j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/jmrt

Original Article

Structural investigation of Cu doped calcium ferrite

(Ca1-xCuxFe2O4; x ¼ 0, 0.2, 0.4, 0.6, 0.8, 1)
nanomaterials prepared by co-precipitation
method

T.L. Ajeesha a, Ayyar Manikandan b,c,*, Ashwini Anantharaman a,

Sagaya Jansi d, M. Durka e, M.A. Almessiere f,g, Y. Slimani g, A. Baykal h,
A.M. Asiri i,j, H.A. Kasmery i, Anish Khan i,j, A.A.P. Khan i,j, P. Madhu k,
Mary George a,**
a
Department of Chemistry, Stella Maris College, Affiliated to the University of Madras, Chennai, 600005, Tamil
Nadu, India
b
Department of Chemistry, Bharath Institute of Higher Education and Research (BIHER), Chennai, 600073, Tamil
Nadu, India
c
Centre for Catalysis and Renewable Energy, Bharath Institute of Higher Education and Research (BIHER), Chennai,
600073, Tamil Nadu, India
d
Department of Bioinformatics, Stella Maris College, Affiliated to the University of Madras, Chennai, 600005, Tamil
Nadu, India
e
Department of Physics, Bharath Institute of Higher Education and Research (BIHER), Chennai, 600073, Tamil Nadu,
India
f
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam,
31441, Saudi Arabia
g
Department of Biophysics, Institute for Research & Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal
University, P.O. Box 1982, 31441, Dammam, Saudi Arabia
h
Department of Nano-Medicine Research, Institute for Research & Medical Consultations, Imam Abdulrahman Bin
Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia
i
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
j
Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589,
Saudi Arabia
k
Department of Mechanical Engineering, Malnad College of Engineering, Hassan, Visvesvaraya Technological
University, Belagavi, India

article info abstract

Article history: Magnetic and optical properties of copper doped spinel calcium ferrite (Ca1-xCuxFe2O4;
Received 23 December 2021 x ¼ 0, 0.2, 0.4, 0.6, 0.8, 1) nanoparticles (NPs) have fascinated the attention of researchers.
Accepted 16 February 2022 Spinel Ca1-xCuxFe2O4 NPs were prepared by co-precipiation technique. The as prepared
Available online 28 February 2022 compositions were subjected to structural, magnetic, electrical and optical properties.

* Corresponding author.
** Corresponding author.
E-mail addresses: manikandana.che@bharathuniv.ac.in (A. Manikandan), marygeorge@stellamariscollege.edu.in (M. George).
https://doi.org/10.1016/j.jmrt.2022.02.081
2238-7854/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
706 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9

Keywords: Cubic spinel phase was observed through powder X-ray diffraction (PXRD) studies and the

Magnetic nanoparticles lattice constant increased with increase in calcium concentration and the average crys-

Cubic ferrites tallite size in the range 32e19 nm. Transmission Electron microscope (TEM) technique

Co-precipitation provided information on the morphology of the synthesized ferrites. FT-IR spectral bands

Photocatalytic degradation observed at 579, 480 and 514 cm1 confirmed the MO vibration for CaeO, FeeO and CueO

Antibacterial activity bands responsible for the formation of spinel. Magnetization, coercivity and retentivity
were calculated from vibrating sample magnetometer (VSM) studies. Hysteresis loops
revealed the magnetic behavior of the prepared Ca1-xCuxFe2O4 NPs. The adsorption and
desorption measurement were achieved from BrunauereEmmetteTeller (BET) analysis.
Band gap of the prepared spinel ferrites were found to be 1.8e2.5 eV revealing semi-
conducting behaviour of the nanocatalysts. Frequency dependent dielectric studies
revealed that at high frequency both dielectric constant and dielectric loss were decreased.
The photocatalytic degradation (PCD) of the synthesized spinel ferrites with methylene
blue (MB) as organic pollutant and their antibacterial activity was also studied. Ca0.2-
Cu0.8Fe2O4 (CCFO-5) nanocatalyst exhibited 96% degradation in 180 min with methylene
blue dye.
© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

ferrite nanomaterials own its advantage to destroy harmful

1. Introduction
Manifestations of hazardous contaminants in water bodies
pose dangers for humans and the environment. Adsorption
of activated carbon, chlorination, ultrafiltration, and ozona-
tion treatment are the methods that have been used to
reduce these hazardous contaminants. Nevertheless, all the
above treatments are not cost effective. Thus the develop-
ment of an ecofriendly, cost effective methodology using
semiconducting catalyst for the degradation of dyes and
pollutants has attracted the attention of researchers [1].
Ferrites are known for their incredible use in opto-magnetic
and photoelectronic materials, facilitating low energy pho-
tons to demonstrate their optical absorption and present
ideal electronic structure for photocatalytic applications.
Bacterial infections are a high risk for human beings; spinel
bacteria. The search for new materials as antibacterial
agents and reviewing their properties has become a potential
research field [2e6].
Calcium ferrite, a semiconductor spinel ferrite with in-
creased chemical stability and more catalytic sites, serves as a
good applicant in photocatalysis [7e10]. Calcium ferrite also
finds application in biomedicine, drug delivery, magnetic
resonance imaging and magnetic hyperthermia, etc [6,11].
Shankar et al. studied the auto combustion derived nano
calcium ferrite with varied temperature and reported the
semiconducting behaviour for different calcination tempera-
tures [12e19]. Additionally, doped calcium ferrites were syn-
thesized by modifying their properties with the incorporation
of transition metal ions. The magnetic and optical properties
of transition metal doped spinel ferrite ferrites have fasci-
nated the attention of researchers in environment

Scheme 1 e Schematic representation of synthesis of Ca1-xCuxFe2O4 nanoferrites.

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Fig. 1 e PXRD pattern for CCFO nanoparticles.

remediation as potential photocatalyst in the degradation of ferrites. Varying mole ratios of calcium nitrate (Nice chem-
dyes and as effective antibacterial agents [20e27]. Hence the icals) Ca(NO3)2,3H2O, copper nitrate trihydrate (Fischer's
present study is to synthesise copper doped calcium spinel scientific), copper nitrate trihydrate Cu(NO3)2,3H2O, ferric
ferrites via coprecipitation technique and explore its appli- nitrate nonahydrate (Merck) Fe(NO3)3.9H2O were liquefied
cation as effective photocatalyst and antibacterial agent in using 50 mL deionized water and 2M NaOH was added to
waste water treatment [28e34]. A number of methods such as maintain the pH at 13 and magnetically stirred at 80  C for
the hydrothermal, ceramic, auto-combustion, mechanical
milling, solegel and coprecipitation techniques are available
for the preparation of spinel ferrite nanomaterials [35e47].
Amongst these, coprecipitation method has more advantages
owing to the high yield, homogeneity and small particle size
[13,14]. Herein we propose to synthesize copper substituted
calcium spinel ferrite (Ca1-xCuxFe2O4 [CCFO-1 (x ¼ 0), CCFO-2
(x ¼ 0.2), CCFO-3 (x ¼ 0.4), CCFO-4 (x ¼ 0.6), CCFO-5 (x ¼ 0.8),
CCFO-6 (x ¼ 1)] via coprecipitation method and study their
structural, morphological, optical, magnetical and electrical
properties. The as prepared nano spinel ferrites will be tested
for its antibacterial activity and for photo catalytic degrada-
tion over methylene blue dye as organic pollutant.

2. Experimental method

2.1. Synthesis

Chemical co-precipitation technique was used to synthesize

nanosized Ca1-xCuxFe2O4 (x ¼ 0.0, 0.2, 0.4, 0.6, 0.8, 1) spinel

Table 1 e PXRD Parameters for CCFO nanoparticles.

Sample D (nm) Lattice dx (g/cm3) V (a3) d (nm1)
code constant
(a)

A
CCFO-1 40 8.5514 0.5925 88.5098 0.00115
CCFO-2 32 8.5245 0.4944 87.4210 0.00111
CCFO-3 29 8.3896 0.3850 87.2703 0.00108
CCFO-4 25 8.1247 0.2587 87.0230 0.00104
CCFO-5 19 8.0796 0.1684 87.0062 0.0094
CCFO-6 22 8.3289 0.3810 88.0100 0.00076
Fig. 2 e FT-IR spectra for CCFO nanoparticles.
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a b c

d e f

g h i

Fig. 3 e TEM and histogram images for CCFO nanoparticles.

3 h until reddish brown precipitate was attained and
then centrifuged and washed with demineralized water.
Sample thus obtained was heated at 75  C in hot air oven
for 24 h and calcined at 650 fx1 C for 8 h in a muffle furnace
to obtain copper doped calcium ferrite nanomaterials
(Scheme 1).
2.2. Characterization studies
The crystallite size and phase pattern of Ca1-xCuxFe2O4
(x ¼ 0.0, 0.2, 0.4, 0.6, 0.8, 1) spinel ferrites were studied using
Powder X-ray diffraction analysis utilizing Brucker AXS D8
Advance instrument through Cua radiation (l ¼ 0.15418 nm).
Infrared spectra of the nano ferrite materials were recorded
on a PERKIN-ELMER spectrometer from 400 to 4000 cm1 by
KBr pellet method. The surface morphology of the nano-
materials was studied using JEOL/JEM 2100 instrument (source
LaB6 with 200K). The magnetic properties of the as synthe-
sized nano ferrite were measured using Lakeshore VSM 7407
magnetometer with magnetic field 2.5 T at room temperature
(303 K) in a maximum applied field of 15,000 Gauss. The pore
size distribution, surface, volume and surface area are given
by BJH (BarretteJoynereHalenda) and BET (BrunauereEette-
Teller) method using the Quantachrome ® ASiQwinTM in-
strument. The dielectric properties of the synthesized
nanomaterials were studied at room temperature (303 K)
using the Digital LCRZ Meter in the frequency region 50 Hz to
200 kHz. The optical properties of the synthesized Ca1-
xCuxFe2O4 (x ¼ 0.0, 0.2, 0.4, 0.6, 0.8, 1) spinel ferrites were
investigated using JASCO V-750 UV-VIS spectrophotometer.
2.3. Photocatalytic studies of Ca1-xCuxFe2O4
nanoparticles
The photocatalytic studies of Ca1-xCuxFe2O4 (x ¼ 0.0, 0.2, 0.4,
0.6, 0.8, 1) spinel ferrites were done using HEBER multilamp
reactor and its degradation efficiency was studied using
UVeVisible spectrophotometer. Photo catalytic activity of Ca1-
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a b

c d

e f

Fig. 4 e BET (aec) and pore diameter graphs (def) for CCFO nanoparticles.

Table 2 e BET Parameters for CCFO nanoparticles.

Sample Surface Pore Pore % Crystallinity
code area (m2/g) volume diameter
(cc/g) (nm)
CCFO-1 2.653 0.005 1.757 0.21
CCFO-4 25.57 0.029 2.13 0.30
CCFO-6 8.314 0.010 1.594 0.20

xCuxFe2O4 nano materials was examined by using 100 ppm of
Methylene blue dye, 2 mL Fenton's agent and 0.1g of spinel
Ca1-xCuxFe2O4 nano photocatalyst. The mixture was then
transferred to quartz tubes and. exposed to the visible lamp
for 180 min at room temperature to study the photocatalytic
property of the synthesized nanoparticles.
2.4. Antibacterial activity
The antibacterial study for the synthesized copper doped
calcium ferrite was carried out for five different bacterial
pathogens, which include both Gram negative and Gram-
positive bacteria. The glassware, media and reagents used
710 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9
Fig. 5 e Hysteresis loop for CCFO nanoparticles.
were pasteurized in an autoclave chamber at 121  C for
15 min. Muller Hinton agar was used as the medium. Gram
negative (Enterobacter aerogenes, Escherichia coli) and Gram
positive (Bacillus subtilis, Staphylococcus aureus, Micrococcus
luteus) were used as the bacterial strains. The antibacterial
liability tests were performed by the agar well diffusion
method, wherein the bacterial strains were lined on the
surface of the medium by a sterile cotton swab, following
which 6 wells (each well of 10 mm diameter) were prepared
using a sterile stopper borer. The prepared nanomaterials of
25 and 50 mg/mL concentrations respectively were then
loaded in the wells. The petri plates were cultured over
night at room temperature and the antimicrobial ability of
the synthesized ferrites was resolved by measuring the
zone of inhibition (ZOI). The tests were done in triplicates
and mean ± standard errors of the mean were used to
demonstrate the data.
3. Results and discussion
3.1. Powder - XRD diffraction studies
The structural properties of Ca1-xCuxFe2O4 (x ¼ 0.0, 0.2, 0.4, 0.6,
0.8, 1) spinel ferrites were studied from the powder X-ray
diffraction pattern. Figure 1 show the existence of (220), (311),
(011), (320), (400), (422), (511), (440) lattice planes in the XRD
patterns elucidates the structure of single phase cubic spinel
structure with space group Fd3m and all the planes are
matched well with the JCPDS number 72e1199. The average
crystallite size (D, nm) was calculated from Scherrer formula
and it ranged from 19 to 32 nm. The as-synthesized spinel Ca1-
xCuxFe2O4 nanomaterials existed in spinel form, where Fe
3þ
ions occupied the tetrahedral (A-) site and Ca 2þ
ions the
octahedral (B-) site [15]. The unit cell volume decreased with
increase in lattice distortion, due to the occupation of Cu2þ
ions in the interstitial sites at higher concentration. However,
the X-ray density decreased with increase in concentration of
Cu2þ ions as dopant and was attributed to the contribution of
Ca2þ ions between the sub lattice and the effect of reduction
on the crystal arrangement.
The XRD density (PXRD) was calculated by the formula:
8M g
dx ¼ ¼ ðax Þð Þ (1)
Na3 cm3
where, M is molecular weight of the sample and N is Avoga-
dro's number and ‘a’ is the lattice parameter. The dislocation
density (d) decreased when Cu2þ ions concentration was
increased upon calcium ferrite ensuring the micro strain of
the lattice.
Volume (V) of the prepared nanomaterials were deter-
mined using,
V ¼ a3 (2)
where V is the volume of cubic cell and a is lattice parameter
of the unit cell. Structural parameters are summarized in
Table 1.
3.2. FT-IR analysis
The FT-IR spectra (PerkinElmer model Spectrum RXI) of the
synthesized copper doped calcium ferrites (Fig. 2) were stud-
ied between 400 and 4000 cm1. The characteristic spinel ab-
sorption bands at 480 and 579 cm1 were accredited to the
stretching vibrations due to the interaction of oxygen and
cations in CaeO and FeeO bond linkages. The bands at 849
and 709 cm1 were due to OeFeeO and FeeOH linkages and
the band at 453 cm1 related to FeeO linkage. The absorption
band at 636 cm1 was attributed to FeeO bond of ferrite
skeleton. The broad bands at 3423 and 1644 cm1 were
assigned to the OeH broadening due to the compaction of KBr
pellets [5,15].
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3.3. TEM analysis

(mb) T or kg s2 A1

Magnetic moment
TEM (Jeol/JEM 2100 and magnification ranges from 2000

0.00242

0.00189
Xe1500000 X) images (Fig. 3) presented the morphology of the

0.0184
0.0291

0.0125

0.0359
prepared spinel iron oxides. TEM images specified that the
materials were mesoporous in nature as the grain size of the
material ranges between 2 and 50 nm. The images indicated
the aggregation of the material with cubical and irregular
morphology for Ca1-xCuxFe2O4 nanoparticles [14,18]. These
high diameter pictures depicted high degree of agglomera-
tions resulting in the formation of heterogeneous surface.
SAED patterns revealed the dotted ring representing
the spinel structure of Ca1-xCuxFe2O4 oxides and the ring
Squareness ratio

patterns matched with the planes obtained from PXRD

(Mr/Ms), emu/g

studies.
0.798
0.354
0.310
0.296
0.252
0.55

3.4. BET analysis

The porosity and N2 adsorptionedesorption measurements

were analyzed from BET studies (Quantachrome Instrument).
The technique provides the pore diameter, pore volume, and
the surface area of the synthesized nanomaterials. Figure 4 (a-
c) showed pure calcium ferrite exhibited type III isotherm
whereas copper doped calcium nanomaterials showed type II
isotherm and the mesoporous in nature. The bending of curve
(Mr), emu/g
Retentivity

at 0.365 m2/g was due to the multi-layer adsorption [19e22].

27.209 E-3
615.79E6

0.32220
0.21595
0.18354
0.43547

Table 2 showed the adsorption and desorption parameters of

the synthesized Ca1-xCuxFe2O4 oxide nanomaterials. Figure 4
Magnetization
(Ms), emu/g

81.284 E-3
11.720E3

0.68569
0.59580
1.1853

1.2431
Table 3 e Magnetic parameters of CCFO nanoparticles.
Coercivity
(Hci), Oe
663.66
343.67
343.57
345.86
337.00
503.69
Sample code

CCFO-1
CCFO-2
CCFO-3
CCFO-4
CCFO-5
CCFO-6

Fig. 6 e UVeVisible spectra for CCFO nanoparticles.

712 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9
Fig. 7 e Band gap for CCFO nanoparticles.
(d-f) confirmed the presence of random pore size distribution
of the synthesized nanomaterials. The diameter of the pore,
volume of the pore and the surface area of the doped spinel
ferrite (CCFO-5) was larger than the as prepared pure nano
spinel oxides (CCFO-1 and CCFO-6). Gradual growth in surface
area, showed the higher reactive sites to adsorb the impurities
from various organic effluents.
3.5. VSM studies
The hysteresis curve (Fig. 5) of the synthesized copper doped
calcium ferrite nanomaterials showed weak ferromagnetic
behavior, indicating the synthesized Ca1-xCuxFe2O4 as soft
ferrites [15]. The coercivity was found to be 663.66 G, 337 G
and 503.69 G for CCFO-1, CCFO-5 and CCFO-6 respectively.
The Ms, Mr, Hc and the squareness ratio value of the hyster-
esis loops along with magnetic parameters are represented
in Table 3. The magnetic moment (mB) was determined by
relationship:
mB ¼ M*MS =
5585 (3)
where M is the molecular weight.
Lower value Hc of the synthesized nanomaterials showed
the magnetically soft ferrite and distortion of spin happens on
the surface due to the magneto-crystalline anisotropy [23e25].
In transition metal oxides the exchange interaction between
magnetic atoms can be studied by the conduction of electrons.
Confined magnetic moment spin in Cu2þ ions polarizes the
conducting electrons and this polarization in turn couples to a
neighboring localized magnetic moment of calcium ferrite
with a distance. The interaction has an oscillatory dependence
on the distance between the magnetic moments. Hence based
on the distance between the magnetic moments copper doped
calcium ferrites showed weak ferromagnetic behaviour.
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Fig. 8 e Photocatalytic degradation of CCFO nanomaterials under UV lamp irradiation.

3.6. Optical studies
The optical studies were done by using Bruker UVeVisible
spectrometer. The absorption peaks of the Ca1-xCuxFe2O4
spinel nanomaterials were found to be 365, 449, 545, 589, 612
and 766 nm for CCFO-1, CCFO-2, CCFO-3, CCFO-4, CCFO-5 and
CCFO-6 respectively (Fig. 6). The band gap (Fig. 7) of 1.87, 1.88,
1.89, 1.91, 1.96 eV corresponded to CCFO-1, CCFO-2, CCFO-3,
CCFO-4, CCFO-5 nanomaterials which may be due to metal to
ligand charge transfer. The band gap of 2.5 eV corresponded to
CCFO-6 nanomaterial, which might be due to the octahedral
field splitting between t2g and eg of iron orbitals [16]. The syn-
thesized nanomaterials being semiconducting in nature can be
used as nano photocatalysts to degrade methylene blue dye.
3.7. Photocatalytic degradation studies
The photocatalytic experiment was done by using 0.1 g of the
prepared nanomaterials and 100 mL of 25 ppm organic
methylene blue (MB) dye solution. The photocatalytic reaction
media was left for stirring for 30 min to get adsorption equi-
librium before the illumination of UV- lamp. The percentage
714 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9

Fig. 9 e Kinetic plot for CCFO nanoparticles.

of decolourization was observed at 1.4%, 2.3%, 3.4%, 3.7%, 5.3%

and 4.3% for CCFO-1, CCFO-2, CCFO-3, CCFO-4, CCFO-5 and
Fe2þþH2O2/Fe3þþOH. þ OH (5)
CCFO-6 spinel oxides respectively. The photo catalytic studies
were performed for 180 min under the irradiation of UV-lamp
Fe3þþH2O2/Fe2þþ .OOHþHþ (6)
and the solutions were drawn every 30 min and measured
with UVeVisible spectrophotometer. Absorption spectra
(Fig. 8) showed 96% degradation for Ca1-xCuxFe2O4 spinel fer- H2O2 þ .OH/H2Oþ .OOH (7)
rites in 180 min attributed to the small crystallite size and
reduced band gap values. This decrease in absorption indi- Ca1-xCuxFe2O4þhþ/Ca1-xCuxFe2O4 (eþhþ) (8)
cated the increased photocatalytic activity of the synthesized
nanocatalysts. Figure 9 demonstrated linear plot for CCFO Methylene blue dye (MB) þ hþ/ MB dye* (9)
nanomaterials, which indicated the photocatalytic degrada-
tion followed pseudo first order kinetics [26,27]. The degra- MB dye*þhþ/MB dyeþ (10)
dation percentage of the as prepared nano photocatalysts was
determined by the following equation, MB dyeþ þ . OH/ Degradation Products (11)

%Degradation ¼ Co  Ct =Co (4)

The photocatalytic efficiency of Ca1-xCuxFe2O4(x ¼ 0, 0.2,
0.4, 0.6, 0.8 and 1) nanomaterials were enhanced by the
addition of hydrogen peroxide. The electrons produced in the
photocatalytic system were captured by Fenton's reagent and
generated hydroxyl radical degrade the methylene blue dye.
The possible reaction mechanism is given below:
3.8. Photodegradation kinetics
Degradation kinetics of copper doped calcium nanomaterials
with methylene blue dye displayed linear plots confirming the
pseudo first order kinetics of the heterogeneous mixture
(Fig. 9). Degradation kinetics of the as synthesized nano pho-
tocatalysts were investigated by following the relation,

Fig. 10 e Recyclability graph for CCFO nanoparticles.

 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9 715

lnðC0 = CÞ ¼ kt (12)

25 mg/mL 50 mg/mL 25 mg/mL 50 mg/mL 25 mg/mL 50 mg/mL 25 mg/mL 50 mg/mL 25 mg/mL 50 mg/mL 25 mg/mL 50 mg/mL
± 0.50
± 0.16
± 0.28

± 0.50
where k is the rate constant, Co is the initial concentration and
C is concentration at time t.

CCFO-6

10
11
12

10
e
3.9. Recyclability

± 0.44
± 0.57
± 0.50

± 0.44
12
18
10

12
Recyclability and stability of the photocatalysts are important

e
for long term degradation applications of effluents from the
± 0.33
± 0.33
± 0.44

± 0.33
aqua system. Being a ferrite material the as synthesized
nanomaterial can be separated by an external magnet. After
CCFO-5

11
10
12

19
e
the first photocatalytic cycle the catalyst was magnetically
taken out and washed numerous times and heated at 75οC for
13 ± 0.44

11 ± 0.33

13 ± 0.44 24 h in hot air oven. Then the catalyst was recycled again to
check its stability and five successive cycles were performed
e

over MB dye. Figure 10 shows the recyclability of CCFO-5

nanomaterial.
0.67
0.33
0.44
0.33
0.33
±
±
±
±
±

3.10. Antibacterial study

CCFO-4

17
12
19
10
11
0.57
0.28
0.67
0.28

The antibacterial activity of the synthesized copper doped

calcium ferrite was investigated for five bacterial pathogens
±
±
±
±
10
11
10
11

comprising both gram positive and gram negative bacterial

e

strains (Table 4) using the disc diffusion method. The anti-

0.33
0.33
0.57
0.33

bacterial activity varied with the bacterial pathogens. This

19 ±
11 ±
17 ±
11 ±

difference was attributed to the variation in cell wall compo-

CCFO-3

sition (Lipid A, lipopolysaccharide and peptidoglycan make

the cell wall of Gram-negative bacteria, Gram-positive bacte-
12 ± 0.67

13 ± 0.33

12 ± 0.16

ria comprises of peptidoglycan) and the interaction with the

membrane at the cell wall or molecular level. Moreover, the
e

size of the agglomerates and structural morphology of the

12 ± 0.33

12 ± 0.67

prepared nanomaterials also affected the antibacterial activ-

ity. Antibacterial tests (Fig. 11) were done in triplet times and
CCFO-2

the inhibition data were specified as mean ± standard error of

e

e
e

the mean (SEM). Statistics were examined by Microsoft Excel.

± 0.60
± 0.16
± 0.33
± 0.16
± 0.60

The results indicated maximum zone of inhibition against

Gram-positive bacteria. Figure 12 displayed the average Zone
16
12
17
12
14

of inhibition in the range between 0 and 19 mm for CCFO

nanomaterials. CCFO-5 (Ca0.4Cu0.6Fe2O4) nanomaterial with
12 ± 0.28

14 ± 0.60

12 ± 0.28
Table 4 e Antibacterial parameters for CCFO nanomaterials.

small size and large surface area exhibited maximum zone of

inhibition (mm) against both gram positive and gram negative
CCFO-1

bacterial strains attributed to increased initiation of Reactive

Oxygen Species (ROS) thus, creating oxidative stress, causing
± 0.44
± 0.44
± 0.28

± 0.44

damage of DNA and cell membrane resulting in bacterial cell

13
13
12

13

death [22,27].
e
Streptomycin

3.11. Dielectric measurements

10 mg/mL

0.76
0.33
0.76
0.16
0.50
±
±
±
±
±

Frequency dependent applications were studied by dielec-

20
25
20
25
21

trical studies. The dielectric properties of spinel Ca1-xCuxFe2O4

nano oxides have been experimented at room temperature
Enterobacter aerogenes
Staphylococcus aureus

and frequency ranged from 50 Hz to 200 kHz. The dielectric

constant ε is;
Micrococcus luteus
Bacteria

Bacillus subtilis
Escherichia coli

Cd
ε¼ (13)
ε0 A
where A is region of permittivity, ε0 is permittivity, d and C
are thickness as well as capacitance. Figure 13 displayed
S. No.

that both dielectric constant (ε0 ) and the dielectric loss (ε") at
low frequency region and independent at high frequency
1
2
3
4
5
716 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9

Fig. 11 e Antibacterial study for CCFO nanoparticles.

Fig. 12 e Zone of Inhibition graphs for CCFO nanoparticles.

region for copper doped calcium spinel ferrites. Semi-
conducting behavior of the ferrites were explained by
electron hopping Koop's theory [15,21]. This behavior was
due to Maxwell Wagner polarization process i.e., the dipoles
follow the applied field at low frequencies and polarizes
calcium ferrite. The variation at high frequencies in the
electric field becomes brisk and hence the dipoles do not
obey, thus decreasing the polarization along with the
high frequency [19]. In AC conductivity the alignment and
the polarization was related to electrical conduction and
the conductivity contributed by electron interchange be-
tween Fe2þ and Fe3þ ions thus decreases values of the ε.
Increased concentration of Cu2þ dopant in calcium ferrite
decreased the dielectric constant and dielectric loss values.
The higher dielectric constant in CCFO-5 (5508) nano-
material was due to the increase of electrons at the inter-
face between grain boundaries and grains below the
external field implication.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9
Fig. 13 e Dielectric graphs for CCFO nanoparticles.
4. Conclusions
Copper doped calcium ferrite nanomaterials Ca1-xCuxFe2O4
(x ¼ 0, 0.2, 0.4, 0.6, 0.8 and 1) were prepared via coprecipitation
technique. The XRD patterns revealed that the synthesized
ferrites were nano crystalline with the average crystallite size
of about 32e19 nm. FT-IR spectral bands observed at 579, 480
and 514 cm1 confirmed the stretching modes of vibration for
CaeO, FeeO and CueO linkages responsible for the formation
of spinel compounds. TEM images displayed cubical and
irregular morphology for the synthesized materials. VSM
analysis indicated that the as prepared ferrites were soft fer-
rites. BET studies revealed the higher surface area for the doped
calcium ferrites. At high frequency both dielectric constant and
dielectric loss of the synthesized nanomaterials decreased.
Band gap of the prepared spinel ferrites were found to be
1.8e2.5 eV revealing the semiconducting behaviour of the as
prepared spinel ferrites. Ca0.2Cu0.8Fe2O4 (CCFO-5) nanocatalyst
exhibited 96% degradation in 180 min with methylene blue dye.
Moreover, the synthesized nanomaterials were recycled for
five cycles without any substantial loss. The nanostructured
spinel ferrites exhibited better antibacterial action against the
Gram positive bacterial strains.
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.
717
Acknowledgment
The Deanship of Scientific Research (DSR) at King Abdulaziz
University, Jeddah Saudi Arabia has funded this project, under
grant number (KEP-16-130-42). The author Ayyar Manikandan
is thankful to Tamil Nadu State Council for Science and
Technology (TNSCST), DOTE Campus, Chennai for the finan-
cial support (S&T Project: TNSCST/STP-PRG/AR/2018e2019/
9307).
references
[1] Casbeer E, Sharma VK, Li XZ. Synthesis and photocatalytic
activity of ferrites under visible light: a review. Separ Purif
Technol 2012;87:1e14. https://doi.org/10.1016/
j.seppur.2011.11.034.
[2] Hussain Fida, Shah Syed Z, Ahmad Habib, Abubshait Samar
A, Abubshait Haya A, Laref A, et al. Microalgae an ecofriendly
and sustainable wastewater treatment option: biomass
application in biofuel and bio-fertilizer production. A review,
Renew Sustainable Energy Rev 2021;137:110603. https://
doi.org/10.1016/j.rser.2020.110603.
[3] Manimegalai DK, Manikandan A, Moortheswaran S,
Antony SA. Magneto-optical and photocatalytic properties of
magnetically recyclable MnxZn1-xS (x¼ 0.0, 0.3, and 0.5)
nanocatalysts. J Supercond Nov Magnetism 2015;28:2755e66.
https://doi.org/10.1007/s10948-015-3089-3.
[4] Ma Almessiere, Slimani Y, Gungunes H, Manikandan A,
Baykal A. Investigation of the effects of Tm3þ on the
structural, microstructural, optical, and magnetic properties
718 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9
of Sr hexaferrites. Results Phys 2019;13:102166. https://
doi.org/10.1016/j.rinp.2019.102166.
[5] Asiri S, Güner S, Demir A, Yildiz A, Manikandan A, Baykal A.
Synthesis and magnetic characterization of Cu substituted
barium hexaferrites. J Inorg Organomet Polym
2018;28:1065e71. https://doi.org/10.1007/s10904-017-0735-1.
[6] Thilagavathi P, Manikandan A, Sujatha S, Jaganathan SK,
Antony S Arul. Solegel synthesis and characterization
studies of NiMoO4 nanostructures for photocatalytic
degradation of methylene blue dye. Nanosci
Nanotechnol Lett 2016;8:438e43. https://doi.org/10.1166/
nnl.2016.2150.
[7] Vellayappan MV, Jaganathan SK, Manikandan A.
Nanomaterials as a game changer in the management and
treatment of diabetic foot ulcers. RSC Adv 2016;6:114859e78.
https://doi.org/10.1039/C6RA24590K.
[8] Seevakan K, Manikandan A, Devendran P, Shameem A,
Alagesan T. Microwave combustion synthesis, magneto-
optical and electrochemical properties of NiMoO4
nanoparticles for supercapacitor application. Ceram Int
2018;44:13879e87. https://doi.org/10.1016/
j.ceramint.2018.04.235.
[9] Bhavani P, Manikandan A, Jaganathan SK, Shankar S,
Antony SA. Enhanced catalytic activity, facile synthesis and
characterization studies of spinel MneCo aluminate nano-
catalysts. J Nanosci Nanotechnol 2018;18:1388e95. https://
doi.org/10.1166/jnn.2018.14112.
[10] Priyadharshini E, Suresh S, Srinivasan S, Manikandan A.
Electrochemical performance of TiO2eC nanocomposite as
an anode material for lithium-ion battery. J Mater Sci Mater
Electron 2020;31:6199e206. https://doi.org/10.1007/s10854-
020-03173-5.
[11] Almessiere MA, Slimani Y, Gungunes H, Korkmaz AD,
Zubar T, Trukhanov S, et al. Influence of Dy3þ ions on the
microstructures and magnetic, electrical, and microwave
properties of [Ni0.4Cu0.2Zn0.4](Fe2exDyx)O4 (0.00  x  0.04)
spinel ferrites. ACS Omega 2021;6:10266e80. https://doi.org/
10.1021/acsomega.1c00611.
[12] Wei QM, Li JB, Chen YJ, Han YS. X-ray study of cation
distribution in NiMn1-xFe2-xO4 ferrites. Mater Char
2001;47:247e52. https://doi.org/10.1016/S1044-5803 (01)
00177-2.
[13] Liu C, Zou B, Rondinone AJ, Zhang ZJ. Chemical control of
superparamagnetic properties of magnesium and cobalt
spinel ferrite nanoparticles through atomic level magnetic
couplings. J Am Chem Soc 2000;122:6263e7.
[14] Shinde BL, Dhale LA, Mandle UM, Lohar KS. An efficient one-
pot synthesis of benzimidazoles using magnetically
recoverable catalyst chromium doped nickel copper zinc
spinel ferrite. Int Res J Pharm 2019;10:50e5. https://doi.org/
10.7897/2230-8407.1008245.
[15] Vara Prasad BBVS, Ramesh KV, Srinivas A. Structural and
magnetic properties of nanocrystalline nickel ferrite
(NiFe2O4) synthesized in sol-gel and combustion routes. Solid
State Sci 2018;86:86e97. https://doi.org/10.1016/
j.solidstatesciences.2018.10.008.
[16] Ateia EE, El-Bassuony AAH, Abdellatif G, Mohamed AT. The
impact of Ni substitution on the structural and magnetic
properties of Mg nano-ferrite. Silicon 2018;10:1687e96.
https://doi.org/10.1007/s12633-017-9653-7.
[17] Lassoued A, Lassoued MS, Karolak F, Garcı́a-Granda S,
Dkhil B, Ammar S, et al. Synthesis, structural, optical,
morphological and magnetic characterization of copper
substituted nickel ferrite (CuxNi1xFe2O4) through co-
precipitation method. J Mater Sci Mater Electron
2017;28:18480. https://doi.org/10.1007/s10854-017-7795-4.
[18] Sathishkumar G, Venkataraju C, Sivakumar K. Synthesis,
structural and dielectric studies of nickel substituted cobalt-
zinc ferrite. Mater Sci Appl 2010;1:19e24. https://doi.org/
10.4236/msa.2010.11004.
[19] Maaz K, Karim S, Mashiatullah A, Liu J, Hou MD, Sun YM,
et al. Structural analysis of nickel doped cobalt ferrite
nanoparticles prepared by coprecipitation route. Phys B
Condens Matter 2009;404:3947e51. https://doi.org/10.1016/
j.physb.2009.07.134.
[20] Vigneswari T, Raji P. Structural and magnetic properties of
calcium doped nickel ferrite nanoparticles by co-
precipitation method. J Mol Struct 2017;1127:515e21. https://
doi.org/10.1016/j.molstruc.2016.07.116.
[21] Velhal NB, Patil ND, Shelke AR, Deshpande NG, Puri VR.
Structural, dielectric and magnetic properties of nickel
substituted cobalt ferrite nanoparticles: effect of nickel
concentration. AIP Adv 2015;5. https://doi.org/10.1063/1.4931908.
[22] Kavitha N, Manohar P. Magnetic and dielectric studies of Ni-
Co-Zn ferrites synthesized by non-conventional combustion
method. Int J Chem Res 2015;8:308e15.
[23] Lazarevic  Jovalekic
 ZZ,  Milutinovic
 C,  A, Sekulic  D,
Ivanovski VN, Rec nik A, et al. Nanodimensional spinel
NiFe2O4 and ZnFe2O4 ferrites prepared by soft
mechanochemical synthesis. J Appl Phys 2013;113. https://
doi.org/10.1063/1.4801962.
[24] Naidu KCB, Madhuri W. Hydrothermal synthesis of NiFe2O4
nano-particles: structural, morphological, optical, electrical
and magnetic properties. Bull Mater Sci 2017;40:417e25.
https://doi.org/10.1007/s12034-017-1374-4.
[25] Bhuvaneswari M, Sendhilnathan S, Tamilarasan R,
Sivakumar V. A study on leakage current and electrical
properties of oleic acid-coated cobalt-doped Mn-Zn ferrite
nanocrystalline powders. J. Anal. Sci. Technol. 2017;8.
https://doi.org/10.1186/s40543-017-0119-8.
[26] Manikandan V, Sikarwar S, Yadav BC, Vigneselvan S,
Mane RS, Chandrasekaran J, et al. Rapid humidity sensing
activities of lithium-substituted copper-ferrite (LiCuFe2O4)
thin films. Mater Chem Phys 2019;229:448e52. https://
doi.org/10.1016/j.matchemphys.2019.03.043.
[27] Ishaq K, Saka AA, Kamardeen AO, Ahmed A, haq
Alhassan MI, Abdullahi H. Characterization and antibacterial
activity of nickel ferrite doped a-alumina nanoparticle. Eng.
Sci. Technol. an Int. J. 2017;20:563e9. https://doi.org/10.1016/
j.jestch.2016.12.008.
[28] Uddin Iftikhar, Akhtar Rizwan, Abdul Rehman
Khan Muhammd, Zhu Zhiyu, Islam Saeed,
Shoaib Muhammad, et al. Numerical treatment for fluidic
system of activation energy with non-linear mixed
convective and radiative flow of magneto nanomaterials
with Navier's velocity slip. AIP Adv 2019;9(5):055210. https://
doi.org/10.1063/1.5099030.
[29] Batoo Khalid Mujasam, Kumar Gagan, Yang Yujie, Al-
Douri Y, Singh Mahavir, Jotania Rajshree B, et al. Structural,
morphological and electrical properties of Cd2þ doped MgFe2-
xO4 ferrite nanoparticles. J Alloys Compd 2017;726:179e86.
https://doi.org/10.1016/j.jallcom.2017.07.237.
[30] Rais A, Taibi K, Addou A, Zanoun A, Al-Douri Y. Copper
substitution effect on the structural properties of nickel
ferrites. Ceram Int 2014;40(9):14413e9. http://doi.org/10.1016/
j.ceramint.2014.06.037.
[31] Romanov Denis, Moskovskii Stanislav, Konovalov Sergey,
Sosnin Kirill, Gromov Viktor, Ivanov Yurii. Improvement of
copper alloy properties in electro-explosive spraying of ZnO-
Ag coatings resistant to electrical erosion. J. Mat Res.Tech.
2019;8(6):5515e23. https://doi.org/10.1016/j.jmrt.2019.09.019.
[32] Acosta-Zepeda C, Saavedra P, Bonse Jo € rn, Haro-
Poniatowski E. Modeling of silicon surface topographies
induced by single nanosecond laser pulse induced melt-
flows. J Appl Phys 2019;125(17):175101. https://doi.org/
10.1063/1.5053918.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 8 : 7 0 5 e7 1 9
[33] Bouhemadou Abdelmadjid, Allali D, Boudiaf Khaouther,
Qarni Bandar Al, Bin-Omran Saad, Khenata Rabah, et al.
Electronic, optical, elastic, thermoelectric and
thermodynamic properties of the spinel oxides ZnRh2O4 and
CdRh2O4. J Alloys Compd 2019;774:299e314. https://doi.org/
10.1016/j.jallcom.2018.09.338.
[34] Ivanov IA, Alin M, Koloberdin MV, Sapar A, Kurakhmedov AE,
Kozlovskiy AL, et al. Effect of irradiation with heavy Xe22þ
ions with energies of 165e230 MeV on change in optical
characteristics of ZrO2 ceramic. Opt Mater 2021;120:111479.
https://doi.org/10.1016/j.optmat.2021.111479.
[35] Monir Mohammed El Amine, Baltach H, Abdiche A, Al-
Douri Y, Khenata R, Omran S Bin, et al. Doping-induced half-
metallic ferromagnetism in vanadium and chromium-doped
alkali oxides K2O and Rb2O: ab initio method. J Supercond
Nov Magnetism 2017;30(8):2197e210. https://doi.org/10.1007/
s10948-017-4021-9.
[36] Bouhemadou A, Boudrifa O, Guechi N, Khenata R, Al-Douri Y,
Ug ur S‚, et al. Structural, elastic, electronic, chemical bonding
and optical properties of Cu-based oxides ACuO (A¼ Li, Na, K
and Rb): an ab initio study. Comput Mater Sci 2014;81:561e74.
http://doi.org/10.1016/j.commatsci.2013.09.011.
[37] Alalousi Mazin A, Odeh Ali Abu, Ibraheam AS, Al-Douri Y.
The effect of Cu/In molar ratio on the analysis and
characterization of CuInS2 nanostructures. Emergent Mater
2021;4(2):413e22. https://doi.org/10.1007/s42247-021-00176-8.
[38] Salik L, Abdelmadjid Bouhemadou K, Boudiaf F, Saoud Saad,
Bin-Omran Saad, Khenata Rabah, et al. Reshak. Structural,
elastic, electronic, magnetic, optical, and thermoelectric
properties of the diamond-like quaternary semiconductor
CuMn2InSe4. J Supercond Nov Magnetism
2020;33(4):1091e102. https://doi.org/10.1007/s10948-019-
05331-1.
[39] Hamri YZ, Bourezig Yamina, Medles M, Ameri Mohammed,
Toumi K, Ameri I, et al. Improved efficiency of Cu (In, Ga) Se2
thinfilm solar cells using a buffer layer alternative to CdS. Sol
Energy 2019;178:150e6. https://doi.org/10.1016/
j.solener.2018.12.023.
[40] Voon Chun Hong, Lim Bee Ying, Bose Gopinath Subash
Chandra, Al-Douri Yarub, Long Foo Kai, Arshad MK Md, et al.
719
Fabrication of CuO nanostructured thin film by anodizing.
Mater Sci-Poland 2018;36(2):209e16. https://doi.org/10.1515/
msp-2018-0035.
[41] Al-Douri Yarub, Odeh AA, Johan MR, Chowdhury ZZ,
Rafique RF, Reshak Ali H, et al. Synthesis and
characterization of Cu2CdSnS4 quaternary alloy
nanostructures. Int J Electrochem Sci 2018;13:6693e707.
https://doi.org/10.20964/2018.07.45.
[42] Odeh Ali Abu, Al-Douri Yarub, Ameri M, Bouhemadou A.
Analysis and characterization of Cu2CdSnS4quaternary alloy
nanostructures deposited on GaN. Indian J Phys
2018;92:695e703. https://doi.org/10.1007/s12648-017-1153-5.
[43] Bedjaoui A, Bouhemadou A, Aloumi S, Khenata R, Bin-
Omran S, Al-Douri Y, et al. Structural, elastic, electronic and
optical properties of the novel quaternary diamond-like
semiconductors Cu2MgSiS4 and Cu2MgGeS4. Solid State Sci
2017;70:21e35. https://doi.org/10.1016/
j.solidstatesciences.2017.06.007.
[44] Odeh Ali Abu, Al-Douri Y, Voon CH, Mat Ayub R,
Gopinath Subash CB, Abu Odeh Raed, et al. A needle-like
Cu2CdSnS4 alloy nanostructure-based integrated
electrochemical biosensor for detecting the DNA of Dengue
serotype 2. Microchim Acta 2017;184(7):2211e8. https://
doi.org/10.1007/s00604-017-2249-5.
[45] Ibraheam AS, Al-Douri Y, Hashim U, Ameri M,
Bouhemadou A, Khenata R. Structural, optical and electrical
investigations of Cu2Zn1-xCdxSnS4/Si quinternary alloy
nanostructures synthesized by spin coating technique.
Microsyst Technol 2017;23(6):2223e32. https://doi.org/
10.1007/s00542-016-2986-0.
[46] Odeh Ali Abu, Al-Douri Y, Ayub RM, Ameri M,
Bouhemadou A, Prakash Deo, et al. Optical analysis of lens-
like Cu2CdSnS4 quaternary alloy nanostructures. Appl Phys A
2016;122(10):1e15. https://doi.org/10.1007/s00339-016-0420-1.
[47] Mujasam Batoo Khalid, Raslan Emad H, Yang Yujie, Adil Syed
Farooq, Khan Mujeeb, Imran Ahamad, et al. Structural,
dielectric and low temperature magnetic response of Zn
doped cobalt ferrite nanoparticles. AIP Adv 2019;9.
055202e10https://doi.org/10.1063/1.5078411.