Journal of Magnetism and Magnetic Materials 564 (2022) 170108

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Journal of Magnetism and Magnetic Materials

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Structure and magnetic properties of (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4

nanocrystalline high-entropy oxide synthesized using a sol-gel auto
combustion approach
Shanigaram Mallesh , Ji-Sub Noh , Young-Woo Nam *
School of Mechanical and Aerospace Engineering, Gyeongsang National University, Composite Structures Laboratory, 501, Jinju-daero, Jinju-si, Gyeongsangnam-do,
Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: A sol–gel auto-combustion method is used in this study to synthesize a new class of single-phase high-entropy
High-entropy oxide oxide (HEO) (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4. The as-synthesized compound exhibits a single-phase spinel
Sol–gel auto combustion structure with an 8.3224 Å lattice parameter and an average crystallite size of 10 nm as determined by X-ray
Spinel structure
diffraction (XRD) data analysis. Raman and Fourier transform infrared results are in agreement with the XRD
X-ray photoelectron spectroscopy
Magnetization
results. A scanning electron microscopy-based energy dispersed spectroscopy study suggests the formation of a
porous structured morphology with a uniform elemental distribution. In addition, high-resolution transmission
electron microscopy and surface analyses further confirm the formation of a pure spinel structure with a particle
size of 12–20 nm and a mesoporous character with a pore size of 4.55 nm. X-ray photoelectron spectroscopy
indicates mixed-valence states of elements (Mn, Fe, Co, and Ni) and their occupations over tetrahedral and
octahedral sites. The temperature-dependent magnetization exhibited a bifurcation between zero-field-cooled
and field-cooled magnetizations. From the M− H curves, the magnetization decreased monotonically with the
increase in temperature (M is 22 emu/g at 2 K and 7.2 emu/g at 300 K). The coercivity decreased by
approximately-one order of magnitude (HC = 1700 Oe at 2 K and HC = 200 Oe at 370 K). Finally, a compre­
hensive magnetic characterization of the as-synthesized HEO indicates their ferrimagnetic nature. The novel
physical properties of the as-synthesized HEO could be useful in various potential applications.

1. Introduction structures among others [5–9]. Owing to their excellent properties,

HEOs have been studied extensively for a variety of potential applica­
Recently, high-entropy oxides (HEOs) have received increased in­ tions, such as catalysts [10], lithium-ion batteries [11], electrochemical
terest owing to their superior physicochemical, catalytic, optical, ther­ water oxidation [12], dielectrics, and electromagnetics [13].
mal, mechanical, electrical, and magnetic properties [1–4]. HEOs are a Ferrites belonging to the cubic spinel structures (Fd-3m) have
new group of materials comprising at least five elements in equiatomic increased interest because their optical, magnetic, dielectric, and pho­
or nearly equiatomic proportions. Owing to the high entropy stabiliza­ tocatalytic properties are helpful in various potential applications
tion, single-phase solid solutions are more likely to form than multi­ [14,15]. The crystallographic unit cell of the spinels is expressed as
( 2+ 3+ )[ 3+ 2+ ]
phase solid solutions. In 2015, Rost et al. developed the first HEO M1− δ Feδ Fe2− δ Mδ O4 (M = Mg2+, Mn2+, Fe2+, Ni2+, Zn2+..). Here
(Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)O with a rocksalt structure [5]. They syn­ parentheses designate the tetrahedral sites, and the square brackets
thesized the single-phase HEO rocksalt structure by heating CoO, CuO, designate the octahedral sites. And the δ is known as the inversion
NiO, MgO, and ZnO oxide materials in an equimolar ratio at 900 ◦ C. parameter. The values of δ are 0 for normal and one inversion spinels,
Subsequently, several research groups have developed a variety of HEO and 0 < δ < 1 for mixed spinels [14–16]. It is well known from the
structures, including pyrochlore, fluorite, perovskite, and spinel literature that synthesis methods, processing conditions, and

Abbreviations: HEOs, High entropy oxides; SAED, selected area electron diffraction; BEs, binding energies; FWHM, full width at half maximum; M, magnetization;
HC, coercivity; ZFC, zero-field-cooled; FC, field-cooled; n(µB), magnetic moment per formula unit.
* Corresponding author.
E-mail address: [email protected] (Y.-W. Nam).

https://doi.org/10.1016/j.jmmm.2022.170108
Received 19 July 2022; Received in revised form 21 October 2022; Accepted 22 October 2022
Available online 27 October 2022
0304-8853/© 2022 Elsevier B.V. All rights reserved.
S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

compositions significantly influence spinel ferrites’ structural and 2. Materials and methods
physical properties. Supriya et al. reported the synthesis of super­
paramagnetic MnFe2O4 nanoparticles using a co-precipitation method 2.1. Chemicals
and magnetic hyperthermia characteristics for application in cancer
treatment [16]. Jadhav et al. studied the photocatalytic activity of High purity metal nitrates, Mg(NO3)2⋅4H2O, Zn(NO3)2⋅4H2O, Mn
NiFe2O4 nanoparticles for toxic dye removal applications [18]. Several (NO3)2⋅4H2O, Co(NO3)2⋅4H2O, Ni(NO3)2⋅4H2O, and Fe(NO3)3⋅9H2O
authors reported the influence of doping on structural and magnetic precursors were used in this study without further purification. Addi­
properties in binary and ternary spinel ferrites [14–19]. The structure tionally, ethylene glycol, 2-propanal, glycerol, and triethylamine were
and magnetic properties are significantly influenced by the high entropy used as solvents and reacting agents.
stabilization of multi-elements in HEOs will be interesting to evaluate.
In 2018, Dabrowa et al. reported the successful synthesis of a spinel- 2.2. Synthesis
type (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4 HEO spinel using high-energy ball
milling, followed by sintering the samples at 1050 ◦ C [9]. The formation The HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals were
of a stable single-phase spinel structure HEO has been confirmed using synthesized via a sol–gel auto combustion method, as previously
X-ray diffraction (XRD) and Raman characterizations. Later, Mao et al. demonstrated [26]. To prepare a typical solution, equimolar (0.025 M)
synthesized (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4 HEO nanoparticles via solu­ amounts of six cationic metal nitrate salts were dissolved in ethylene
tion combustion synthesis and annealed the samples in the temperature glycol and stabilized by adding drops of glycerol. The solution was
range of 623–1123 K. All the annealed samples exhibited ferrimagnetic heated at 90 ◦ C for 40 min under magnetic stirring and then cooled to
properties with random variation of the magnetic moment for various 30 ◦ C. To further increase the homogeneity and solubility of the solution
annealing temperatures [20]. Furthermore, they studied the structure for cationic salts, 2-propanal was added. Subsequently, triethylamine
and magnetic properties of (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4 HEO by was added to the solution. This was followed by magnetic stirring for
replacing Co and Ni with Zn. Their results indicated a decrease in approximately 30 min until a thick brown gel formed. The thick brown
magnetization when magnetic Co2+ or Ni2+ was substituted for gel was heated. The heating temperature was continuously increased to
nonmagnetic Zn2+ [21]. Styger et al. synthesized (Mg, Cr, Fe, Mn, initiate combustion. Combustion began when the heating temperature
Ni)3O4 and (Co, Cr, Fe, Mn, Mg)3O4 HEOs by substituting Mg for Co and reached 300 ◦ C. It took another hour at this heating temperature to
Ni and examined the electric conductivity of these systems [22]. An complete the reaction of the spinel structure formation. Finally, the
increase in electrical conductivity (102 – 103 S.m− 1) and activation en­ combusted powder was ground to obtain the as-synthesized HEO
ergies (0.3–0.6 eV) has been observed when the temperature increases nanocrystals for further characterization.
from 400 ◦ C to 1000 ◦ C). In 2021, Shaw et al. reported the ferrimagnetic
properties of (AlCoFeMnNi)3O4 HEO synthesized via microwave- 2.3. Characterization
assisted coprecipitation [23]. X-ray photoelectron spectroscopy (XPS)
results on the compound indicated that Fe3+ ions were present at both The phase formation of the as-synthesized HEO was investigated
tetrahedral and octahedral sites, whereas Al3+ was preferentially pre­ using XRD data (Rigaku, D/max 2000) with CuKα (λ = 1.54059 Å) line
sent at the octahedral site. Furthermore, they reported a decrease in the in a 2θ range of 20–80◦ . The vibrational characteristics of the samples
magnetic moment when Al was substituted for Cr in (CrCoFeMnNi)3O4. were studied using a Raman spectrometer (RAMANtouch) and Fourier
In 2020, Mao et al. used a combustion method to synthesize a novel transform infrared (FT-IR) spectrometer (Spectrum Two). Scanning
six-component (Al1/6Co1/6Cr1/6Mn1/6Ni1/6Fe1/6)3O4 oxide with a high- electron microscopy was used to characterize their morphology, porous
entropy spinel structure, [24]. The detailed temperature- and structure, and elements (SEM, Tescan, Mira3 LM). The microstructures
magnetic-field-dependent characterizations indicated a ferrimagnetic and nanoparticle sizes were investigated using high-resolution trans­
(3.16 to 13.42 emu/g) behavior of a stable high-entropy oxide in its mission electron microscopy (HR-TEM, H-7650). XPS was used to
native state, with a Curie temperature (TC) of 248 K [24]. Later, Zhu determine the surface composition and chemical structure (XPS, Thermo
et al. synthesized six-component (Al1/6Co1/6Cr1/6Mn1/6Ni1/6Fe1/6)3O4 Fisher Scientific Multilab 2000). Magnetic characterizations at temper­
HEOs via solution combustion synthesis and investigated the impacts of atures ranging from 2 to 370 K and magnetic fields up to 70 kOe were
annealing temperature and substitution of nonmagnetic Al for magnetic performed using a quantum design SQUID magnetic property mea­
Co, Mn, and Ni. Al substitutions for Mn and Ni resulted in increased surement system (MPMS3, Evercool).
magnetization when compared with that of Co substitutions [25]. An
XPS analysis revealed the various oxidation states of elements and their 3. Results and discussion
fractions. Therefore, the multiple elements, their oxidation states, and
their relative distributions across tetrahedral and octahedral sites The XRD pattern and Rietveld refinement of as-synthesized nano­
together contribute significantly to the magnetic properties of HEOs. crystalline HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 are depicted in
To the best of our knowledge, this is the first time that a novel six- Fig. 1. Refinement was performed using the GSAS software with the Fd-
component HEO nanocrystal with a single-phase spinel structure, 3 m (2 2 7) space group. We achieved best fit the for cationic distribution
(Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4, has been synthesized using a of (Zn0.5Mg0.2Mn0.2Fe0.1)[Mg0.3Mn0.3Fe0.4Ni0.5Co0.5] by trying the
one-pot sol–gel auto combustion process. The sol–gel combustion random variation of elements in tetrahedral and octahedral sites. The
method facilitates facile, large-scale synthesis of nanoparticles with the excellent agreement between experimental and calculated XRD patterns
desired crystal structure in a single-step synthesis [26]. The selection of with values of the weighted profile R-factor (Rwp), weighted factor (Rp),
the elements in the present compound is based on their similar atomic and goodness of the fit (χ2) were 3.84 %, 4.99 %, and 2.05, respectively,
numbers and solubilities for single-phase formation. Moreover, we indicating that nanocrystals formed a pure single-phase spinel structure
replaced Al and Cr with Zn and Mg. Zn occupies the tetrahedral site, free of impurities. In general, the crystallographic representation of the
whereas Al occupies the octahedral site. Therefore, the tetrahedral site cubic spinel ferrite unit cell is AFe2O4 (A = Mg2+, Mn2+, Fe2+, Ni2+,
preference of nonmagnetic Zn, as against the preferences of nonmag­ Zn2+). For normal spinels, divalent cations occupy tetrahedral sites,
netic Al to occupy the octahedral site, can increase the resultant mag­ whereas trivalent cations occupy octahedral sites. For inverse spinels,
netic moment. Microstructural, vibrational, and surface composition divalent cations prefer octahedral sites, whereas trivalent cations prefer
analyses confirmed the formation of single-phase HEO in as-synthesized tetrahedral and octahedral sites in equal proportions [26,27]. Addi­
nanocrystals. In addition, we examined the magnetic properties of HEO tionally, bulk ZnFe2O4 comprises a complete normal spinel [28],
in detail as functions of temperature and magnetic field. whereas bulk CoFe2O4 and NiFe2O4 comprise complete inverse spinels

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S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

[33–35]. The lattice parameter of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/

6)3O4 increased when compared with an earlier report on the six-
component HEO (Al1/6Co1/6Cr1/6Fe1/6Mn1/6Ni1/6Fe1/6)3O4 [24]. The
difference in the lattice parameters between this and other spinel HEOs
is attributed to the presence of mixed-valence cations and their random
distribution in tetrahedral and octahedral sites. The divalent cations
Mn2+, Fe2+, Co2+, Ni2+, and Zn2+ have cationic radii of 0.83 Å, 0.77 Å,
0.74 Å, 0.69 Å, and 0.74 Å, respectively. The trivalent cations Mn3+,
Fe3+, Co3+, and Ni3+ have cationic radii of 0.65 Å, 0.67 Å, 0.69 Å, and
0.6 Å, respectively [20–25,36,37]. Therefore, the increase in the lattice
parameter is caused by the substitution of divalent Mg2+ and Zn2+ for
trivalent Al3+ and Cr3+. However, although Mg2+ (0.65 Å) has a cationic
radius similar to that of Cr3+ (0.64 Å), Zn2+ (0.65 Å) has a larger cationic
radius than that of Al3+ (0.53 Å), thereby increasing the lattice param­
eter [20–25]. Furthermore, charge conversion from divalent to trivalent
or vice versa, the presence of multiple charge states to maintain charge
balance neutrality, and the relative distribution of cations between
tetrahedral and octahedral sites have a significant impact on the lattice
parameter. The experimental evidence for oxidation states and their
distribution over tetrahedral and octahedral sites will be discussed in
Fig. 1. Rietveld refinement of XRD patterns of as-synthesized HEO (Mg1/6Zn1/ detail later.
6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals. The Raman spectrum of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4
exhibits the Raman modes at 120, 336, 504, 533, 550–685 cm− 1, as
[29,30]. Furthermore, when divalent cations are present in both tetra­ depicted in Fig. 2(a). The observed results are in good agreement with
hedral and octahedral sites, the crystal structure is called mixed spinels. earlier reports on MnZn ferrites, Ni ferrites, and (Co, Cr, Fe, Mn, Ni)3O4
Conversely, ferrites composed of MgFe2O4, MnFe2O4, and MnZn exhibit [26–29,9]. Under normal conditions, the factor group theory expects
mixed spinel structures [26,31,32]. While the relative distribution of five Raman (A1g + Eg + 3T2g) modes for spinel ferrites. The A1g Raman
cations over tetrahedral and octahedral sites changes significantly from mode observed in the broad frequency range of 550–685 cm− 1 is
bulk to nanoscale, mixed spinels are formed [25–32]. Therefore, we attributed to the presence of multiple cations at the tetrahedral site. The
obtained the converges fit to the XRD in this present study based on A1g mode is ascribed to the symmetric stretching of oxygen ions in the
particular elements and their specific site distribution information from AO4 species. The T2g(2) mode observed at 504 cm− 1 is attributed to the
earlier reports [20–23]. asymmetric stretching of oxygen and octahedral site cations. The T2g(3)
The crystallite size was calculated using Scherrer’s equation as fol­ mode (533 cm− 1) is attributed to the asymmetric bending of oxygen ions
lows [15]. associated with octahedral cations. In contrast, the Eg and T2g(1) modes
at 336 and 120 cm− 1 are associated with symmetric bending vibration
0.9λ
t= (1) and the translational vibration mode, respectively [26]. The FTIR
βcosθ
spectra of the HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 are presented
where λ is the X-ray wavelength, β is the full-width at half-maximum, in Fig. 2(b). For spinel ferrites, the two main broad metal–oxygen bonds
and θ is the diffraction peak angle. The calculated average crystallite size are observed in FTIR spectra. The υ2 mode detected around 614 cm− 1 is
is 10 nm. caused by the intrinsic stretching vibration of metal cations at the
The lattice constant evaluated from Rietveld refinement of XRD tetrahedral site Mtetra ↔ O, whereas the υ1 mode around 483 cm− 1 is
pattern as follows. attributed to the intrinsic stretching vibration of metal cations at the
octahedral site MOcta ↔ O [25]. Therefore, the Raman and FT-IR
λ
a = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅ (2) vibrational characterizations further confirm the formation of the pure
sin2 θ
2 h2 +k 2 +l2 spinel phase in as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/
6)3O4 and corroborate well with XRD results.
where θ is the Bragg angle for the (hkl) reflection. Further, the
To study the structural stability as a function of temperature, we
hopping lengths (LA and LB) are evaluated as follows [33,34].
have performed a TGA-DSC analysis in the temperature range from 30 to
1000 ◦ C at a ramp rate of 10 ◦ C min− 1 for HEO (Mg1/6Zn1/6Mn1/6Co1/
√̅̅̅
3
(3)
6Ni1/6Fe1/6)3O4, as depicted in Fig. 3. We have noticed a weight loss of
LA = a
4
about 6.3 % in the temperature region of 30–420 ◦ C, and the DSC curve
√̅̅̅
2 displayed an exothermic peak corresponding to the sample weight loss,
LB = a (4)
4 associated with the decomposition of the sample and combustion of
Ethylene glycol (EG decomposition temperature is ~ 400 ◦ C) [26]. We
The values of the lattice parameter, LA, and LB are 8.3224 Å, 3.6037
have observed a slight increase of sample mass (0.3) in the temperature
Å, and 2.9424 Å, respectively.
range of 500 ◦ C to 800 ◦ C, resulting in an oxidation peak at approxi­
The tetrahedral and octahedral bond lengths (dAx and dBx) are as
mately 555 ◦ C. These observations agree with the previous reports on
follows [33–35].
HEOs [25]. Thermal analysis showed that the spinel structure of the as-
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
)̅
(
1 prepared HEO is stable up to 555 ◦ C and slightly oxidized above this
dAX = a 3 u − (5) temperature.
4
The SEM images, EDX pattern, and element mapping were used to
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ investigate the morphology, microstructure, chemical composition, and
11 43
dBX = a 3u2 − u+ (6) elemental distribution of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4
4 64
nanoparticles (Fig. 4). The SEM images of the as-synthesized sample
The values of the dAx, and dBx are 1.8475 Å, and 2.05446 Å, indicate a porous structure caused by gas release during the auto com­
respectively. These results are in agreement with previous reports bustion process (Fig. 4(a–c)) [38]. These results are consistent with

3
S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

Fig. 2. (a) Raman and (b) FT-IR spectra of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals.

compositions [24,25]. The EDX analysis indicates the presence of Mg,

Zn, Mn, Fe, Co, Ni, and O elements in the as-synthesized HEOs. The
additional peak in the EDX spectrum is due to the Pt coating on the
surface of the sample [Fig. 4(d)]. Element mapping revealed that the
distribution of elements are more or less uniform, as depicted in Fig. 4
(e). The atomic and weight ratios of Mg, Zn, Mn Co, Ni, Fe, and O ob­
tained from the EDX pattern and theory values are listed in Table (inset
of EDX pattern). These values were determined by analyzing the
chemical composition of the powder using the EDX pattern. The atomic
percentages of elements evaluated from the experiment are considerably
near with the desired ratios for HEO. However, the difference in weight
ratios of Mg and Zn is due to the difference in their atomic masses. The
results demonstrate that the as-synthesized HEO, a desired single-phase
spinel structure, was successfully formed using many elements, as
confirmed by XRD and Raman analyses.
The morphology and the size of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/
6Fe1/6)3O4 nanoparticles are depicted in Fig. 5. It is evident from Fig. 5
(a,b) that HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 has a porous
Fig. 3. TGA-DSC profiles of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/ structure, with an irregular cross-linked nanoparticle size of 12–20 nm.
6Fe1/6)3O4 nanocrystals. The HR-TEM image in Fig. 5(c) depicts the lattice fringes of 0.21, 0.25,
and 0.49 nm belonging to the (4 0 0), (3 1 1), and (1 1 1) crystal planes of
those obtained from the solution combustion synthesis of similar HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanoparticles. Further, the

Fig. 4. (a–c) FESEM images, (d) EDX pattern (inset Table; the measured atomic and weight ratios were compared with desired stoichiometric values), and (e)
element mapping of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals.

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S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

Fig. 5. (a,b) TEM images, (c) HR TEM image, and (d) SAED pattern of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals.

selected area electron diffraction pattern (SAED) analysis suggests a

polycrystalline structure of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4,
as shown in Fig. 5(d). The observed diffraction rings match well with
lattice planes (2 2 0), (3 1 1), (4 0 0), (5 1 1), and (4 4 0). The HR-TEM
analysis further confirms the formation of a pure spinel structure and
supports the results obtained from structural and vibrational
characterizations.
To further investigate the specific surface area, porous characteris­
tics of HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanoparticles, ‘Bru­
nauer-Emmett-Teller’ (BET) N2 gas adsorption–desorption experiments
were carried out at 77 K as depicted in Fig. 6 with inset corresponding to
Barrett- Joyne-Halenda (BJH) pore size distribution. Fig. 6 reveals the
Type V N2 adsorption isotherm with a type H1 hysteresis loop [33,35].
This result indicates the mesoporous feature of the sample. The pore size
distribution curve reveals the mesoporous character of the nano­
structure. From BET analysis, we have obtained a specific surface area of
32.577 m2/g and a pore volume of 0.0317 cm3/g with a pore size of 4.55
nm.
XPS is a powerful technique to analyze the surface composition,
oxidation states, and relative cationic distributions over tetrahedral and
Fig. 6. BET N2 adsorption–desorption curves and the pore size distribution
octahedral sites. The photoelectrons emitted from the 2p core level
(inset) of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4
contain different binding energies (BEs) related to different oxidation
nanocrystals.
states [36–39]. Based on the BEs of the elements and full width at half
maximum (FWHM), several authors have investigated various spinel
Mn3+ at 641.8 (61.6 %), and Mn4+ at 643.6 (20.6 %), respectively [42].
structures addressing the oxidation states of cations and their presence
In Co3O4, Co 2p3/2 spectrum reported the peak at 779.6 eV assigned to
over tetrahedral and octahedral sites. In MgAl2O4, the BE (FWHM) for
the Co3+ at the octahedral site and 781.2 eV assigned to the Co2+ at the
Mg 2p is reported at 49.8 eV (3.00 eV) assigned Mg2+ [40]. The XPS
tetrahedral site. The relative concentration of Co3+/Co2+ is about 45.42
spectrum of Ni substituted MnZn ferrites; the Zn 2p3/2 revealed a peak at
% [36]. In nickel ferrite, the 2p3/2 spectrum, the BEs of Ni2+ (octahedral)
1021.0 eV with an FWHM value of 2.0 eV associated with Zn2+ at the
and Ni3+(tetrahedral) are reported at 854.4 eV, and 856.0 eV with
tetrahedral site [41]. The Mn 2p3/2 core-level photoelectron spectrum
relative concentrations of 66.3 % and 32.7 % [36,41,42]. Thota et al.
observed different peaks with their fractions Mn2+ at 640.4 (17.8 %),

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S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

reported BEs (FWHM) at 710.8 and 713.2 (3.2) eV corresponding to the ions in octahedral and Mn4+ ions in octahedral are 18.36 %, 66.17 %,
Fe3+ (octahedral sites) and Fe3+ (tetrahedral sites) ions, respectively. and 15.47 %, respectively. As illustrated in Fig. 7(e), the high-resolution
Whereas, the 2p3/2 core-level spectrum reported BEs (FWHM) at 709.3 XPS spectrum of Co 2p exhibits two main peak positions at 781.7 and
(2.3), 710.8(2.3), and 712.9(2.6) eV, ascribed to Fe2+ (tetrahedral sites), 796.2 eV associated with Co 2p3/2 and Co 2p1/2, respectively [42].
Fe3+ (octahedral sites), and Fe3+ (tetrahedral sites), respectively [14]. Deconvolution of high-resolution XPS spectra of Co revealed peaks at
The broad XPS spectrum of the sample (Fig. 7(a)) demonstrates the 780.5 eV (Co 2p3/2) and 795.8 eV (Co 2p1/2) corresponding to the Co3+
presence of Mg, Zn, Mn, Co, Ni, Fe, and O elements in the as-synthesized state at octahedral, and peaks at 783.1 eV (Co 2p3/2) and 797.5 eV (Co
HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 [39]. From the high- 2p1/2) corresponding to the Co2+ state at tetrahedral. Furthermore, two
resolution XPS spectra, we obtained various BEs of the peaks, their satellite peak positions for Co 2p3/2 and Co 2p1/2 at 785.4 and 802.9 eV,
FWHM values, and percentages of cations in tetrahedral and octahedral respectively, confirm the presence of Co2+ and Co3+ states [23,42].
sites (evaluated using the areas under the curves). Mg 2p exhibits a Therefore, for Co 2p3/2, the relative contributions of Co3+ at octahedral
characteristic Mg2+ peak at 49 eV in its high-resolution XPS spectrum, as and Co2+ at tetrahedral sites are 77.33 % and 22.67 %, respectively.
depicted in Fig. 7(b) [40]. The binding energies (FWHM) of Zn 2p at Furthermore, the peaks in the Ni spectrum at 855.5 eV (Ni 2p3/2) and
1022.5 (1.85) and 1045.7 eV (1.92) are consistent with those of Zn 2p3/2 873.8 eV (Ni 2p1/2) correspond to the Ni2+ species contributions from
and Zn 2p1/2, respectively, thereby confirming the Zn2+ state occupying octahedral, whereas the peaks at 856.6 eV (Ni 2p3/2) and 874.4 eV (Ni
the tetrahedral site [41]. The high-resolution Mn XPS spectrum confirms 2p1/2) correspond to the Ni3+ species contributions from tetrahedral, as
two prominent peaks corresponding to Mn 2p3/2 and Mn 2p1/2. The illustrated in Fig. 7(f) [41,43]. Therefore, for Ni 2p3/2, the relative
deconvolution of the Mn XPS spectrum suggests that the two peaks at contributions of Ni2+ at octahedral and Ni3+ at tetrahedral are 69.12 %
640.5 eV (Mn 2p3/2) and 652.1 eV (Mn 2p1/2) correspond to the Mn2+ and 30.82 %, respectively. Moreover, Fe 2p3/2 and Fe 2p1/2 exhibit two
state, whereas the two binding energy positions at 641.7 eV and 653.8 representative binding energies in the high-resolution XPS spectra. The
eV correspond to the Mn3+ state. Furthermore, the peaks at 643.7 eV fit indicates that the peaks at 710.0 and 711.8 eV correspond to Fe2+ and
(Mn 2p3/2) and 659.0 eV (Mn 2p1/2) could be attributed to the Mn4+ Fe3+ in Fe 2p3/2, respectively, and the peak at 724.4 eV corresponds to
species as depicted in Fig. 7(d) [41,42]. For Mn 2p3/2, the relative Fe 2p1/2 (Fig. 7(g)) [41–44]. For Fe 2p3/2, the relative contributions of
contributions to the complete intensity of Mn2+ in tetrahedral and Mn3+ Fe2+ at tetrahedral and Fe3+ at octahedral are 59.86 % and 40.14 %,

Fig. 7. (a) wide-scan and (b–h) high-resolution XPS spectra of as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals.

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S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

respectively. Furthermore, the O 1 s spectra indicate that the peaks at 70 kOe. Fig. 9(b) depicts the explicit hysteresis loops observed at the
529.5, 531.2, 532.3, and 532.4 eV correspond to lattice oxygen (O Latt, measured temperatures and indicates the ferrimagnetic nature of the
M− O), oxygen vacancy (OV), and surface absorbed species (Os), system [23,24]. Fig. 9(c) illustrates the initial magnetization prolifera­
respectively (Fig. 7(h)) [39,42]. The percentages of OL, OV, and Os are tion at low magnetic fields, followed by a linear increase (non-situation)
49.73, 29.59, and 20.68, respectively. at high magnetic fields. Magnetization is non-saturating even at low
Fig. 8 depicts the temperature-dependent zero-field-cooled (ZFC) temperatures and high magnetic fields due to cationic and surface dis­
and field-cooled (FC) magnetizations of the sample determined in the orders caused by symmetry-breaking effects [23,24]. Magnetization (M)
temperature range of 2–370 K in the presence of various magnetic fields at 70 kOe and coercivity (HC) (derived from the M− H curves) are plotted
(100 Oe and 1000 Oe). The magnetization of the ZFC exhibits a broad as a function of temperature, as shown in Fig. 9(d). M is 22 emu/g at 2 K
peak around 280 K and then decreases as the temperature decreases. and decreases monotonically with an increase in temperature to 7.2
Furthermore, the ZFC and FC curves exhibit strong bifurcation in the emu/g at 300 K. At 2 K, a large value of HC = 1700 Oe is observed. When
measured temperature range, indicating the presence of ferrimagnetic the temperature reaches 370 K, it decreases by approximately-one order
interactions in the sample [45]. The FC magnetization increases rapidly of magnitude (HC = 200 Oe). The decrease in HC is rapid up to 50 K; it
as the temperature decreases, which is typical of noninteracting mag­ normally decreases above 50 K. At low temperatures, the large value of
netic particles [46,47]. In addition, the bifurcation between the ZFC and HC is again attributed to the magnetic anisotropy of the system [47,48].
FC curves increases as temperature decreases, which is attributed to the The magnetic properties are in agreement with previous reports on
high anisotropy energy due to magneto-crystalline and surface energy similar compositions [12,13,20–24]. The values of M (4.85–15.98 emu/
[47,48]. Magnetization curves for ZFC and FC are similar to those for g) and HC (176.5–21.39 Oe) were achieved at room temperature for the
magnetization in 100 Oe when measured with a field of 1000 Oe. HEO (CoCrFeMnNi)3O4 annealed at various temperatures (523–1123 K)
However, the ZFC peak (140 K) and irreversible temperature (270 K) are [20]. The M (9.86 emu/g) and HC (183 Oe) values reported for the HEO
significantly shifted to lower temperatures, indicating a decrease in (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)3O4 decreased to 8.08 emu/g and 5.60 emu/g
anisotropy energy as the applied magnetic field increases [47,48]. and 64.47 Oe and 90.86 Oe, respectively, when Co and Ni were replaced
To gain a deeper understanding of the magnetic behavior of the with Zn [21]. Further, in the HEO (AlCoFeMnNi)3O4, M and HC values
sample, we measured the magnetic field-dependent magnetization at reported at 2 K and 300 K are 29.15 and 14.25 emu/g and 2630 and 25.4
several fixed temperatures, as illustrated in Fig. 9(a). At all measured Oe, respectively [22]. The magnetic properties of the HEO (Mg1/6Zn1/
temperatures, the M− H curves exhibited no saturation tendency up to 6Mn1/6Co1/6Ni1/6Fe1/6)3O4 system described in this report were
enhanced compared with those reported previously on HEO (Al1/6Co1/
6Cr1/6Mn1/6Ni1/6Fe1/6)3O4. At 50 K, magnetic parameters M, MR, and
HC were 13.4, 5.3 emu/g, and 2277.6 Oe, respectively; at 300 K, they
were 3.2, 0.2 emu/g, and 205.4 Oe, respectively [24]. Owing to the
addition of nonmagnetic Al3+, the magnetic moment was reduced in
comparison to the five-component HEO (CoCrFeMnNi)3O4 [25]. Previ­
ous research has established that nonmagnetic Al3+ , which preferentially
occupies the octahedral, reduces the net magnetic moment. We
enhanced the magnetic moment in the present study by substituting
Zn2+ and Mg2+ for Al3+ and Cr3+. Nonmagnetic Zn2+, which preferen­
tially occupies the tetrahedral site, decreases the A-sublattice magnetic
moment, whereas the ferrimagnetic moment increases as a result of the
presence of magnetic cations at octahedral sites (B-sublattice). There­
fore, the net magnetic moment in spinel ferrites is expressed as MB – MA,
where MB and MA indicate the octahedral and tetrahedral magnetic
moments. The magnetic moment (nµB) per formula unit was calculated
as follows:
Mol.wt × MS
n(μB ) = (7)
5585
where MS is the saturation magnetization (emu/g) measured for
M− H curves at various temperatures. Neel’s two sublattice model [49]
and Chikazumi’s approach [50] considered that the site occupation of
cations mainly contributes to the resultant magnetic moment, and other
effects, such as the finite size and surface, were negligible. The values of
the calculated magnetic moments were 0.75, 0.77, 0.66, 0.45, and 0.34
µB for the M− H curves measured at 2, 10, 100, 200, and 300 K,
respectively. The decrease in a magnetic moment with an increase in
temperature is attributed to the increase in the thermal fluctuations in
the sample. We used the XPS analysis to obtain various oxidation states
of elements. Based on oxidation states and their magnetic moments
[Zn2+(0 µB), Mg2+(1 µB), Mn2+(5 µB), Mn3+(4 µB), Mn4+(3 µB), Co2+(3
µB), Co3+(4 µB), Ni2+(2 µB), Ni3+(1 µB), Fe2+(4 µB) and Fe3+(5 µB)] of
cations [20–25]. The cationic distribution for magnetic moment 0.75 µB
obtained for the M− H at 2 K is expressed as (Zn0.3Mn0.3Co0.1Fe0.3)
[Zn0.2Mn0.2Co0.4Fe0.2Ni0.5Mg0.5]O4, where round and square brackets
represent the tetrahedral (A) and octahedral (B) sites, respectively. The
estimated magnetic moment for the given cation distribution is
Fig. 8. ZFC and FC magnetization curves of as-synthesized HEO (Mg1/6Zn1/
approximately 0.9 µB. The difference between the calculated and
6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals obtained under various mag­
netic fields. experimental magnetic moment values can be ascribed to the presence

7
S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

Fig. 9. (a–c) M− H curves, low field M− H curves, and initial magnetization obtained at various temperatures, respectively; (d) M and HC plotted as functions of
temperature for as-synthesized HEO (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/6)3O4 nanocrystals.

of multiple elements, sizes, and surface features of the sample. There­ Supervision.
fore, advanced characterizations are needed to understand the spin
configuration over tetrahedral and octahedral sites when multiple cat­
ions are present in the system. Declaration of Competing Interest

4. Conclusions The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
A sol–gel auto combustion method was used to successfully synthe­ the work reported in this paper.
size a new class of single-phase HEOs (Mg1/6Zn1/6Mn1/6Co1/6Ni1/6Fe1/
Data availability
6)3O4. The XRD, Raman, and FT-IR analyses revealed the formation of a
single-phase spinel structure in the as-prepared sample. SEM and TEM
analyses confirmed the formation of a porous structure and the uniform Data will be made available on request.
distribution of elements throughout the system with an average particle
size of 12–20 nm. BET analysis obtained a specific surface area of Acknowledgments
32.577 m2/g and a pore volume of 0.0317 cm3/g with a pore size of
4.55 nm. The surface composition analysis revealed that (Mg2+, Zn2+, This study was supported by the National Research Foundation of
Mn2+/3+/4+, Co2+/3+, Ni2+/3+, and Fe2+/3+) cations have mixed valance Korea, South Korea, grant funded by the Ministry of Science and ICT
states. Furthermore, the temperature- and field-dependent magnetiza­ (NRF-2020R1C1C1006166) and the National R&D Program through the
tion analyses revealed the ferrimagnetic behavior of the sample. The National Research Foundation of Korea, South Korea, funded by the
magnetic properties of cations are intimately related to their valence Ministry of Science and ICT (NRF-2017R1A5A1015311).
states and their distribution over tetrahedral and octahedral sites. This
study described a facile and low-cost method for the synthesis of a novel References
equiatomic six-element HEO. The superior physical/chemical properties
of the synthesized HEO make it useful for a broad range of potential [1] H. Xiang, Y. Xing, F.-Z. Dai, H. Wang, L. Su, L. Miao, G. Zhang, Y. Wang, X. Qi,
L. Yao, H. Wang, B. Zhao, J. Li, Y. Zhou, High entropy ceramics: present status,
applications.
challenges and a look forward, J. Adv. Ceram. 10 (3) (2021) 385–441, https://doi.
org/10.1007/s40145-021-0477-y.
[2] A. Sarkar, Q. Wang, A. Schiele, M.R. Chellali, S.S. Bhattacharya, D.i. Wang,
CRediT authorship contribution statement
T. Brezesinski, H. Hahn, L. Velasco, B. Breitung, High-entropy oxides: Fundamental
aspects and electrochemical properties, Adv. Mater. 31 (26) (2019) 1806236,
Shanigaram Mallesh: Conceptualization, Data curation, Formal https://doi.org/10.1002/adma.201806236.
analysis, Investigation, Methodology, Writing – original draft, Writing – [3] Y. Sun, S. Dai, High-entropy materials for catalysis: a new frontier, Sci. Adv. 7
(2021) 1, https://doi.org/10.1126/sciadv.abg1600.
review & editing. Ji-Sub Noh: Data curation, Methodology. Young- [4] A. Sarkar, R. Kruk, H. Hahn, Magnetic properties of high entropy oxides, Dalton
Woo Nam: Funding acquisition, Project administration, Resources, Trans. 50 (6) (2021) 1973–1982, https://doi.org/10.1039/D0DT04154H.

8
S. Mallesh et al. Journal of Magnetism and Magnetic Materials 564 (2022) 170108

[5] C.M. Rost, E. Sachet, T. Borman, A. Moballegh, E.C. Dickey, D. Hou, J.L. Jones, [26] S. Mallesh, V. Srinivas, A comprehensive study on thermal stability and magnetic
S. Curtarolo, J.-P. Maria, Entropy-stabilized oxides, Nat. Commun. 6 (1) (2015), properties of MnZn-ferrite nanoparticles, J. Magn. Magn. Mater. 475 (2019)
https://doi.org/10.1038/ncomms9485. 290–303, https://doi.org/10.1016/j.jmmm.2018.11.052.
[6] Z. Teng, L. Zhu, Y. Tan, S. Zeng, Y. Xia, Y. Wang, H. Zhang, Synthesis and structure [27] C.N. Chinnasamy, A. Narayanasamy, N. Ponpandian, K. Chattopadyay, K. Shinoda,
of high-entropy oxides, J. Eur. Ceram. Soc. 40 (2020) 1639–1643, https://doi.org/ B. Jayadevan, K. Tohji, K. Nakatsuka, T. Furubayashi, Nakatani, Mixed spinel
10.1016/j.jeurceramsoc.2019.12.008. structure in nanocrystalline NiFe2O4, Phys. Rev. B 63 (2001) 184108, doi:
[7] J. Gild, M. Samiee, J.L. Braun, T. Harrington, H. Vega, P.E. Hopkins, K. Vecchio, 10.1103/PhysRevB.63.184108.
J. Luo, High-entropy fluorite oxides, J. Eur. Ceram. Soc. 38 (10) (2018) [28] S. Mallesh, M. Vasundhara, V. Srinivas, The effect of cationic disorder on low
3578–3584, https://doi.org/10.1016/j.jeurceramsoc.2018.04.010. temperature magnetic properties of MnZn ferrite nanoparticles, IEEE Trans. Magn.
[8] S. Jiang, T. Hu, J. Gild, N. Zhou, J. Nie, M. Qin, T. Harrington, K. Vecchio, J. Luo, 51 (11) (2015) 1–4, https://doi.org/10.1109/TMAG.2015.2440478.
A new class of high-entropy perovskite oxides, Scripta Mater. 142 (2018) 116–120, [29] X. Zeng, J. Zhang, S. Zhu, X. Deng, H. Ma, J. Zhang, Q. Zhang, P. Li, D. Xue, N.
https://doi.org/10.1016/j.scriptamat.2017.08.040. J. Mellors, X. Zhang, Y. Peng, Direct observation of cation distribution of ideal
[9] J. Dąbrowa, M. Stygar, A. Mikuła, A. Knapik, K. Mroczka, W. Tejchman, inverse spinel CoFe2O4 nanofibers and correlated magnetic properties, Nanoscale 9
M. Danielewski, M. Martin, Ni)3O4 high entropy oxide characterized by spinel (2017) 7493–7500, https://doi.org/10.1039/C7NR02013A.
structure, Mater. Lett. 216 (2018) 32–36, https://doi.org/10.1016/j. [30] V.G. Ivanov, M.V. Abrashev, M.N. Ilive, M.M. Gospondinov, J. Meen, M.I. Aroyo,
matlet.2017.12.148. Short-range B-site ordering in spinel ferrite NiFe2O4, Phys. Rev. B 82 (2010),
[10] S.H. Albedwawi, A. Aljaberi, G.N. Haidenopoulos, K. Polychronopoulou, High 024104, https://doi.org/10.1103/PhysRevB.82.024104.
entropy oxides-exploring a paradigm of promising catalysts, Mater. Des. 202 [31] S. Mallesh, D. Prabu, V. Srinivas, Thermal stability and magnetic properties of
(2021), 109534, https://doi.org/10.1016/j.matdes.2021.109534. MgFe2O4@ZnO nanoparticles. AIP Adv. 7 (2017) 056103, doi: 10.1063/
[11] Q. Wang, A. Sarkar, D.i. Wang, L. Velasco, R. Azmi, S.S. Bhattacharya, T. Bergfeldt, 1.4975355.
A. Düvel, P. Heitjans, T. Brezesinski, H. Hahn, B. Breitung, Multi-anionic and [32] B.D. Cullity, C. Graham, Introduction to magnetic materials, Jhon Wiley and Sons
-cationic compounds: new high entropy materials for advanced Li-ion batteries, Inc., Publications, Piscataway, NJ, 2009.
Energy. Environ. Sci. 12 (8) (2019) 2433–2442, https://doi.org/10.1039/ [33] S.B. Somvanshi, M.V. Khedkar, P.B. Kharat, K.M. Jadhav, Influential diamagnetic
C9EE00368A. magnesium (Mg2+) ion substitution in nano-spinel zinc ferrite (ZnFe2O4): thermal,
[12] D. Wang, Z. Liu, S. Du, Y. Zhang, H. Li, Z. Xiao, W. Chen, R.u. Chen, Y. Wang, spectral and physisorption analysis, Ceram. Int. 46 (2020) 8640–8650, https://doi.
Y. Zou, S. Wang, Low-temperature synthesis of small-sized high-entropy oxides for org/10.1016/j.ceramint.2019.12.097.
water oxidation, J. Mater. Chem. A 7 (42) (2019) 24211–24216, https://doi.org/ [34] V.A. Bharati, S.B. Somvanshi, A.V. Humbe, V.D. Murumkar, V.V. Sondur, K.
10.1039/C9TA08740K. M. Jadhav, Influence of trivalent Al-Co co-substitution on the structural,
[13] A. Randon, L. Hawelek, D. Lukowiec, J. Kubacki, P. Wlodarczyk, Dielectric and morphological and Mossbauer properties of nickel ferrite nanoparticles, J. Alloy.
electromagnetic interference shielding properties of high entropy (Zn, Fe, Ni, Mg, Compd. 821 (2020), 153501, https://doi.org/10.1016/j.jallcom.2019.153501.
Cd)Fe2O4 ferrite, Sci. Rep. 9 (2019) 20078, https://doi.org/10.1038/s41598-019- [35] S.B. Somvanshi, S.A. Jadhav, M.V. Khedkar, P.B. Kharat, S.D. More, K.M. Jadhav,
56586-6. Structural, thermal, spectral, optical and surface analysis of rare earth metal ion
[14] S. Mallesh, P. Mondal, S. Kavita, V. Srinivas, Y.-W. Nam, Effect of Ni substitution (Gd3+) doped mixed Zn-Mg nano-spinel ferrites, Ceram. Int. 46 (9) (2020)
and annealing temperature on structural and magnetic properties of MnZn-Ferrites: 13170–13179, https://doi.org/10.1016/j.ceramint.2020.02.091.
cytotoxicity study of ZnO and SiO2 coated core shell structures, Appl. Surf. Sci. 605 [36] F. Qu, N. Zhang, D. Liu, S. Zhang, B. Talluri, Y. Zheng, B. Talluri, Y. Zheng,
(2022) 154648, https://doi.org/10.1016/j.apsusc.2022.154648. T. Thomas, R. Zhao, S. Ruan, M. Yang, Engineering Co3+ cations in Co3O4
[15] S.B. Somvanshi, S.R. Patade, D.D. Andhare, S.A. Jadhav, M.V. Khedkar, P. multishelled microspheres by Mn doping: the roles of Co3+ and oxygen species for
B. Kharat, P.P. Khirade, K.M. Jadhav, Hyperthermic evaluation of oleic acid coated sensitive xylene detection, Sens. Actuat. B. Chem. 308 (2020), 127651, https://doi.
nano-spinel magnesium ferrite: enhancement via hydrophobic-to-hydrophilic org/10.1016/j.snb.2019.127651.
surface transformation, J. Alloy. Compd. 835 (2020) 155422, https://doi.org/ [37] S. Joshi, V.B. Kamble, M. Kumar, A.M. Umarji, G. Srivastava, Nickel substitution
10.1016/j.jallcom.2020.155422. induced effects on gas sensing properties of cobalt ferrite nanoparticles, J. Alloy.
[16] S.R. Patade, D.D. Andhare, S.B. Somvanshi, S.A. Jadhav, M.V. Khedkar, K. Compd. 654 (2016) 460–466, https://doi.org/10.1016/j.jallcom.2015.09.119.
M. Jadhav, Self-heating evaluation of superparamagnetic MnFe2O4 nanoparticles [38] A. Ashok, A. Kumar, J. Ponraj, S.A. Mansour, Preparation of mesoporous/
for magnetic fluid hyperthermia application towards cancer treatment, Ceram. Int. microporous MnCo2O4 and nanocubic MnCr2O4 using a single step solution
46 (16) (2020) 25576–25583, https://doi.org/10.1016/j.ceramint.2020.07.029. combustion synthesis for bifunction oxygen electrocatalysis, J. Electrochem Soc.
[17] P.B. Kharat, S.B. Somvanshi, P.P. Khirade, K.M. Jadhav, Induction heating analysis 167 (5) (2020) 054507, https://doi.org/10.1149/1945-7111/ab679d.
of surface-functionalized nanoscale CoFe2O4 for magnetic fluid hyperthermia [39] J.F. Moulder, W.E. Stickle, P.E. Sobol, K.D. Bomben, Handbook of X-ray Photo-
application toward noninvasive cancer treatment, ACS Omaga 5 (2020) electron Spectroscopy, Perkin Elmer Corporation, 1992.
23378–23384, https://doi.org/10.1021/acsomega.0c03332. [40] B.R. Strohmeier, Magnesium aluminate (MnAl2O4) by XPS, Surf. Sci. Spectra 3
[18] S.A. Jadhav, M.V. Khedkar, S.B. Somvanshi, K.M. Jadhav, Magnetically retrievable (1994) 121, https://doi.org/10.1116/1.1247772.
nanoscale nickel ferrites: an active photocatalyst for toxic dye removal [41] S. Thota, S. Kashyap, S. Sharma, V.R. Reddy, Cation distribution in Ni-substituted
applications, Ceram. Int. 47 (20) (2021) 28623–28633, https://doi.org/10.1016/j. Mn0.5Zn0.5Fe2O4 nanoparticles: a Raman, Mossbauer, X-ray diffraction and
ceramint.2021.07.021. electron spectroscopy study, Mater. Sci. Eng. B 206 (2016) 69–78, https://doi.org/
[19] S. Mallesh, W. Jang, K.H. Kim, Synthesis and electromagnetic properties of porous 10.1016/j.mseb.2016.01.002.
MnFeCoO4 structures by a facile sol-gel auto combustion method, Appl. Surf. Sci. [42] T.X. Nguyen, J. Patra, J.-K. Chang, J.-M. Ting, High entropy spinel oxide
553 (2021) 149532, https://doi.org/10.1016/j.apsusc.2021.149532. nanoparticles for superior lithiation-delithiation performance, J. Mater. Chem. A 8
[20] A. Mao, F. Quan, H.Z. Xiang, Z.-G. Zhang, K. Kuramoto, A.-L. Xia, Facile synthesis (36) (2020) 18963–18973, https://doi.org/10.1039/D0TA04844E.
and ferrimagnetic properties of (CoCrFeMnNi)3O4 high-entropy oxide [43] N.S. McIntyre, M.G. Cook, X-ray photoelectron studies on some oxides and
nanocrystalline powder, J. Mol. Strut. 1194 (2019) 11–18, https://doi.org/ hydroxides of cobalt, nickel, and copper, Anal. Chem. 47 (13) (1975) 2208–2213,
10.1016/j.molstruc.2019.05.073. https://doi.org/10.1021/ac60363a034.
[21] A. Mao, H.-Z. Xiang, Z.-G. Zhang, K. Kuramoto, H. Zhang, Y. Jia, A new class of [44] H. Bi, S. Li, Y. Zhang, Y. Du, Ferromagnetic-like behavior of ultrafine NiO
spinel high entropy oxides with controllable magnetic properties, J. Magn. Magn. nanocrystallites, J. Magn. Magn. Mater. 277 (3) (2004) 363–367, https://doi.org/
Mater. 497 (2020) 165884, https://doi.org/10.1016/j.jmmm.2019.165884. 10.1016/j.jmmm.2003.11.017.
[22] M. Stygar, J. Dabrowa, M. Mozdzierz, M. Zajusz, W. Skubida, K. Mroczka, [45] S. Mallesh, A. Sunny, M. Vasundhara, V. Srinivas, Structure and magnetic
K. Berent, K. Swierczek, M. Danielewski, Formation and properties of high entropy properties of ZnO coated MnZn ferrite nanoparticles, J. Magn. Magn. Mater. 418
oxides in Co-Cr-Fe-Mn-Ni-O system: novel (Cr, Fe, Mg, Mn, Ni)3O4 and (Co, Cr, Fe, (2016) 112–117, https://doi.org/10.1016/j.jmmm.2016.03.017.
Mg, Mn)3O4 high entropy spinels, J. Eur. Ceram. Soc. 40 (2020) 1644–1650, [46] J.A. De Toro, P.S. Normile, S.S. Lee, D. Salazar, J.L. Cheong, P. Muniz, J.M. Riveiro,
https://doi.org/10.1016/j.jeurceramsoc.2019.11.030. M. Hillenkamp, F. Tournus, A. Tamion, P. Nordblad, Controlled close-packing of
[23] S.K. Shaw, A. Gangwar, A. Sharma, S.K. Alla, S. Kavita, M. Vasundhara, S.S. Meena, ferrimagnetic nanoparticles: an assessment of the role of interparticle
P. Maiti, N.K. Prasad, Structural and magnetic properties of nanocrystalline equi- superexchange verses dipolar interactions, J. Phys. Chem. C 117 (2013)
atomic spinel high-entropy oxide (AlCoFeMnNi)3O4 synthesized by microwave 10213–10219, https://doi.org/10.1021/jp402444x.
assisted co-precipitation technique, J. Alloy. Compd. 878 (2021), 160269, https:// [47] S.P. Mathew, S.N. Kaul, Magnetization process in nanocrystalline gadolinium,
doi.org/10.1016/j.jallcom.2021.160269. J. Phys: Condense. Mater. 24 (2012), 256008.
[24] A. Mao, H.-X. Xie, H.-Z. Xiang, Z.-G. Zhang, H. Zhang, S. Ran, A novel six- [48] M. Suzuki, S.I. Fullem, I.S. Suzuki, L. Wang, C.-J. Zhong, Observation of super-glass
component spinel-structure high-entropy oxide with ferrimagnetic property, behavior in Fe3O4 nanoparticles, Phys. Rev. B 79 (2009), 024418, https://doi.org/
J. Magn. Magn. Mater. 503 (2020) 166594, https://doi.org/10.1016/j. 10.1103/PhysRevB.79.024418.
jmmm.2020.166594. [49] M.L. Néel, Propriétés magnétiques des ferrites; ferrimagnétisme et
[25] H. Zhu, H. Xie, Y. Zhao, S. Dai, Y. Zhao, M. Li, X. Wang, Structure and magnetic antiferromagnétisme, Ann. Phys. 12 (3) (1948) 137–198, https://doi.org/10.1051/
properties of a class of high-entropy oxides, J. Magn. Magn. Mater. 535 (2021), anphys/194812030137.
168063, https://doi.org/10.1016/j.jmmm.2021.168063. [50] S. Chikazumi, Physics of Ferromagnetism, second ed., Clarendon Press, Oxford,
1997.