
Ce Mn0.05 O2,, Ce
Ce0.95 Fe0.05 −1
0.95
Ce 0.95Mn 0.05O2 0.95Fe O2Onanoparticles
0.05 2 nanoparticles
at at a scan
a scan rate
rate ofof 10 mV
10mV S−1S
. .
4. Conclusions
4. Conclusions
The undoped and Ce0.95 X0.05 O2 (X: Fe, Mn) nanoparticles, synthesized using the
The undoped
coprecipitation route, and
areCe 0.95X0.05O2 (X: Fe, Mn) nanoparticles, synthesized using the co‐
studied for their structural, morphological, optical, magnetic,
precipitation route, are studied
electronic, and electrochemical properties. for their structural,
The Rietveld morphological,
refinement has optical,
revealedmagnetic, elec‐
the single-
tronic, and electrochemical properties. The Rietveld refinement
phase formation of the face-centered fluorite structure of CeO2 . The Fe and Mn have been has revealed the single‐
phase formation
successfully of the face‐centered
incorporated into the CeO fluorite structure of CeO2. The Fe and Mn have been
2 matrix. The lattice parameters and crystallite
successfully incorporated into the CeO 2 matrix. The lattice parameters and crystallite di‐
dimensions are found to be lowest for Fe-doped CeO2 , mainly because of the lowest ionic
mensions
radii of Fe asare found totobeMn
compared lowest for The
and Ce. Fe‐doped
reduced CeO 2, mainly because of the lowest ionic
dimensions led to the enhanced strain
radii of Fe as compared to Mn and Ce. The reduced
in Fe-doped CeO2 nanoparticles. The particle size obtained from dimensions ledtheto TEM
the enhanced
micrographsstrain
in Fe‐doped CeO 2 nanoparticles. The particle size obtained from
also favored the XRD results. The band gap is also found to be minimal for Fe-doped CeO2 the TEM micrographs
also favored the
nanoparticles. TheXRDRaman results.
spectraTherevealed
band gap theis maximum
also foundoxygen
to be minimal for Fe‐doped
non-stoichiometry inCeO
the 2
Fe-doped CeO2 nanoparticles. The ferromagnetism can be seen for all the nanoparticlesin
nanoparticles. The Raman spectra revealed the maximum oxygen non‐stoichiometry
the aFe‐doped
with CeO2 nanoparticles.
small hysteresis The ferromagnetism
at room temperature. The smallest value can be of seen for allmagnetization
saturation the nanoparti‐
clesthe
and with a small
magnetic hysteresis
moment at room
has been foundtemperature.
for pure CeO The
2 smallest
nanoparticles value and ofissaturation
observed tomag‐
be
netization
enhanced as and the magnetic
a consequence moment
of doping, hasthe
with been found
highest for pure
value for CeCeO F2 nanoparticles
0.95 0.05 2O and
nanoparticles. is
observed
The presence toofbeoxygen
enhanced as a isconsequence
vacancies confirmed byofRaman doping, andwith
NEXAFS the highest
analyses, value
which for
Ce0.95
also F0.05O2a nanoparticles.
exhibit mixed valenceThe statepresence
for Fe-ions (Fe3+ and
of oxygen Fe2+ ) and
vacancies is confirmed
Ce-ions (Ceby 3+ Raman
and Ce4+ and
).
NEXAFS
The analyses, which
cyclic voltammetry alsodemonstrate
results exhibit a mixed thatvalence
the Ce0.95state for
F0.05 O2Fe‐ions
electrode (Fe displayed
3+ and Fe )the
2+ and
Ce‐ions (Ce
maximum 3+ and
value Ce4+). The
of specific capacitance (945 F g−1 )results
cyclic voltammetry recorded at 10 mVs−that
demonstrate 1 scan
therate.
Ce0.95F0.05O2
electrode displayed the maximum value of specific capacitance (945 F g−1) recorded at 10
Author
mVs−1Contributions:
scan rate. Conceptualization, S.K.; data curation, N.M.S.; formal analysis, F.A., N.A.
and S.D.; investigation, F.A., N.M.S., N.A. and K.H.C.; resources, S.D. and K.H.C.; supervision, S.K.;
Materials 2023, 16, 2290 14 of 15

validation, S.K.; writing—original draft, S.K.; writing—review and editing, S.K., F.A., N.M.S., N.A.
and S.D. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Deputyship for Research and Innovation, Ministry of
Education in Saudi Arabia, for funding this research work through the project number INSTR002.
Data Availability Statement: Available on request.
Acknowledgments: The authors extend their appreciation to the Deputyship for Research and
Innovation, Ministry of Education in Saudi Arabia, for funding this research work through the project
number INSTR002.
Conflicts of Interest: The authors declare no conflict of interest.

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