Ceramics International 47 (2021) 28623–28633

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Magnetically retrievable nanoscale nickel ferrites: An active photocatalyst

for toxic dye removal applications
Swapnil A. Jadhav *, Mangesh V. Khedkar *, Sandeep B. Somvanshi *, K.M. Jadhav *
Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad, 431004, MS, India

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

Keywords: Nickel ferrite (NiFe2O4) nanoparticles were synthesized through the sol-gel auto-combustion method using urea
Nanoferrites and glycine as mixed fuel. The prepared nanoparticles were investigated for their structural, optical, and mag­
Nano-photocatalyst netic characterizations. Rietveld refined X-ray diffraction (XRD) patterns revealed the development of single-
Toxic dye removal
phase cubic spinel. The crystallite size was calculated by using Modified Scherrer’s method and the W-H plot
Photo reactor
was found in the order of 26.6 nm and 25.4 respectively which are nearly the same. The infrared spectrum
showed the typical characteristic absorption bands in the range of 400 cm-1 to 600 cm-1 belonging to cubic spinel
structure. Scanning electron microscopy images showed the spherical nature of the nanoparticles along with
agglomeration to some extent. As per the optical study, the prepared nanoparticles have an optical bandgap of
2.59 eV. The magnetic properties were studied through the M − H hysteresis curve showing superparamagnetic
nature, the value of saturation magnetization (Ms), coercivity (Hc) was observed 46.20 emu/gm, and 383.2 Oe
respectively. The photocatalytic activity of nickel ferrite was studied based on the degradation of methylene blue
(MB) dye as a model compound, where the result showed that prepared nanoparticles possessed a good pho­
tocatalytic activity against dye degradation. Up to four times catalyst exhibits nearly the same reutilization.

1. Introduction of these may be increased. For the decolorization of dye contaminants,

The increasing human population contributes to more air, water, and
soil pollution day by day. Pollution directly affects human health, na­
ture, animals, underwater creatures, and birds. Due to environmental
pollution, serious issues are occurring nowadays [1]. Due to air pollu­
tion, asthma and other diseases of the lungs have increased rapidly. The
soil pollution occurring due to heavy metals has a direct impact on
agriculture; therefore, many types of stomach diseases are observed [2].
Water pollution is the most serious issue nowadays, which occurs due to
the generation of huge amounts of wastewater from the textile and other
chemical industries [3–5]. About 70% of diseases are caused due to
polluted water; therefore, water purification is the best and prime option
to restrict this problem. From the last few decades, semiconductor ma­
terials were employed for various wastewater treatments and water
purification processes [6,7]. However, the main problem with semi­
conductors is that visible light cannot be absorbed by the semiconductor
nanomaterials having a wide band difference. Through mixing active
metal and/or non-metal into bulk semiconductor materials, the activity
semiconductor photocatalysts such as TiO2, ZnO, CdO, NiO, and Fe2O3
have been used [8–10]. However, the use of these materials in waste­
water treatment is restricted due to some crucial issues which need to be
tackled as early as possible [11]. The first issue is that these materials are
only effective in the UV range and ineffective in the visible spectrum
range. Second, recovery of these materials after their use is complex and
thus, they are non-reusable. Lastly, these materials are not scalable to
large applications [12–14].
Magnetic nanoparticles with a spinel structure are known as spinel
ferrites. Ferrites are a kind of spinel that has the general formula of
MFe2O4 (M = Fe, Zn, Ni, Co, etc.), based on their crystal structures and
magnetic properties [15]. The M and Fe are the metallic cations that are
found at two separate locations, namely tetrahedral (A-site) and octa­
hedral (B-site), respectively, in the case of normal spinel and some M
preferred B-site in the case of inverse spinel [16]. Nickel ferrite
(NiFe2O4), a well-known inverse spinel, is extremely valuable due to its
numerous applications. One of its most common spinel ferrites is nickel
ferrite (NiFe2O4). Its characteristics such as high magnetocrystalline

* Corresponding authors.
E-mail addresses: phy.patil007@gmail.com (S.A. Jadhav), mkhedkar899@gmail.com (M.V. Khedkar), physics.sbs@bamu.ac.in (S.B. Somvanshi), drjadhavkm@
gmail.com (K.M. Jadhav).

https://doi.org/10.1016/j.ceramint.2021.07.021
Received 24 May 2021; Received in revised form 1 July 2021; Accepted 2 July 2021
Available online 3 July 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S.A. Jadhav et al.
anisotropy, high saturation magnetization, and peculiar magnetic
composition catch the attention of the researchers [17]. NiFe2O4 has a
wide range of magnetic properties based on its particle size and
morphology, such as paramagnetic, superparamagnetic, or ferrimag­
netic conduct [18]. The magnetic nature such as paramagnetic, super­
paramagnetic, or ferrimagnetic of NiFe2O4 depends on its particle size
and morphology.
Different synthesis methodologies have been introduced to produce
materials with suitable physicochemical properties such as sol-gel auto-
combustion method, hydrothermal, and co-precipitation. The sol-gel
auto-combustion method is a two-step procedure that includes the
analysis of a precursor and its auto-ignition [19]. This process has the
advantages such as homogeneous molecules, high purity and uniformity
of the sample, and application of simple laboratory equipment. Indi­
vidual and complex metal oxides were synthesized using a variety of
fuels such as urea, glycine, citric acid, EDTA, PVA, sucrose, dextrose, and
others [20]. The surface region, particle size distribution, and agglom­
eration of solution combusted powders are all affected by flame tem­
perature and the volume of emitted gaseous compounds, which are in
turn influenced by the type of fuel and the fuel-to-oxidant ratio [21]. As
opposed to a substance formed with a single fuel, the use of a mixture of
fuels allows for a decrease in particle size due to its better regulation of
flame temperatures as well as the form and quantity of gaseous goods
released.
Sen et al. reported that the nickel ferrite nanoparticles were syn­
thesized by the sol-gel method using urea as fuel and studied its struc­
tural, morphological, elemental, and optical properties [22].
Shanmugam et al. synthesized cobalt ferrite nanoparticles applying urea
and citric acid as the fuels through the sol-gel method [23]. They
concluded that the different fuels affected the structural, elemental, and
morphological properties of cobalt ferrite.
This research aims to show how the fuel mixing ratio of urea and
glycine affects the structure, morphology, magnetic, and catalytic
properties of NiFe2O4 nanoparticles made by the sol-gel auto-combus­
tion method. The prepared NiFe2O4 nanoparticles exhibit highly
remarkable structural, magnetic, optical, and photocatalytic activity.
The obtained results demonstrate excellent magnetic, optical, and
photocatalytic actives.
2. Experimental section
2.1. Preparation of ferrite nanoparticles
The sol-gel auto-combustion process was used to make NiFe2O4
Fig. 1. Flowchart of prepared NiFe2O4 nanoparticles.
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nanoparticles. The raw materials used were nickel nitrate (Ni
(NO3)2.6H2O), ferric nitrate (Fe(NO3)3.9H2O), urea (CH4N2O), glycine
(C₂H₅NO₂), and ammonia (NH3), all of which was 99.9% pure. The
overall oxidizing and reducing valences of the materials were used to
test the Stoichiometric compositions of metal nitrates and fuels, and the
oxidizer to fuel ratio was set to 1: (60:40). To make a blended solution,
metal nitrates were first dissolved in deionized water. With the addition
of ammonia, a constant pH of 7 was achieved. The collected mixture
solution was heated for 6 h at 80 ◦ C–90 ◦ C. The fluid formed during
evaporation resembled a viscous gel. The viscous gel was then heated to
130 ◦ C to start a self-propagating combustion reaction, yielding burnt
powder. In the furnace, this bursting powder was annealed at 650 ◦ C for
300 min. The prepared nanoparticles were designed as NiFe2O4. The
flowchart of the prepared nanoparticles is shown in Fig. 1.
2.2. Photocatalytic performance
Fig. 2 shows that the photodegradation experiment was carried out
in a homemade reactor. A stainless cylinder provides the reactor’s wall,
with the connections of cooling water. The experiment used a 200-W
halogen lamp as the visible source. Magnetic pellets were used to
continually stir the organic pollutants containing photocatalyst. To
analyze the photocatalytic activity of the NiFe2O4 nanoparticle catalyst,
the sample was collected constantly via the outlet port.
The following equation was used to quantify the photocatalytic
degradation efficiency,
( )
C
D% = 1 − X 100 (1)
Co
where C is the original MB concentration and Co is the MB concentration
after t minutes.
2.3. Characterization
The decomposition mechanism and change in mass of nickel ferrite
sample were studied by TG-DTA (Shimazdu DTA-60H) technique. The
structural properties of prepared samples which were investigated from
the XRD pattern were recorded with the help of an X-ray diffractometer
(Bruker) at room temperature with Cu Kα (λ = 1.5406Å) radiation,
operated at the 40-kV voltage and 20-mA current. The functional group
analysis was done by using FTIR spectra, which were recorded at room
temperature by applying Shimadzu FTIR spectrometer in the range of
wavenumber from 350 cm-1 to 2000 cm-1. Raman spectra of the sample
S.A. Jadhav et al.
Fig. 2. A photocatalytic reactor for the degradation of MB.
were recorded by using Raman spectroscopy (Jobin Yvon Horibra
LABRAM-HR 800) in the frequency range of 100 cm-1 to 700 cm-1 at
room temperature. The analysis of the surface morphology of the pre­
pared sample was carried out by using SEM (JSM-5600). The M − H loop
was recorded at room temperature with the help of VSM (Quantum
Design–Modular control system) to study its magnetic properties. The
light absorption spectrum in the UV–visible range between 200 nm and
800 nm was recorded using UV–vis spectroscopy.
3. Results and discussion
3.1. Thermal analysis
The thermal analysis was performed to understand the decomposi­
tion of metal hydroxide, removal of water, and ferritization temperature
of the prepared NiFe2O4 nanoparticles under a nitrogen atmosphere as
shown in Fig. 3. And in the temperature range from 27 ◦ C to 1200 ◦ C
Fig. 3. TG-DTA curve of NiFe2O4 nanoparticles.
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with a heating rate of 20 ◦ C/min, the TG-DTA curve of the NiFe2O4
nanoparticles is shown in Fig. 3 From TG-DTA analysis, it is clear that
those three different events of weight loss were exhibited in the TGA
curve and one exothermic and one endothermic peak were also observed
in the DTA curve corresponding to the weight decrease. The first weight
loss was observed to be 17.7%, due to the removal of moisture, with no
corresponding endothermic peak observed in DTA analysis. The second
weight loss found to be 5.37% with a corresponding exothermic peak at
100 ◦ C of DTA curve indicates the decomposition of metal hydroxide.
The third weight loss of 4.14% with an endothermic peak at 423 ◦ C
shows the ferritization or the formation of ferrite. The total weight loss
in the NiFe2O4 sample, i.e., 27.21%, was completed up to the temper­
ature of 835 ◦ C. The prepared samples were sintered at 650 ◦ C for 300
min.
3.2. Study of X-ray diffraction
FullProf program was used to perform Rietveld refinement on XRD
data of NiFe2O4 nanoparticles as shown in Fig. 4. The experimental data
are represented by the black-colored points, while the measured in­
tensity is denoted by red-colored points. The positions of Bragg’s angle
are indicated by the pink-colored vertical lines, and at the bottom, the
blue-colored lines stand for the difference between the estimated and
measured intensity. The technique of Rietveld refinement showed the
phase identity of the samples. The Rietveld refined X-ray diffraction
(XRD) result presents that the prepared samples have a single-phase
cubic spinel arrangement similar to the ICDD cartel (No. 86-2267).
The χ2, profile factor (Rp), weighted profile factor (Rwp), and pre­
dicted R-factor (Rexp) are all considered to be the durability factors that
suggest refinement efficiency. All of the prepared nanoparticles had a
value of χ2 that was close to 1 indicating good refinement. All of the
variables are shown in Table 1. With the split pseudo-Voigt function, the
cubic phase was measured, and the XRD pattern was fitted with a whole
powder pattern fitting software. During refinement, no other extra
phases were identified. The low value of χ2 confirms the success of the
refinement process. The peaks identified at 2θ values are 30.28◦ , 35.5◦ ,
37.1◦ , 43.2◦ , 53.6◦ , 57.7◦ , and 63.8◦ and peaks allocated to the planes
are (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), and (4 4 0). In order to
S.A. Jadhav et al. Ceramics International 47 (2021) 28623–28633

various useable peaks, since the (β.cosθ) multiple is not a constant value
for all the peaks, the negative slopes are attributed to the assumption
that at higher angles of 2θ with lower values of cosθ and higher values of
ln(1/cosθ), meaning that linear plots with a 45◦ slope are difficult to
obtain. The key source of scattering of the points is errors involved in
Scherrer’s equation by applying multiple peaks. Measuring lnβ and ln(1/
Cosθ) are the two other points of error. The importance of this work is to
minimize errors by employing the least-squares method to achieve sig­
nificant results.

3.2.2. Williamson-Hall analysis

The Williamson-Hall analysis only takes into account the effect of
crystalline on the XRD peak broadening, and it cannot be considered for
microstructures of the lattice, i.e., strain formed in nanocrystals as a
result of a point defect and grain boundary. Considering the effect of the
XRD peak broadening induced by the strain and intrinsic strain, as well
as the particle size, the method is called the W-H method, which is
simple and effective. This strain has a direct impact on the physical
broadening of the XRD profile, and the peak broadening affected by this
strain is shown in,

Fig. 4. Rietveld refined the X-ray diffraction pattern of NiFe2O4 nanoparticles. ε=

βs
(5)
4tanθ
verify nanocrystalline structure, the XRD pattern was studied with help The distinction of size and strain broadening in Williamson-Hall’s
of Rietveld refinement data using modified Scherrer’s method and study was based on the distinct θ dependencies of both the results. By
Williamson-Hall (W-H plot) analysis. adding Eqs. (3) and (5), it has been found that
kλ
3.2.1. Modified Scherrer’s method βcosθ = + 4εsinθ (6)
D
The Debye-Scherrer formula was used to calculate the average
crystalline size, where D and ε correspond to the value of crystalline size and the
Kλ kλ microstrain, respectively [25]. For prepared NiFe2O4 nanoparticles, a
D= or β = (2) plot is drawn with 4sinθ on the x-axis and β.cosθ on the y-axis, as shown
βhkl cosθ Dcosθ
in Fig. 6.
where D is the crystalline size, k is the shape factor of 0.9, λ is the The crystalline size was calculated using the y-intercept of a linear fit
wavelength of the X-ray source, β is the FWHM, and θ is the peak po­ to the results, and strain ε was estimated applying the fit’s slope.
sition. Eq. (2) is given by Ref. [24],
1 kλ
β= x (3)
cosθ D cosθ
Taking log on both sides,
( ) ( )
1 kλ
ln(β) = ln + ln (4)
cosθ D
Eq. (4) is the modified Scherrer’s equation. Now, calculating crys­
talline size from the y-intercept and taking exponential on both sides,
( )
kλ
y intercept = ln
D
( )
ln kλ
D
ey intercept = e
In Eq. (4) ln(1/cosθ) is plotted on the x-axis, while ln(β) is plotted on
the y-axis as-prepared NiFe2O4 nanoparticles as shown in Fig. 5.
The values of crystallite size calculated are shown in Table 1. The
equations of the least-squares method obtained from linear regression of
data in Excel plots are presented in Fig. 5, indicating plots ln(β) vs ln(1/
cosθ). Because of the sources of error in calculating β and treating for Fig. 5. Modified Scherrer’s plot of NiFe2O4 nanoparticles.

Table 1
Values of crystallite size (D) determined by the modified Scherrer’s method and W-H analysis and lattice constant (a) by experimental, Nelson-Riley for NiFe2O4
nanoparticles.
Lattice constant (a) Å D (nm)

Rp Rwp Rexp χ2 Experimental Rietveld refined Nelson-Riley Modified Scherrer’s W-H Plot
NiFe2O4 65.0 29.9 26.979 1.35 8.3415 8.3519 8.3151 26.6 25.4

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Fig. 8. FTIR spectra of NiFe2O4 nanoparticles.

Fig. 6. Williamson-Hall plot of NiFe2O4 nanoparticles. caused by the metal-oxygen bond (C=O) stretching at the tetrahedral
site (A) and the lower frequency band ν2 found in the range of 450 cm-1
–380 cm-1 corresponds to the octahedral site (C=O) stretching (B) [27].
kλ
D= (7) These bands are known as the traditional spinel bands. According to
y − intercept
Waldron’s analysis, the force constant for tetrahedral (Kt) and octahe­
where was, the strain was supposed to be uniform along the crystallo­ dral (KO) sites is [28],
graphic course, taking into account the nanocrystalline nature of the Kt = 7.62 x MA x ν21 x 10− 7
(8)
material.
K0 = 5.31 x MB x ν22 x 10− 7
(9)
3.2.3. The lattice constant (a)
The lattice constant was calculated by the Nelson-Riley function for And,
NiFe2O4 nanoparticles as shown in Fig. 7.
K1 + K2
The lattice constants calculated by the experimental and Nelson- Kav = (10)
2
Riley functions are nearly the same. The lattice constant of NiFe2O4
nanoparticles matches the literature value well [26]. where Kt and Ko are the force constants corresponding to tetrahedral and
octahedral metal complexes. MA is the mass of the tetrahedral site, while
MB is the mass of the octahedral site, and υ1 and υ2 are the frequencies of
3.3. FTIR analysis
the tetrahedral and octahedral sites, i.e., 559 and 401.
The Debye temperature of NiFe2O4 nanoparticles is calculated by,
Fourier transform infrared (FTIR) spectrum of the NiFe2O4 nano­
particles was recorded in the range of 350 cm-1 - 4000 cm-1 as shown in hcν12
θD = (11)
Fig. 8. Kβ
The higher frequency band ν1 between 600 cm-1 and 500 cm-1 is
where h is Planck’s constant, c is the speed of light, Kβ is the Boltzmann’s
constant, and ν12 is the average wave number of absorptions. The elastic
stiffness constant Cij is calculated with the help of force constant as given
by,
Kav
Cij = (12)
a

where Kav is the average force constant and a is lattice constant

(experimental). Stiffness constant Cil is calculated using elastic stiffness
constant and Poisson’s ratio as shown in,
σ x Cij
Cil = (13)
1− σ

where Cij is the elastic stiffness constant and σ is the Poisson’s ratio
(0.3227).
In order to measure the different elastic constants such as Young’s
modulus, bulk modulus, longitudinal elastic wave velocity, transverse
elastic wave velocity and modulus of rigidity, lattice energy, and their
values are presented in Table 2. The Young’s modulus is shown as,
( )
Cij − Cil (Cil + 2Cil )
Y= ( ) (14)
Cij + Cil
Fig. 7. Nelson-Riley function plot of NiFe2O4 nanoparticles.

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Table 2
Calculated values of force constants (Kt and Ko), avg. force constant (Kavg.),
Debye temperature (θD), elastic stiffness constant (Cij), stiffness constant (Cil),
Young’s modulus (Y), bulk modulus (B), longitudinal wave velocity (Vl), trans­
verse wave velocity (Vt), elastic wave velocity (Vm), rigidity modulus (R), lattice
energy (UL) for NiFe2O4 nanoparticles.
Frequency Band (cm-1) ν1 ν2
559 401

a (Å) 8.34
X-ray density (ρx) 5.3605 g/cm3
Force Constant (Kt) 2.72 × 102 N/m
Force Constant (Ko) 0.978 × 102 N/m
Avg. Force Constant (Kavg.) 1.852 × 102 N/m
Debye temperature (θD) 691 K
Elastic stiffness constant (Cij) 222 GPa
Stiffness constant (Cil) 110.71 GPa
Young modulus (Y) 148.39 GPa
Bulk modulus (B) 110.42 GPa
longitudinal elastic wave velocity (Vl) 6.435 × 103 m/s
transverse elastic wave velocity (Vt) 3.715 × 103 m/s
Mean elastic wave velocity (Vm) 2.402 × 103 m/s
Rigidity modulus (R) 73.93 GPa
Lattice energy (UL) -435 eV

Fig. 9. Raman spectra of NiFe2O4 nanoparticles.

where Cij is the elastic stiffness and Cil is the stiffness constant. The bulk
modulus is presented by,
Raman active modes (A1g, Eg, and 3T2g) observed in the case of spinel
1[ ] ferrites. The clear visibility of these five modes confirms the cubic phase
B = Cij + Cil (15)
3 of the prepared sample. The A1g is the higher frequency mode that in­
dicates the symmetric stretching of M − O at the tetrahedral site and the
The longitudinal elastic wave velocity (Vl) and transverse elastic
remaining four are lower frequency modes, in which T2g (1) and T2g (2)
wave velocity (Vt) are given by,
modes indicate asymmetric bending and stretching of M − O at the
√̅̅̅̅̅̅
Cij octahedral site, respectively. The Eg and T2g (3) modes are attributed
V; = (16) due to the symmetric and asymmetric bending of O-M, respectively [30].
ρx
As shown by the Raman spectra of the prepared sample, the value of A1g,
√̅̅̅̅̅̅̅ Eg, T2g (1), T2g (2), and T2g (3) modes is 460.59 cm-1, 276.53 cm-1,
Vt =
Cij
(17) 151.89 cm-1, 232.91 cm-1, and 519.70 cm-1, respectively. The Raman
3 ρx study of the prepared sample confirms that the nanoparticles have a
cubic spinel structure and Fd-3m space group.
where Cij is the elastic stiffness constant and ρx is the X-ray density
(5.3605). Further, the calculated value of mean elastic wave velocity is
3.5. Surface morphology analysis (SEM)
explained as,
[ ( )]− 1/3
1 2 1 The morphological study and grain size evaluation was investigated
Vm = 3
+ 3 (18) by FE-SEM analysis as shown in Fig. 10. The micrograph shows the
3 Vt Vl
homogeneous spherical structure with a narrow size distribution, and
where (Vl) is the longitudinal elastic wave velocity and (Vt) is the the grain size was found to be 39 nm. The agglomerated grainy structure
transverse elastic wave velocity. The rigidity modulus is shown as, can be seen in the micrograph, and the morphology of the surface is
found to be almost uniform, with a spherical shape. It is difficult to
R = ρx Vt2 (19) determine the exact size and shape of the particles as they are often
aggregated.
where (ρx) is the X-ray density (5.3605) and (Vt) is the transverse elastic
wave velocity. The lattice energy is presented through,
( ) 3.6. Magnetic analysis
UL = − 3.108 MVm2 x 10− 5 eV (20)
The M − H loop of NiFe2O4 nanoparticles was recorded at room
where M is the molecular weight of NiFe2O4 nanoparticles and Vm is the temperature with an applied magnetic field ±15 kOe as shown in
mean elastic wave velocity. Fig. 11.
Both elastic parameter and Debye temperature collected from FTIR The saturation magnetization (Ms), coercivity (Oe), remanence
data are in perfect agreement with other ferrite materials [29]. magnetization (Mr), remanence ratio (Mr/Ms), and magneton number
(nB) were determined from the M − H plot and presented in Table 3. The
3.4. Raman analysis magneton number was calculated by using,
[Ms × Mw ]
The Raman analysis of prepared samples was studied from Raman nB = (21)
5585
spectra recorded within the frequency range of 100 cm-1-700 cm-1 at
room temperature. where Mw is the molecular weight, Ms represents saturation magneti­
The Raman spectra of NiFe2O4 nanoparticles are shown in Fig. 9. The zation of the sample, and nB is the magneton number. The high satura­
detailed peak study of Raman spectra was done through the best peak tion magnetization and very low coercivity were found in the M − H
fitting procedure using the Lorentzian function. There are main five loop. The prepared sample shows ferromagnetic nature at room

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Fig. 10. a) FE-SEM micrograph and b) grain size distribution histogram of NiFe2O4 nanoparticles.

Fig. 11. Magnetic hysteresis loops of NiFe2O4 nanoparticles.

Fig. 12. PL spectra of NiFe2O4 nanoparticles.

Table 3 3.8. UV–vis spectroscopy studies

The values of magnetic parameters such as saturation magnetization (Ms),
coercivity (Hc), remanence magnetization (Mr), remanence ratio (Mr/Ms), and The UV–vis spectroscopy is used to study the optical activity,
magneton number (nB) as calculated from the M − H loop of nickel ferrite including absorbance, absorption coefficient, refraction index, optical
nanoparticles. conductivity, extinction coefficient, and percentage transmittance of
Sample Ms (emu/g) Mr (emu/g) Hc (Oe) Mr/Ms nB (μB) NiFe2O4 nanoparticles. For the prepared sample, broad absorption is
Nickel ferrite 46.20 25.27 383.2 0.5469 1.9388 observed at ⁓301 nm, which is visible in the region as shown in Fig. 13.
The optical properties of prepared nanoparticles were evaluated at
room temperature using UV–vis spectroscopy, and the energy bandgap
temperature. was determined using Tauc’s plot relation,

3.7. Photoluminescence (PL) αhν = A (hν − Eg)1/2 (22)

The examined specimens’ photoluminescence (PL) properties were
determined by observing the PL spectra with a spectroscope as shown in
Fig. 12.
The PL spectra were captured with the aid of a 360-nm excitation
wavelength. Within the specimens, the characteristic NBE, or near band
edge emission was observed in the wavelength range of 380 nm–390 nm.
The larger NBE that was near the visible region at 385 nm, all of the
specimens were acquired. This broader NBE was responsible for the
reformation of holes created by photonic and electronic transitions
trapped within the oxygen vacancy [31].
where α is the absorption coefficient, hv is the photon energy, A is the
proportionality constant, and Eg is the bandgap. The bandgap for pre­
pared nanoparticles was determined by plotting the linear portion of the
αhν vs hν plot along the horizontal axis, as shown in Fig. 14. The optical
band of NiFe2O4 nanoparticles is 2.59 eV.
Mostly absorption coefficient is the measure of light that might be
absorbed by the thickness of the pallet of prepared NiFe2O4 nano­
particles. It indicates how much light corresponding to a specific
wavelength will be absorbed by materials. The absorption coefficient
was calculated by the given relation,
2.303 x absorbance
α= (23)
l

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Fig. 15. The absorption coefficient of NiFe2O4 nanoparticles.

Fig. 13. UV–vis spectra of NiFe2O4 nanoparticles.

Fig. 16. Refractive index of NiFe2O4 nanoparticles.

Fig. 14. The bandgap of NiFe2O4 nanoparticles.
shows variation in refractive index as a function of wavelength of the
where α is the absorption coefficient, l is the thickness of the pallet of light, refractive index initially decreases and then increases to its
NiFe2O4 nanoparticles. maximum value at 289 nm. After approaching this graph value, again it
From Fig. 15, it has been observed that NiFe2O4 nanoparticles show decreases.
the maximum absorption at 301 nm so that these can absorb light Optical conductivity is a very important property to measure the
wavelength at 301 nm more efficiently. Moreover, it has been also found electronic states of materials. It is closely related to dielectric function.
that the absorption graph initially increases and then decreases, due to The optical bandgap, refractive index, absorption coefficient, incident
the defects in nanocrystalline materials. photon frequency, extinction coefficient, and other factors all contribute
The value of the refractive index is the measurement of how light to studying the variation of optical conductivity as a function of the
propagates in materials that change their direction. It is very essential wavelength of light [33]. The optical conductivity plot as shown in
optical constant and plays an important role in designing the optical Fig. 17 is calculated in the given relation,
device. It provides information related to the local field, polarization, αnc
σ opt = (26)
and phase velocity of light. Refractive index as shown in Fig. 16 is 4π
calculated by this given relation [32],
√̅̅̅̅̅̅̅̅̅̅̅̅̅ where α is the absorption coefficient, n is the refractive index, and c is
1 1 the speed of light in a vacuum (299792458). Fig. 17 shows that the
n= + (24)
Ts Ts − 1 optical conductivity initially decreases with increasing wavelength. As
light energy approaches 289 nm, it starts to increase and the maximum
Ts = 10(− absorbance)
x 100 (25) optical conductivity is observed at 299 nm.

where n is the refractive index and Ts is percent transmittance. Fig. 16

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Fig. 17. Optical conductivity plot of NiFe2O4 nanoparticles.
3.9. Photocatalytic studies
Methylene blue is the dangerous natural color dye that is found in
industrial wastewater and causes open ecological issues. We need to
utilize this color as a typical example to assess the photocatalytic
decolorization of NiFe2O4 nanoparticles. The photocatalytic properties
mostly depend on the surface area, particle size, bandgap energy, and
concentration of the prepared samples. The concentration of MB dye is
estimated using the linear part of the absorbance concentration curve
(Beer’s law) [34].
Fig. 18 shows the absorbance spectra of the NiFe2O4ferrite nano­
particles. The domination of MB color dye is measured utilizing the
direct section of the absorbance concentration curve (Beer’s law).
Fig. 19 shows the absorbance spectra of the NiFe2O4 ferrite nano­
particles’ 22.25% degradation, which was observed without catalysis,
similarly, the degradation increases up to 98.23% within 60 min under
the visible light in the presence of NiFe2O4 ferrite nanoparticles.
3.9.1. Effect of spinel ferrite nanoparticles
The photocatalytic degradation of spinel ferrite nanoparticles
generally relies on the efficiency required to separate electron/hole,
Fig. 18. Absorbance spectra on the photocatalytic degradation of MB with
NiFe2O4 nanoparticles.
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Ceramics International 47 (2021) 28623–28633
Fig. 19. The photocatalytic degradation efficiency of NiFe2O4 nanoparticles.
surface area, and bandgap. Because of their high surface area, they show
a high photocatalytic degradation when related to the bulk materials. At
the point when daylight moves to the NiFe2O4 ferrite nanoparticles, the
electron also moves from valence band to conduction band to deliver
electron/hole pairs. This because of the nickel ferrite nanoparticle
structure Fermi energy level just underneath the conduction band inside
the energy band hole [35].
3.9.2. Effect of dye concentration
Fig. 20 presents that degradation of color dye under the daylight
mostly relies upon the concentration to determine its grouping; for
example, 10 ppm, 15 ppm, and 20 ppm concentration with NiFe2O4
ferrite nanoparticles. At the point when the color dye concentration
increases, the photocatalytic degradation is observed to decrease
because of the adsorption of more color atoms on the surface of the
materials, which, therefore, reduces the thorough rate of light into the
materials; hence, the photocatalytic degradation of color dye decreases.
Because of this, the generation rate of hydroxyl radicals and superoxide
radicals was revealed to be lower. Subsequently, the low concentration
Fig. 20. Different color dye concentrations (10 ppm, 15 ppm, and 20 ppm).
(For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)
S.A. Jadhav et al. Ceramics International 47 (2021) 28623–28633

of color dye, i.e., 10 ppm shows a higher percentage of color dye pho­
tocatalytic degradation [36,37].

First-order decay kinetics study of photocatalytic

The photocatalytic degradation of MB follows the reaction rate
constant that was evaluated as given,
( )
C
In = kt (27)
Co

where C is the concentration of MB after degradation, Co is the initial

concentration of MB and k is the rate constant and t is the photocatalytic
degradation reaction, which implies the first-order decay kinetics reac­
tion. The slope of the straight line gives the rate constant (k) that was
calculated to be 0.00233 min-1 and also fitted line was determined to be
R2 = 0.99, as shown in Fig. 21. Fig. 22. Photocatalytic degradation of methylene blue.
The photocatalytic degradation mechanism of MB color dye over
NiFe2O4 ferrite nanoparticles is shown in Fig. 22. The energetic species the rate of degradation. The active species for MB degradation was the
for photocatalytic degradation of shading color ought to be created by hydroxyl radical formed by the earlier three pathways.
three pathways. When light exits on the surface of NiFe2O4 ferrite
nanoparticles, they are illuminated. The electron is exited from the
valence band to the conduction band by creating the electron/hole pairs 3.10. Recyclability of the NiFe 2O4 nanoparticles
on the surface of the NiFe2O4 ferrite nanoparticles.
( ) The same catalyst was washed with ethanol and purified water five
NiFe2 O4 + hv →NiF2 O4 e−CB + h+
VB (28) times and dried at room temperature. Up to four runs, the catalyst
The hole reacts with water molecules or hydroxyl ions to create exhibited nearly the same quality, as shown in Fig. 23. The active sites of
hydroxyl radicals. the catalyst are replaced after the reutilization of the catalyst, resulting
in a reduction in efficiency after four cycles, as a result, the activity of
h+ +
VB + H2 O →H + OH (29) the catalyst can be lost during washing and drying.

h+ −
VB + OH →OH
The photo-induced electron CB could be captured by C2H2O4 to yield
OH, enhancing photocatalytic activity by limiting the recombination of
hole and electron.
C2 H2 O4 + e−CB →OH− + OH. + CO2
C2H2O4 reacts with Fe(III) and Fe(II) on the surface of ferrite to form
Fenton reagent, which produces hydroxyl radical.
Fe3+ + C2 H2 O4 →Fe2+ + HOO. + H+ + CO2
Fe2+ + C2 H2 O4 →Fe3+ + OH. + OH− + CO2
Since OH is generated by three pathways, there was an increase in
(30) 4. Conclusion
In conclusion, urea and glycine as mixed fuel have been used to
synthesize NiFe2O4 nanoparticles. The processes of NiFe2O4 develop­
ment, as well as the characterization of the resulting compounds, were
(31) carried out with the help of X-ray diffraction, FTIR, Raman spectra,
UV–vis diffuse reflectance spectroscopy, and FE-SEM. The values of
crystalline size calculated from Modified Scherer’s and W-H plot are
nearly the same and exhibit nanocrystalline nature. The Debye tem­
(32) perature calculated from FTIR was found in order of 691 K. The mag­
netic properties of NiFe2O4 nanoparticles show superparamagnetic
(33) nature, where the saturation magnetization, coercivity, and remanence
magnetization values are 46.20 emu/gm, 383.2 Oe, and 25.27 emu/gm
respectively. The photocatalytic properties of NiFe2O4 as-synthesized
were also tested by degrading MB as a water contaminant. All the

Fig. 21. The plot of pseudo-first-order kinetics of photodegradation of MB dye. Fig. 23. Photocatalyst reusability studies of NiFe2O4 nanoparticles.

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outcomes revealed that, the prepared nanoparticles demonstrate good
photocatalytic activity and reusability against degradation of dye.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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