Nano-Structures & Nano-Objects 19 (2019) 100322

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Nano-Structures & Nano-Objects

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Green synthesis of zinc doped cobalt ferrite nanoparticles: Structural,

optical, photocatalytic and antibacterial studies
∗
M. Madhukara Naik a , H.S. Bhojya Naik a , , G. Nagaraju b , M. Vinuth c , K. Vinu d ,
R. Viswanath a
a
Department of Studies and Research in Industrial Chemistry, School of Chemical Sciences, Kuvempu
University, Shankaragatta 577451, Karnataka, India
b
Department of Chemistry, Siddaganga Institute of Technology, Tumakuru 572103, Karnataka, India
c
Department of Chemistry, NIE Institute of Technology, Mysuru 570018, Karnataka, India
d
Department of Applied Botany, Kuvempu University, Shankaragatta 577451, Karnataka, India

highlights graphical abstract

• Green synthesized zinc doped cobalt

ferrite nanoparticles for wastewater
treatment.
• Zn-doping in cobalt ferrite enhanced
the photocatalytic activity as visible
active.
• The photocatalyst used for the degra-
dation of Congo red and Evans blue
dyes.
• Zn-doped cobalt ferrite nanoparti-
cles for food packaging and biomed-
ical applications.
• Mechanisms for the degradation of
dyes and antibacterial activity have
been proposed.

article info a b s t r a c t

Article history: The nanostructured zinc-doped cobalt ferrites (Znx Co1−x Fe2 O4 where x ranges from 0.0 to 0.6 with the
Received 11 February 2019 step of 0.2) were prepared by combustion method using curd as a green fuel. The prepared nanopar-
Received in revised form 20 April 2019 ticles were further characterized using XRD, SEM with EDAX, TEM, FTIR, UV-DRS, and luminescence
Accepted 2 May 2019
spectroscopy. From the XRD, it shows that these nanomaterials exhibit average crystallite size in the
Keywords: range ∼12-21 nm with inverse cubic spinel structure. The agglomerated and spherical structure of
Green synthesis the nanoparticles is confirmed by SEM and TEM. The vibrational stretching modes of tetrahedral
CoFe2 O4 (582 cm−1 ) and octahedral (385 cm−1 ) sites were confirmed by FTIR. Further, density functional
Curd theory (DFT) analysis was carried out in order to study the electronic properties of cobalt ferrite
DFT and zinc-doped cobalt ferrite nanostructures. The band gap results for pure CoFe2 O4 and Zn-doped
Optical property CoFe2 O4 nanoparticles were closer to the experimental values. The luminescence spectrum shows
Photocatalytic peaks correspond to violet, blue, green, yellow and orange emission. The photodegradation studies
Antibacterial activity
of obtained nanoparticles were evaluated for the degradation of Congo red and Evans blue dyes under
visible light irradiation. Pure CoFe2 O4 and Zn-doped CoFe2 O4 nanoparticles were inspected against
both gram-positive (Staphylococcus aureus) and the gram-negative (Salmonella typhi) bacteria for

∗ Corresponding author.
E-mail address: hsb_naik@rediffmail.com (H.S. Bhojya Naik).

https://doi.org/10.1016/j.nanoso.2019.100322
2352-507X/© 2019 Elsevier B.V. All rights reserved.
2 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322
antibacterial studies. The gram-negative bacterium Salmonella typhi shows high antibacterial activity
with the inhibition zone of Zn-doped CoFe2 O4 (22 mm) compared to pure CoFe2 O4 (16 mm)
1. Introduction
Magnetic nanoparticles (MNP) are attracting much attention
from many researchers due to their unique properties that are
disclosing from its bulk counterparts [1]. Spinel ferrites have
been studied extensively more than a half-century in nanostruc-
ture because they possess many interesting properties like op-
tical, chemical, electrical and magnetic properties [2–4]. Spinels
are the magnetic semiconductors with general formula MFe2 O4
(where M = Ni, Zn, Co, Mn, etc.) used in diverse technological
fields such as magnetic sensing, solar hydrogen production, spin-
tronics, data storage, catalysts, ferrofluid, inductors, converters,
antennas, magneto-optical recording, humidity sensors, magneto-
resonance imaging (MRI) and energy storage fields [5–8]. Among
ferrites, cobalt ferrite (CoFe2 O4 ) is of extreme prominence and
ferromagnetic material which exhibits unique properties such
as high coercivity (Hc = 1049.6 Oe), cubic magneto-crystalline
anisotropy (Kc = 0.05 erg/cm3 ), narrow bandgap, ease of avail-
ability, saturation magnetization (Ms = 76.08 emu/g), remanence
(Mr = 36.31 emu/g), high Curie temperature (870 K), and high
chemical and mechanical stability [9–11].
Environmental pollution is increasing rapidly with the de-
velopment in the population growth and industries. Due to the
discharge of toxic substances and is threatening the human soci-
ety for sustainable development. Many manufacturing industries
like textile, printing, fabric, leather, etc. were discharge wastew-
ater effluents [12,13]. The synthetic dyes are the major part of
it and were a major concern to the environment because of its
toxicity and carcinogenic properties. Dying, scouring, finishing
and other processes are the major sources of contamination of
water sources from the textile industry [14]. During these pro-
cesses, 10%–15% of the dye does not bind the fibers and released
as effluent. Among the dyes produced in the world, it is estimated
that about 50% of the industrial dyes are azo dyes. The azo groups
(- N = N -) are responsible for the coloration of dyes [15]. At very
low concentration also these dyes are observable in the textile
effluent and have adverse effects on humans (like carcinogenic
and mutagenic effects). Most of these dyes have high chemical
stability, low biodegradability and complicated constitution in
water [16,17].
During the past several decades, to investigate the removal
of hazardous organic dye molecules a number of studies like
ozonation, adsorption on activated carbon, reverse osmosis, chlo-
rination, ultrafiltration, biodegradation, and photocatalytic degra-
dation have been undertaken [18,19]. Recently, to overcome the
environmental and water pollution problems photocatalysis has
emerged as a promising method. Semiconductor photocatalysis
has gained much interest as a green technology among various
reported techniques in harvesting solar energy and destroying or-
ganic or inorganic contaminants in water or air. For photocatalytic
applications, numerous photocatalyst such as TiO2 , ZnO, Fe2 O3 ,
CuO, have been applied actively [20–23].
In recent years bacterial diseases are one of the main reasons
for death. The antibiotics reduced the death caused by bacte-
rial infections. Regularly using traditional medicines avoid the
effect of bacterial growth [38]. Magnetic nanoparticles (NPs) has
been attracted the scientific society because they offer promising
applications in the biomedical field such as genetic screening,
targeted drug delivery, ferrofluids, magnetic resonance imaging,
© 2019 Elsevier B.V. All rights reserved.
magnetic hyperthermia, radiation cancer therapy and medical di-
agnostics [39,40]. These NPs can be easily operated by applying an
external magnetic field. The colloidal stability and targeting of the
nanostructure can be improved with higher the sensitivity of the
NPs which depend on the surface area to volume ratio. These ap-
plications and properties depend on the size, shape, composition,
dopants, microstructure and preparation methods of the NPs [41].
In medicine, the iron oxide NPs have been prepared and applied
for several applications such as targeted drug delivery, bacteri-
cides, and magnetic hyperthermia [42]. Among ferrites, cobalt
ferrite has gained much interest due to unusual physical and mag-
netic properties which lead to its wide applications in the medical
field. In the literature, clinical and biomedical applications of
cobalt ferrite NPs are well recognized and have a wide range of
antimicrobial activity against various human pathogens. There-
fore, to extend their utility in the biomedical field they are in-
corporated by metals/nonmetals into cobalt ferrite matrices [32,
43].
Many researchers have tried to enhance the properties of
cobalt ferrite by incorporating metals and synthesizing with dif-
ferent methods. Ghayour et al. have observed that the specific
absorption rate (SAR) increases with an increase in Zn2+ substitu-
tion into CoFe2 O4 NPs applicable for magnetic hyperthermia stud-
ies [39]. Tatarchuk et al. have studied optical properties with an
increase in band gap (1.17–1.34 eV) and saturation magnetization
(Ms = 91–114 emu/g) also increase as of Zn-dopant in CoFe2 O4
NPs up to certain content [44]. Ansari et al. have prepared Al-
doped CoFe2 O4 NPs which shows the optical bandgap increases
and saturation magnetization decreases with an increase in the
dopant [45]. Sharma et al. have improved the performance of
the catalytic activity by doping yttrium in the spinel structure
of CoFe2 O4 NPs prepared by sol–gel technique [46]. Sundarajan
et al. have studied the photocatalytic degradation of Rhodamine
B under visible light irradiation using Mg-doped cobalt ferrite NPs
prepared by microwave combustion method [47].
Both ZnFe2 O4 and CoFe2 O4 are crystallized in the inverse
spinel structure, represented by (Zn2+ )[Fe2 3+ ]O4 2− and (Co2+ )
[Fe2 3+ ]O4 2− where generally Fe3+ and Zn2+ /Co2+ ions shared
the sites of octahedral (A-site) while Fe3+ ions occupied the
tetrahedral (B-site), respectively [27]. Several methods have been
adopted for the preparation of CoFe2 O4 NPs such as
co-precipitation, solvothermal, sol–gel, hydrothermal, reverse mi-
celle, combustion, microemulsion, microwave and electrochem-
ical, respectively [48]. Combustion method is found to be a
prominent choice for the synthesis of ferrite NPs because it is
efficient and inexpensive with good control of stoichiometry in
production. Additionally, combustion reaction is an exothermic
reaction with a high rate of heat release. Moreover, the method
displays acceleration in saving time, rate of reaction, small and
narrow particle size distribution with good crystallinity, and high
yield [49].
The present work designates the preparation of zinc doped
cobalt ferrite NPs using curd as fuel via combustion method. Curd
is a dairy product obtained in a process called curdling by coagu-
lating milk. Curd contains lactic acids and carbohydrates which
acts as a powerful reducing agent and capable of scavenging
reactive oxygen species which is responsible for the combustion
process. Further, the structural, optical, morphological, and lu-
minescence properties of prepared NPs were studied. Afterward,
photocatalytic and antibacterial applications were studied.
 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322 3

Table 1
Comparison table of biosynthesized ferrite NPs.
Ferrite Method of synthesis Green materials Morphology Calcination temperature (◦ C) Ref.
NiFe2 O4 Sol–gel combustion Honey-mediated Octahedron 1100 [24]
NiFe2 O4 Modified sol–gel Aloe vera extract Agglomerated 900 [25]
CuFe2 O4 Modified sol–gel Aloe vera extract Agglomerated 900 [25]
ZnFe2 O4 Modified sol–gel Aloe vera extract Agglomerated 900 [25]
ZnFe2 O4 Sol–gel combustion Honey-mediated Spherical 1000 [26]
ZnFe2 O4 Conventional heating Opuntia dilenii haw Spherical 900 [27]
ZnFe2 O4 Microwave assisted Hibiscus rosa-sinensis Nanoparticles 900 [28]
ZnFe2 O4 Hydrothermal Aloe vera extract Nanoparticles – [29]
ZnFe2 O4 Green Aegle marmelos leaves extract Spherical 900 [30]
ZnFe2 O4 Combustion Sugarcane juice Agglomerated 600 [31]
CoFe2 O4 Combustion Honey Spherical 600 [32]
CoFe2 O4 Co-precipitation Caffeine Agglomerated 500 [33]
CoFe2 O4 Self-combustion Hibiscus leaf extract Agglomerated 800 [34]
CoFe2 O4 Wet fertilization Hibiscus leaf extract Agglomerated 800 [35]
CoFe2 O4 Conventional heating Okra extract Spherical 1000 [36]
CoFe2 O4 Microwave heating Okra extract Spherical 1000 [36]
CoFe2 O4 Biosynthesis Yeast Spherical – [37]
CoFe2 O4 Combustion Curd Spherical 650 Present work

Table 2
Physical parameters of ZCF NPs.
x D (nm) d (Å) a (Å) δ (×1015 ) lines/m2 V (Å)3 ρx (g/cm3 ) LA (Å) LB (Å)
0 21 2.5273 8.3820 2.268 588.9019 0.5292 3.6294 2.9630
0.2 18 2.5301 8.3913 3.086 590.8642 0.5304 3.6334 2.9663
0.4 14 2.533 8.4009 5.102 592.8945 0.5314 3.6375 2.9697
0.6 12 2.5365 8.4125 6.944 595.3539 0.5328 3.6426 2.9738

2. Material and methods 2.4. Photoreactor setup

2.1. Materials For the photodegradation of wastewater, a visible annular type

In this report, all the materials used were of analytical grade
and used without further purification. Zinc nitrate hexahydrate
[Zn(NO3 )2 •6H2 O], cobalt nitrate hexahydrate [Co(NO3 )2 •6H2 O],
ferric nitrate nonahydrate [Fe(NO3 )3 •9H2 O] were procured from
HIMEDIA, India. Congo red (CR) dye was supplied by SD Fine
Chemicals Limited. Curd is obtained from the Nandini, KMF, Kar-
nataka, India.
2.2. Experimental
Cobalt ferrite NPs with different Zn2+ content with the general
formula [Znx Co1−x Fe2 O4 (x = 0.0, 0.2, 0.4 and 0.6); ZCF] were
prepared using combustion method. Metal nitrates served as
oxidizers and curd as fuel. Metal nitrates of known stoichiometric
ratio were dissolved in curd (2.5 mL) and stirred continuously for
30 min to get a homogeneous mixture. The mixture was kept in a
preheated muffle furnace at 500 ◦ C for about 5 min. The obtained
combustion powder was calcined at 650 ◦ C for about 5 h. These
calcined powders were further used for different characterization
techniques.
2.3. Instrumentation
The phase composition, crystal structure, and size of the ZCF
NPs were studied using Rigaku Smart Lab XRD (Tokyo, Japan) with
Cu-Kα radiation source (λ = 1.5406 Å). The functional groups of
ZCF NPs were analyzed using FTIR (Bruker alpha-P) spectropho-
tometer in the range 4000–350 cm−1 . Zeiss electron microscope
was used to study the surface morphologies of the samples.
Field Emission Gun-Transmission Electron Microscope 300 kV
(high-resolution transmission electron microscope, HR-TEM) was
used to observe the shape and morphology of prepared. UV–
Visible diffused reflectance spectra were recorded in reflectance
mode by a Varian Cary 5 spectrophotometer. For luminescence
studies, Agilent technology Cary Eclipse Spectrofluorometer was
used. During degradation, the absorbance of the organic dye was
recorded by Agilent technology Cary-60 spectrophotometer.
photoreactor (Heber: HVAR 123) was used. There is a cylindrical
jacket made up of quartz placed in the middle of the photoreactor
with a 300 W tungsten visible light source. The cold water is
circulated continuously through the jacket to reduce the heat
generated from the lamp. Around the lamp, eight quartz tubes
(100 mL of volume) were surrounded, with a height of 37 cm
and the inner diameter of 2.3 cm. The photoreactor consists
of cooling fans adjusted at the four corners. For the equal dis-
tribution of photocatalyst in the suspension, air bubbling was
maintained [50].
2.5. Computational details
In order to further study the electronic properties of cobalt
ferrite nanostructures, we used density functional theory (DFT)
analysis. In the present work, the open source SIESTA package is
utilized for studying the electronic properties of cobalt ferrites
(CoFe2 O4 ) [51]. Furthermore, the GGA/PBE exchange–correlation
functional [52,53] has been chosen in the calculation. For struc-
tural optimization of CoFe2 O4 , the energy cutoff is adjusted to 500
eV. The design of CoFe2 O4 is built precisely with exercising double
zeta polarization (DZP) and conjugate-gradient algorithm [54,55]
until the Hellmann–Feynman forces were converged to 0.02 eV/Å.
Besides, Troullier–Martins Pseudo potential is used in the present
work for investigating the core-valence interaction. The CoFe2 O4
Brillouin-zone integration is computed via 15 × 15 × 1 gamma
centered Monkhorst–Pack k-grid [56].
2.6. Photocatalytic degradation of the pollutant
In a visible annular type photoreactor, the aqueous solution of
Congo red (CR) and Evans blue (EB) dyes degradation was carried
using prepared ZCF NPs. In the photocatalytic degradation (PCD)
process, a known weight of ZCF photocatalyst added to a known
volume of an aqueous solution of dyes. For 30 min this reaction
mixture was kept for bubbling to attain the adsorption/desorption
4 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322
equilibrium. The aliquots were taken out of the reaction mixture
at an interval of 30 min under visible light irradiation and cen-
trifugation was employed to separate the photocatalyst from the
collected samples.
The decrease in the absorbance of CR and EB dyes during
degradation was observed in UV–Vis absorption spectrophotome-
ter at the maximum wavelength of 496 and 606 nm. The percent-
age degradation of the aqueous dye solution was calculated by
the relation given below
[ ]
C0 − Ct
η= × 100
C0
Here, η is the degradation percentage (%), C0 is the initial
absorbance of the dye (mg/L); Ct is the absorbance of the dye at
a selected time interval (mg/L).
2.7. Antibacterial activity
The antibacterial activity of prepared CoFe2 O4 and Zn-doped
CoFe2 O4 NPs was screened by agar well diffusion method against
gram-negative (Salmonella typhi) and gram-positive (Staphylo-
coccus aureus) bacterial strains. At room temperature, 100 ml
sterilized agar medium was spread in a 250 mL conical flask. The
nutrient broth for agar media was sub-cultured by taking clinical
isolates of gram negative and gram positive bacterial strains for
24 h at 37 ◦ C. Then, throughout the medium, the media was
mixed thoroughly to make sure the uniform distribution of or-
ganisms. After the distribution of the medium, the sterilized petri
dish was allowed for solidification. In sterile distilled water the
prepared (1 mg/mL) NPs were mixed for about 15 min sonicated
to ensure the uniform distribution of NPs. Further, the sonicated
samples were loaded onto the well at the concentration of 25, 50
and 100 µg/mL. Cefolac (5 mg/mL) has been used as the standard
antibiotic for positive control. After 24 h of incubation at 37 ◦ C,
the inhibition zone was measured and the values were noted.
3. Results and discussion
3.1. XRD analysis
Fig. 1 shows the X-ray diffraction patterns of ZCF NPs prepared
via combustion method calcined at 650 ◦ C. The formation of cubic
spinel structure of CoFe2 O4 NPs (JCPDS 3–864) with Fd3m space
group can be observed in the obtained patterns. There is no sec-
ondary phase was observed in the sample. The average crystallite
size was decreased with an increase in Zn-dopant (Table 2) and
calculated using the following Debye–Scherrer’s relation
kλ
D=
β Cosθ
where k = is the crystallite shape constant (0.89), λ is the wave-
length of X-ray light source (1.540 Å), β is full width at half
maximum (FWHM) and θ is the glancing angle. Further, the
lattice parameter (a) values were calculated using the relation
√ the grain size is affected by the dopant at nano-regime. The
a = dhkl h2 + k2 + l2
where, d is the interplanar distances between two planes and (h,
k, l) are the Miller indices.
The increase in Zn-dopant, the lattice parameter also increases
from 8.3820 to 8.4125 Å. This is because the ionic radius of Zn2+
(0.74 Å) is larger than the ionic radius of Co2+ (0.70 Å) which lead
to the expansion of unit cell [57].
The volume of the unit cells given by
V = a3
Table 3
FTIR assignments (υ1 and υ2 ) for ZCF NPs.
Composition (x) Absorption bands
υ1 (cm−1 ) υ2 (cm−1 )
0 582 385
0.2 578 391
0.4 573 399
0.6 569 403
(1) The theoretical X-ray density (ρx ) was calculated using the
formula given below
ZM
ρx = (5)
Na3
where Z is the number of molecules per unit cell (Z = 8), M is
the molecular weight, N is the Avogadro’s number (6.0223×1023
particles/mole), and a is the lattice parameter.
The magnetic hoping length in the tetrahedral A-sites (LA ) and
octahedral B-sites (LB ) is calculated using the formula given below
(√ )
3
LA = a (6)
4
(√ )
2
LB = a (7)
4
where a is the lattice constant. Table 2 gives the physical param-
eters obtained from XRD spectra of ZCF NPs.
3.2. FTIR analysis
Fig. 2 shows the FTIR spectra of ZCF NPs are recorded in
the range of 4000–350 cm−1 to identify the presence of vibra-
tional bands present in the samples. At 3415–3428 cm−1 a band
observed for all sample attributed to the vibrational stretching
frequencies of adsorbed H − O − H or free molecule of water. The
peak at 1618–1632 cm−1 is assigned to the stretching vibration
of C-O bond [58]. At 1101–1113 cm−1 the bands assigned to
the water molecule retained in the prepared NPs. The two main
bands at 569–582 cm−1 and 385–403 cm−1 are attributed to
the intrinsic vibrational stretching frequency of Fe-O (tetrahedral
sites) and Co-O (octahedral site) respectively. There is a linear
increase in the molecular mass which leads to the vibrational
frequency shifting towards the lower value (Table 3) because of
Zn2+ doping in the cobalt ferrite lattice [59,60].
3.3. Morphological analysis
(2)
The scanning electron micrographs (SEM) and uniform dis-
tribution of CoFe2 O4 and Zn-doped CoFe2 O4 NPs (with x = 0.0
and x = 0.4) shown in Fig. 3(a & b). The images indicate the
formation of agglomerated particles with spherical shape and
(3) internal heat energy produced during combustion causes the
interfacial surface friction leads to the agglomeration of particles.
TEM images of Zn0.4 Co0.6 Fe2 O4 NPs are represented in Fig. 3(c–
d). The images confirm the uniform distribution of particles and
are in the nanometer range, it clearly shows that the spherical
and agglomerated particles of Ni0.5 Co0.5 Fe2 O4 NPs. Fig. 4(a–b)
show the EDAX spectra of CoFe2 O4 and Zn0.4 Co0.6 Fe2 O4 samples.
In Fig. 4(a) the corresponding peaks of Co, Fe and O elements can
be observed, whereas Fig. 4(b) shows the peak for doped Zn2+ in
(4) CoFe2 O4 sample.
 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322 5

Fig. 1. (a) XRD patterns of ZCF NPs calcined at 650 ◦ C synthesized by combustion method (b) XRD patterns of the shift in intense peak (2 2 0) and (3 1 1) with an
increase in Zn-doping concentration.

Fig. 3. (a & b) SEM micrographs of pure CoFe2 O4 and (b) Zn0.4 Co0.6 Fe2 O4 NPs (c
& d) TEM images of Zn0.4 Co0.6 Fe2 O4 NPs.

3.4. Electronic properties of CoFe2 O4 and Zn-doped CoFe2 O4 nanos-

tructures

Fig. 5 illustrates the schematic diagram and band structures

of pristine and Zn-doped CoFe2 O4 nanostructures. Moreover, the
band structure studies give in-depth knowledge regarding the
Fig. 2. FTIR spectra of ZCF NPs. energy band gap of pristine and Zn-doped CoFe2 O4 nanostruc-
tures [61–63]. Hence, we carried out to determine the band
6 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322
gap of pristine and Zn doped CoFe2 O4 nanostructures. For pris-
tine CoFe2 O4 the band gap of 1.56 eV is observed, which is in
agreement with the reported work of K. Dileep et al. [64]. How-
ever, the substitution of Zn in CoFe2 O4 leads to slightly increase
the band gap compared to pristine CoFe2 O4 . The calculated value
of band gap observed from the band structures is noticed to be
1.67 eV, which is attributed to the fact owing to the mismatch
with the ionic radii of zinc ion upon incorporation in CoFe2 O4
nanostructure.
3.5. Optical studies
Diffused reflectance spectra of ZCF NPs were showed in
Fig. 6(a). A large dip in the reflectance spectra observed between
700–850 nm for all the samples, which is significant for the
application in photocatalytic activity. For cobalt ferrite, at 720 nm
the band edge absorption was observed. The absorption edge
sequentially decreases with an increase in Zn2+ doping. The band-
edge absorption values for ZCF NPs were 720, 690, 650 and
625 nm, respectively. The following Kubelka-Munk relation is
used for the determination of bandgap,
1 − R2
F (R) = (8)
2R
where, R is the diffused reflectance. The intercept of the straight
line obtained from the plot of F(R) versus wavelength (λ) on the
λ-axis gives the bandgap value (Fig. 6(b)). For x = 0.0, 0.2, 0.4, and
0.6, the assessed bandgap values were found to be 1.50, 1.54, 1.59,
and 1.67 eV, respectively [65]. There was a significant variation
was observed with Zn2+ doping in energy bandgap values. In
the NPs, due to the sub-bandgap and defects in the formation
of energy level, a redshift for the Zn2+ doping in the cobalt
ferrite was observed. From these results, it can be concluded that
Zn-doped CoFe2 O4 NPs are visible active materials [66,67].
3.6. Luminescence studies
Fig. 7(a) shows the luminescence spectra of ZCF NPs excited
at the wavelength of 310 nm and recorded at room temperature.
The emission peaks are in the range of visible region which is
independent of particle size owing to the charge transfer between
tetrahedral (Zn2+ ) and octahedral (Fe3+ ) sites surrounded by O2−
ions. The emission peaks observed at 410 (violet), 448 (violet),
489 (blue), 546 (green), 572 (yellow) and 605 (orange) which may
be due to the presence of grain boundaries, oxygen vacancies, and
lattice defects in Co1−x Znx Fe2 O4 (x = 0.0, 0.2, 0.4 and 0.6) spinel
NPs. The increase in the Zn2+ doping leads to the decrease in
luminescence intensity which is due to the decrease in the recom-
bination of photogenerated e− /h+ pairs, higher separation rate
and from the valence band to conduction band when irradiated
to visible light [68,69]. The chromaticity coordinates were used
to express the color clarity of any luminescent material, called
as Commission International De I’Eclairage (CIE) [70]. Fig. 7(b)
shows the CIE chromaticity diagram of ZCF NPs at the excitation
of 310 nm. In the inset of Fig. 7(b), the corresponding coordinates
(x, y) are noted. The pure CoFe2 O4 emits green light and shifts
towards bluish light as the Zn-doping increases at the excitation
wavelength of 310 nm which can be observed in the CIE diagram.
3.7. Photodegradation studies
The photocatalytic activity of CoFe2 O4 NPs limited to the re-
combination rate of photo-induced e− /h+ pairs. To avoid the
recombination rate and to improve the photocatalytic activity
of CoFe2 O4 doping of Zn+ ion in the site of Co was carried
out. The enhancement in the photodegradation is due to the
Table 4
Rate constant (k) of CR and EB in the presence of ZCF nanoparticles.
x k × 10−2 min−1
Congo red Evans blue
0 0.72 0.88
0.2 1.25 1.40
0.4 2.11 2.17
0.6 1.69 1.71
prevention of the recombination of e− /h+ pairs and formation of
Fermi energy levels below the conduction band. During degra-
dation, the decrease in the absorbance of CR and EB dyes for
CoFe2 O4 and Zn0.4 Co0.6 Fe2 O4 in the presence of prepared NPs
with respect to irradiation time can be observed in Fig. 7(a, b)
and (c, d). Fig. 8(a, b) shows the comparison study of PCD of
CR and EB dye under visible light irradiation in the presence of
ZCF NPs with respect to irradiation time. In presence of CoFe2 O4 ,
Zn0.2 Co0.8 Fe2 O4 , Zn0.4 Co0.6 Fe2 O4 , and Zn0.6 Co0.4 Fe2 O4 the degra-
dation of CR reached nearly 66, 85, 96 and 92%, respectively. At
the same time, the degradation of EB reached 73, 88, 96 and 93%,
respectively. For both CR and EB dyes, Zn0.4 Co0.6 Fe2 O4 NPs show
the highest photocatalytic activity in 150 min of irradiation time
(Fig. 9). Tables 5 and 6 gives the comparison results of previously
published reports for the degradation of CR and EB dyes.
3.8. Degradation kinetics
The kinetic performance of ZCF NPs for the degradation of
CR and EB was quantitatively measured and fitted using the
Langmuir–Hinshelwood model (Eq. (9)). This model describes rate
constant of photodegradation of the CR and EB in Fig. 10 which
gives the chemical kinetics for the degradation of CR and EB dyes
fits pseudo-first order kinetic model [71].
C0
ln = kt (9)
Ct
where C0 is the initial absorbance of CR dye at time t = 0, Ct is
the change in absorbance of dye at selected intervals of time, and
k is the first order rate constant.
The obtained linear fit plot of ln(C0 /Ct ) v/s irradiation time
gives the rate constant value from the obtained slope. The ob-
tained rate constant for CoFe2 O4 , Zn0.2 Co0.8 Fe2 O4 , Zn0.4 Co0.6
Fe2 O4 , and Zn0.6 Co0.4 Fe2 O4 for CR and EB are depicted in Table 4.
Under visible light irradiation, the photocatalytic activity of Zn0.4
Co0.6 Fe2 O4 shows superior activity when compared to pure
CoFe2 O4 for both CR and EB dyes. Thus, the photocatalytic activity
of Znx Co1−x Fe2 O4 photocatalyst increases with an increase in
zinc doping. Due to the fast recombination rate of e− /h+ pairs,
the efficiency of photocatalytic activity decreases after reaching
its optimal limit. After crossing the optical limit of zinc dop-
ing, the space charge region becomes narrower and the surface
charge barrier becomes higher [69]. Hence, recombination of
photo-generated e− /h+ pair becomes easier and photodegrada-
tion efficiency decreases. Therefore, in the photocatalytic process,
the deformation generated is more in Zn0.4 Co0.6 Fe2 O4 NPs com-
pared to pure CoFe2 O4 NPs which is strongly influenced by the
zinc doping.
3.9. Reaction mechanism of photocatalytic activity
The photocatalytic activity of ferrite NPs is mainly related to
its crystallite size, different preparation conditions, morphology
and surface properties. In the photodegradation process, the con-
centration of surface defects also make a difference and also trap
the electron to inhibit the recombination rate of photogenerated
 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322 7

Fig. 4. EDAX spectra of (a) pure CoFe2 O4 and (b) Zn0.4 Co0.6 Fe2 O4 NPs.

Fig. 5. Schematic diagram and bandstructure of (a) pristine and (b) Zn-doped CoFe2 O4 .

e− /h+ pairs [72–76]. The oxidation and reduction of organic Fig. 11).
pollutants boosted by the hydroxyl (• OH) and superoxide radicals Znx Co1−x Fe2 O4 + hυ (Vis) → Znx Co1−x Fe2 O4 (e− CB + h+ VB ) (10)
• −
( O2 ) produced when the light hits [77–80]. Hence, oxygen
Znx Co1−x Fe2 O4 (e− CB ) + O2 →• O2 − (11)
vacancies also favor photocatalytic activity [81]. The general re-
•
action mechanism was presented in the following relations (see O2 − + H+ ↔ HOO• (12)
8 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322

Fig. 6. (a) UV-DRS spectra of ZCF NPs (b) Plots of F(R)2 versus hυ showing the energy bandgap of ZCF NPs.

Fig. 7. (a) Luminescence spectra and (b) CIE diagram of ZCF NPs. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)

Table 5
Photocatalytic degradation efficiency of CR dye compared with some other ferrite
•
2HOO → H2 O2 + O2 (13) nanoparticles.
Photocatalyst Synthesis method Degradation Ref.
efficiency (%)
H2 O2 → 2HO• (14)
BaFe12 O19 –ZnO Facile chemical 50 [82]
method
+ • +
Znx Co1−x Fe2 O4 (h VB ) + H2 O → HO + H (15) CoFe2 O4 Solution 69.07 [83]
combustion
CoFe1.9 Bi0.1 O4 Solution 73.19 [83]
Dye + HO• +• O2 − →CO2 + H2 O (By-product) (16) combustion
Cu0.5 Co0.5 Fe1.9 Bi0.1 O4 Solution 87.76 [83]
combustion
Dye + Znx Co1−x Fe2 O4 (h+ VB ) → Oxidation product (17) Ni0.6 Co0.4 Fe2 O4 Sol–gel 66.08 [84]
autocombustion
Dye + Znx Co1−x Fe2 O4 (e− CB ) → Reduction product (18) CoFe2 O4 Solution 69.24 [85]
combustion
Co0.5 Cu0.5 Fe2 O4 Solution 71.23 [85]
combustion
3.10. Antibacterial activity MgFe1.5Cr0.5O4 Sol–gel 35 [86]
auto-combustion
The antibacterial activity of prepared CoFe2 O4 and Zn-doped route
SrFe12 O19 Microwave 90 [87]
CoFe2 O4 NPs were performed against gram-negative (Salmonella combustion
typhi) and gram-positive (Staphylococcus aureus) bacterial strains Zn0.4 Co0.6 Fe2 O4 Green combustion 96 Present
by agar well diffusion method. The concentration of NPs is varied work
between 25, 50 and 100 µg/mL. Fig. 12 shows the prepared
NPs shows significant antibacterial activity against the selected
pathogens compared with the standard antibiotic (Cifolac). The
 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322 9

Fig. 8. Time-dependent absorbance spectra of (a, b) CR dye and (c, d) EB dye during degradation using CoFe2 O4 and Zn0.2 Co0.4 Fe2 O4 NPs.

Fig. 9. Control experiments over photocatalytic activity CR and EB dye using ZCF NPs.

Table 6 against S. typhi (22 mm) was high compared to gram-positive S.

Photocatalytic degradation efficiency of EB dye compared with some other metal
aureus.
oxide nanoparticles.
The bacteriostatic activity pure CoFe2 O4 and Zn-doped
Photocatalyst Synthesis Degradation Ref.
method efficiency (%) CoFe2 O4 NPs mainly depends on the reactive oxygen species
(ROS) produced. It also depends on the size, morphology, surface
ZnFe2 O4 Green synthesis 82 [31]
Undoped BiFeO3 Hydrothermal 34.71 [88] area, increase in oxygen vacancies, chemical molecule diffusion
Co-doped BiFeO3 Hydrothermal 39.23 [88] ability, an also the discharge of metal ions. The mechanism of
Cu2 V2 O7 Wet chemical 77.78 [89] bactericidal activity of NPs includes sterilization by absorption,
Cr2 V4 O13 Wet chemical 79 [89]
Zn0.4 Co0.6 Fe2 O4 Combustion 96 Present work
complex function, and discharge of particles. Many previous
reports have studied the photogeneration of ROS on the surface
of the ferrite NPs [90]. The generation of ROS (• O2 − ;, • OH, and
HOO• ) have substantial biological effects and it depends on the
zone of inhibition diameter in mm is measured of selected food- rate of generation, rate of migration and energy levels of the
borne pathogens were depicted in Table 7. For the concentration excited e− /h+ pairs. When the light irradiated on the ZCF NPs, the
of 100 µg/mL, the antibacterial effect of Zn-doped CoFe2 O4 NPs holes (h+ ) created in the valence band and electrons (e− ) excited
10 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322

Fig. 10. Photodegradation kinetics of CR and EB dyes intended with ZCF NPs as photocatalyst.

Fig. 11. Possible reaction mechanism for the photocatalytic degradation of CR and EB dyes over ZCF NPs.

Table 7
Antimicrobial activity of CoFe2 O4 and Zn-doped CoFe2 O4 NPs.
Samples Concentration (µg/mL) ZOI (mm)
Gram positive Gram negative
S. aureus S. typhi
25 09 ± 0.3 08 ± 0.1
50 11 ± 0.6 10 ± 0.4
CoFe2 O4
100 19 ± 0.7 16 ± 0.7
Standard (Cefolac) 16 ± 0.2 17 ± 0.2
25 04 ± 0.3 07 ± 0.5
50 09 ± 0.8 12 ± 0.3
Zn-doped CoFe2 O4
100 15 ± 0.5 22 ± 0.8
Standard (Cefolac) 14 ± 0.9 16 ± 0.6

the cell membranes and damages the cellular proteins, carbohy-

Fig. 12. Antibacterial activity plate photos of pure CoFe2 O4 and Zn-doped
CoFe2 O4 NPs.
to the conduction band. The oxygen molecule reacts with the
excited e− ; to produce • O2 − ; and thereafter, H+ reacts with • O2 − ;
to form HOO• radical. The H2 O molecule undergoes reaction with
h+ to generate • OH and then H+ ion reacts with HOO• to give
hydrogen peroxide (H2 O2 ). This generated H2 O2 infiltrates into
drates, amino acids, nucleic acids, lipids, deoxyribonucleic acid
and then destroys the microbes. Especially, the death of the
microorganisms is because of the stress caused on the surface of
the microorganism cells by the generated ROS in the presence of
light. ROS contains less toxic superoxide radical (• O2 − ), reactive
hydroxyl radical (• OH) and hydrogen peroxide (H2 O2 ) as a weak
oxidizer. Smaller the crystallite size more will be the ROS with the
increase in the surface defects and high specific surface area [91].
Fig. 13 shows the possible reaction mechanism of antibacterial ac-
tivity of Zn-doped CoFe2 O4 NPs. From these studies, it reveals that
the correlation between bactericidal activity and nanostructures.
The prepared CoFe2 O4 and Zn-doped CoFe2 O4 NPs releases the
heavy metal ions (Zn2+ , Co2+ , Fe3+ ) and come in contact with
the cell membranes of microbes. The metal ions with a positive
charge and negatively charged cell membrane attracted mutually
and the metal ions penetrate into the cell membrane. The pres-
ence of metal ions on the surface of bacterial cell showed by the
 M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju et al. / Nano-Structures & Nano-Objects 19 (2019) 100322
Fig. 13. Possible reaction mechanism of antibacterial activity of Zn-doped CoFe2 O4 NPs.
thiol groups (-SH) turns with proteins [92]. The nutrients carried
by the produced proteins penetrate through the cell membrane,
and the inactivation of proteins caused by the NPs and reduces
the cell permeability leads to the death of the bacteria. From the
above results, the synthesized NPs directly act on the bacterial
pathogens to damage the membrane integrity and cells which
ends up in the fatal of pathogenic bacteria [93,94].
4. Conclusion
The nanocrystalline zinc doped cobalt ferrite NPs were suc-
cessfully prepared using curd as a fuel through the combustion
method. The characteristic reflections in XRD patterns reveal
the formation of cubic spinel structure. TEM images confirm
the spherical structure of the NPs. FTIR confirms the vibrational
stretching modes of metal-oxygen bonds in the prepared fer-
rite NPs. Density functional theory (DFT) analysis confirms the
band gap values matches with the experimental values. The op-
tical energy band gap confirms that all the samples were visi-
ble active materials. The recombination rate of photogenerated
electron–hole pairs decreases with increase in Zn-doping can be
observed in dropping of luminescence intensity of cobalt ferrite.
The efficiency of photocatalytic activity of cobalt ferrite increases
with increase in Zn-doping up to x = 0.4 then decrease at x =
0.6 mole fraction. Due to effective separation and inhibition of
e− /h+ pair recombination, relatively highest PCD of Congo red
and Evans blue were achieved for Zn0.4 Co0.6 Fe2 O4 when com-
pared to CoFe2 O4 . The first order rate constant for Zn0.4 Co0.6 Fe2 O4
is faster than CoFe2 O4 . The Zn-doped CoFe2 O4 NPs were revealed
effective antibacterial activity against the human pathogens when
compared to CoFe2 O4 NPs. The prepared NPs were suitable for
optoelectronic, photocatalytic and pharmaceutical applications.
Acknowledgments
One of the authors, M. Madhukara Naik expresses their grat-
itude to the University Grants Commission (UGC), New Delhi
for providing RGNF (SRF-RGNF-2015-17-SC-KAR-8007) and Ku-
vempu University. One of the authors, Dr. G. Nagaraju thanks
DST-SERB (SB/FT/CS-083/2012) Govt. of India, New Delhi for pro-
viding characterization techniques and the Principal, Siddaganga
11
Institute of Technology. One of the authors, Dr. M. Vinuth thanks
to the Principal and Board of Management, NIE-IT for encouraging
the research activity. The authors thank Dr. R. Chandiramouli,
School of Electrical and Electronics Engineering, SASTRA Deemed
University, Thanjavur for DFT simulation studies.
Declaration of competing interest
The authors declare no conflict of interest.
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