Journal of Physics and Chemistry of Solids 138 (2020) 109231

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Journal of Physics and Chemistry of Solids

journal homepage: http://www.elsevier.com/locate/jpcs

Magnetically recoverable multifunctional ZnS/Ag/CoFe2O4 nanocomposite

for sunlight driven photocatalytic dye degradation and
bactericidal application
G. Palanisamy a, K. Bhuvaneswari a, A. Chinnadurai a, G. Bharathi b, T. Pazhanivel a, *
a
Smart Materials Interface Laboratory, Department of Physics, Periyar University, Salem, 636 011, Tamilnadu, India
b
Key Laboratory of Optoelectronic Devices and Systems of Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen, Guangdong
Province, 518060, PR China

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

Keywords: Sunlight driven photocatalysis is the next step of environmental remediation, which can utilize the renewable
ZnS/Ag/CoFe2O4 nanocomposite energy to cure environmental problems. Herein we report a magnetically recoverable ZnS/Ag/CoFe2O4 nano­
Sunlight composite photocatalyst for sunlight driven photocatalytic dye degradation. The composition, structure,
Organic pollutants
morphology, magnetic and photophysical properties of the as prepared samples were investigated by a wide
Antibacterial activity
range of characterization methods. The ZnS/Ag/CoFe2O4 nanocomposite demonstrated sunlight driven photo­
catalytic activity towards the degradation of two different organic dye pollutants. The radical scavenging tests
were conducted to examine the role of different radicals in degrading the dye pollutants. With demonstrated
ferromagnetic behavior, the ZnS/Ag/CoFe2O4 nanocomposite was magnetically recoverable using a commercial
bar magnet. The antibacterial activity of the nanocomposite were also examined against both Gþ (Staphylococcus
aureus) and G (Escherichia coli) bacteria’s. Relatively, the ZnS/Ag/CoFe2O4 nanocomposite showed better
antibacterial activity as compared to CoFe2O4 NPs and Ag/CoFe2O4 samples.

1. Introduction
In the current scenario, it is necessary to turn towards the renewable
energy resource based wastewater treatment strategies [1]. Solar energy
has been extensively used for clean energy production and environ­
mental remediation [2]. However, the use of solar energy for semi­
conductor photocatalysis based wastewater treatment requires a lot
more advancement. Most of the reported semiconductor based photo­
catalysts exhibited high photocatalytic efficiencies only under the
UV-light [3]. In general, scientist use artificial/commercial lamps as
UV-light source, because the solar spectrum contains only a small frac­
tion of the ultraviolet radiation (4–5%). But the visible light covers
nearly 46% of the solar spectrum, which could be effectively utilized for
photocatalytic applications [4]. As stated above, the widely investigated
semiconductor photocatalysts perform poorly under visible light. This
poor performance has been equally affected by the poor visible light
absorption and large trap states that hinder the effective utilization of
photoseparated charge carriers in oxide semiconductors.
Recently, chalcogenide based semiconductors are experimented for
the photocatalytic water treatment, which have the advantage of good
light absorption and comparatively reduced trap state issues. The toxic
nature chalcogenide semiconductors kept them away from the photo­
catalytic applications for a while. The strategy of using comparatively
less-toxic chalcogenides such as ZnS and complete recovery of chalco­
genide photocatalysts after the photocatalytic reaction, give hope for
their application in the field of semiconductor photocatalysis based
organic pollutant degradation. For example, Kula Kamal Senapati. et.al.
reported the uses magnetically recoverable CoFe2O4–ZnS nano­
composite for degradation of methyl orange dye [5]. While addressing
the trap state short comings, such less toxic chalcogenides also suffer
from poor light absorption in the visible region. By preparing composite
with a non/less-toxic and good visible light absorbing material, the
photocatalytic performance of ZnS can be greatly enhanced.
Noble metals are known to have excellent absorption in the visible
region. Amongst Ag nanoparticles exhibit good visible light absorption
owing to the interband transition (4d band to 5sp band) [6]. In addition
the local surface plasmon resonance (SPR) effect makes it a better
candidate for the visible light driven applications [7]. There are several

* Corresponding author.
E-mail address: pazhanit@gmail.com (T. Pazhanivel).

https://doi.org/10.1016/j.jpcs.2019.109231
Received 8 September 2019; Received in revised form 11 October 2019; Accepted 17 October 2019
Available online 18 October 2019
0022-3697/© 2019 Elsevier Ltd. All rights reserved.
G. Palanisamy et al.
Fig. 1. XRD pattern of (a) ZnS QDs (b) CoFe2O4 NPs (c) Ag/CoFe2O4 and (d)
ZnS/Ag/CoFe2O4 nanocomposites.
reports on using the Ag nanoparticle-semiconductor nanocomposites,
such as Ag/NiFe2O4 [8], Ag/CuO/WO3 [9] and g-C3N4/Ag/TiO2 [10] in
order to achieve better photocatalytic performances. In the present
study, Ag nanoparticles has been used to enhance the visible light ab­
sorption of ZnS.
Another challenge in using the chalcogenide semiconductors is the
recovery of the used photocatalysts after the photodegradation experi­
ments. While the aqueous-route-prepared chalcogenides are mostly
soluble in water, their recovery is a difficult process, even using the high
speed centrifugation. One alternate is the magnetic field assisted sepa­
ration. The used photocatalysts can be separated by using a commercial
magnet, provided the photocatalysts are highly magnetic and attract­
able. Unfortunately, chalcogenides possess weak magnetic behavior and
will not be attracted by a magnet. Only the magnetic nanoparticles
(MNPs) will respond to the commercial magnets by showing attraction/
repulsion. Among several categories of MNPs, spinel ferrites are unique
and versatile due to their wide range of applications, viz., supercapacitor
[11], photocatalytic [12], magnetic hyperthermia [13], sensors [14],
and photovoltaic application [15] Cobalt ferrite (CoFe2O4) is a
well-known ferromagnetic material due to its remarkable physical
properties, such as high coercive field, high magnetocrystalline anisot­
ropy, chemical stability, high resistivity and good mechanical hardness
[16]. The CoFe2O4 spinel structure is equally distributed and it has
predominant superexchange interaction between octahedral (Co2þ ions)
site to tetrahedral sites (Fe3þ ions) via Oxygen ions [17]. CoFe2O4
Fig. 2. (a) HRTEM image and (b) EDAX spectra of ZnS QDs and insert of Fig. 2 (a) is SAED pattern of ZnS QDs.
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Journal of Physics and Chemistry of Solids 138 (2020) 109231
nanoparticles can be easily recovered through a commercial bar magnet
and therefore by preparing a composite containing CoFe2O4, the chal­
cogenide semiconductor photocatalysts can be completely recovered for
the reaction medium. In the present study, the magnetically separable
semiconductor photocatalysts has been prepared by using the Ag/Co­
Fe2O4 with ZnS quantum dots (QDs).
The wastewater not only contains the industrial waste pollutants, but
also several microorganisms, which can harm human beings. While the
bacterial infections can create diseases like typhoid, cholera, and para­
typhoid fever, bacillary dysentery and skin diseases. Several materials
exhibit antibacterial/antimicrobial activity, i.e., the materials can stop
the growth and/or can kill the harmful bacterias [18]. Scientists have
always been keen to develop multifunctional materials, which can be
used for more than one application. For example, M. Madhukara Naik
et al. [19]., prepared zinc doped cobalt ferrite nanoparticles and used it
for the degradation of congo red and antibacterial applications.
Recently, Jing Xu et al. [20] have prepared porous g-C3N4 by loading Ag
nanoparticles used for both pollutant degradation and disinfection
under visible light irradiation.
In the present work, we have prepared the magnetically-recoverable
ZnS/Ag/CoFe2O4 nanocomposite by simple precipitation and wet
impregnation methods. The as-prepared ZnS/Ag/CoFe2O4 nano­
composite exhibited enhanced sun-light photocatalytic degradation of
methylene blue (MB) and Rhodamine B (RhB) dyes. The possible reac­
tion mechanism for the enrichment of photocatalytic activity was
investigated. The antibacterial activities of the as-prepared ZnS/Ag/
CoFe2O4 nanocomposite was also studied against gram positive (Staph­
ylococcus aureus) and gram negative (Escherichia coli) bacteria’s. The
experimental results were discussed in detail.
2. Experimental
2.1. Materials
Chemicals used for experiments are Cobalt (II) nitride hexahydrate
(Co (NO3)2⋅6H2O), Iron(III) nitrate nonahydrate (Fe (NO3)2⋅9H2O), Zinc
chloride (ZnCl2), sodium sulfide (Na2S), Silver nitrate (AgNO3), Sodium
hydroxide (NaOH), Trisodium citrate (Na3C6H5O7), Ethanol
(CH3CH2OH). All the chemicals are of analytical grade purchased from
Merck and Aldrich. MB and RhB dye powders were purchased from
Merck chemical company. All the substances were used without further
purification. Deionized water (DI) was employed as the solvent.
2.2. Preparation of ZnS QDs
In a typical synthesis, 0.1 M zinc chloride was dissolved in DI water,
then an equimolar solution of newly prepared 0.1 M of sodium sulfide
G. Palanisamy et al.
Fig. 3. (a, c and e) FESEM images and (b, d and f) EDAX spectra of CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposites.
solution was added dropwise to the above solution. The product was
precipitated and the sample was subjected to purification process by
washing with ethanol and water, in order to remove the byproducts in
the reaction mixture. The obtained mixture was heated at 60 � C for 12 h
to get the sample.
2.3. Preparation of pure CoFe2O4
Pure CoFe2O4 nanoparticles were synthesized through a simple wet
precipitation method [21]. A 2 M of Fe (NO3)3. 9H2O and 1 M of Co
(NO3)2⋅6H2O were dissolved in DI by magnetic stirring for 30 min to
obtain the homogeneity. After that, 1 M of NaOH (precipitating agent)
was added dropwise into the above solution until the pH reached 12 and
the solution was then kept at 85 � C for 60 min, in order to form the spinel
ferrite from hydroxides [17]. The obtained precipitate was collected by
centrifugation and washed with ethanol and DI for several times to
remove the byproducts in the reaction mixture. The resulting product
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Journal of Physics and Chemistry of Solids 138 (2020) 109231
was dried at 60 � C for overnight. The dried powder was then, calcinated
at 900 � C for 3 h in order to obtain the well crystallized sample.
2.4. Preparation of Ag/CoFe2O4 nanocomposites
The same procedure (pure CoFe2O4) was carried out with AgNO3 to
prepare the Ag/CoFe2O4 nanocomposite and also 0.4 M of Na3C6H5O7
was used to reduce the silver nitrate in to silver.
2.5. Preparation of ZnS/Ag/CoFe2O4 nanocomposites
ZnS/Ag/CoFe2O4 nanocomposites were prepared through wet
impregnation technique [22]. The equal weight percentages of the
as-prepared ZnS QDs and Ag/CoFe2O4 nanocomposite were added into
30 mL of ethanol. The obtained solution was continuously stirred and
subsequently heated at 70 � C to evaporate the solvent. Then, the ob­
tained ZnS/Ag/CoFe2O4 nanocomposites were dried for overnight,
G. Palanisamy et al.
Fig. 4. FTIR spectra of (a) ZnS QDs (b) CoFe2O4 NPs (c) Ag/CoFe2O4 and (d)
ZnS/Ag/CoFe2O4 nanocomposites.
collected and stored for further processes.
2.6. Characterization method and instrumentation
The crystal structure and phase purity of all prepared materials were
tested by X-ray diffraction (XRD, Rigaku Mini Flex II powder X-ray
diffractometer) with Cu Kα radiation (1.541 Å). The vibrational spec­
troscopic measurement was carried out using a Fourier transform
infrared spectroscopy (FTIR, PerkinElmer spectrometer). The surface
morphology, chemical composition and elemental mapping of the Ag/
CoFe2O4and ZnS/Ag/CoFe2O4 nanocomposite were examined by field
emission scanning electron microscopy (FESEM, FEI Quanta FEG 200).
The detailed morphology of ZnS QDs was carried out using a high res­
olution transmission electron microscope (HRTEM, JEOL JEM-2000EX
electron microscope). Optical absorption spectra were recorded by
SHIMADZU 3600 UV–Vis model spectrophotometer in the wavelength
range between 200 and 800 nm. The room temperature photo­
luminescence (PL) spectra were carried out on a Horiba Jobin Yvon
Spectro Fluromax 4. The strain state distribution of the as prepared
samples were carried out by Enwave Optronics Field-type EZ Raman
spectrometer. To determine ferromagnetic properties of the synthesized
samples were measured with Lakeshore VSM 7410 vibrating sample
magnetometer. The surface chemical bonding characterized by X-ray
photoelectron spectroscopy (XPS) was performed on a PHI 5000 Ver­
saProbe III.
2.7. Photocatalytic activity test
The photocatalytic behavior of the as-synthesized samples was
evaluated by the photodegradation of MB and RhB dye under the direct
natural sunlight irradiation. The photocatalytic experiments were
executed on the days of bright sunny light in between 10 a.m. and 2 p.m.
in the summer session of Salem city in India. 0.04 g of ZnS/Ag/CoFe2O4
nanocomposite was added to 100 mL of an aqueous solution of dyes
(50 ppm). The solution was placed in the darkroom for 20 min under
constant stirring to achieve the adsorption-desorption equilibrium of
dye on the photocatalyst surface. Photocatalytic degradation was per­
formed by illuminating the suspension under natural sunlight. The
degradation of dyes was examined by UV–Vis spectroscopy at different
time intervals. For comparison, the photocatalytic activity of other
nanocatalyst was also investigated under the same conditions.
The dye (MB & RhB) degradation efficiency was calculated by using
the following equation [23].
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Journal of Physics and Chemistry of Solids 138 (2020) 109231
� �
C0 C
Efficiency % ¼ ​ � 100 (1)
C0
Where, C0 and C are the dye concentrations before and after photo-
irradiation, respectively.
ZnS/Ag/CoFe2O4 nanocomposite photocatalytic activity stability
and reusability was assessed with the same sunlight irradiation and after
each degradation cycle, the catalyst was separated from the MB and RhB
solutions through bar magnet.
2.8. Detection of reactive oxygen species test
One of the important themes in the photocatalytic degradation
process was the detection of reactive species. The different scavengers
were added into the RhB aqueous solution prior to the addition of ZnS/
Ag/CoFe2O4 catalyst such as p-benzoquinone (BQ), triethanolamine
(TEOA) and isopropyl alcohol (IPA). The same above mentioned process
was repeated with different scavengers under the same sunlight radia­
tion to detect the role of active species [24].
2.9. Antibacterial activity evolution
The antibacterial activity of as-prepared samples were studied by
Agar well diffusion method to determine their ability as a potential
antimicrobial agent [25]. The human pathogenic strain such as Escher­
ichia coli (E. coli) and Staphylococcus aureus (S. aureus) were cultured on
nutrient agar plates. 150 mg of as-prepared samples were pressed at
~20 MPa to form a disc of 13 mm diameter and 1 mm thickness. The
presence and the extent of the inhibition zone around the samples were
studied after incubation for 24 h at 37 � C. The same experiments were
repeated in triplicate and zone of inhibition (width) was measured in all
the experiments.
3. Results and discussion
Fig. 1 shows the XRD patterns of the as-prepared samples. As shown
in Fig. 1 (a), the ZnS QDs show three strong and distinct peaks at 2θ of
28.9� , 47.6� and 57.5� corresponding to the (111), (220) and (311)
diffraction planes, reflecting the standard ZnS (JCPDS card # 05-0566)
[22]. For the pure CoFe2O4 (Fig. 1 (b)), the diffraction peaks at 30� ,
35.4� , 43.02� , 53.4� , 57.2� and 62.2� correspond to the (220), (311),
(400), (422), (411) and (440) diffraction confirming the formation of
spinel cubic structured CoFe2O4 nanoparticles (JCPDS card # 22-1086)
[26]. Fig. 1 (c) clearly indicates the contribution of the cubic Ag NPs
diffraction peaks (JCPDS card # 65-2871) [27] which are encompassed
by the broad peaks of CoFe2O4 spinel ferrite (cubic phase, Fd3m) [28].
The recorded diffraction pattern of ZnS/Ag/CoFe2O4 nanocomposite
contains the contributory peaks corresponding to ZnS, Ag and CoFe2O4,
which indicates the formation of the ZnS/Ag/CoFe2O4 ternary nano­
composite (Fig. 1 (d)). By using the Debye-Scherer formula, we have
calculated the average crystallite size values which are about 2.45,
21.72, 28.08 and 36 nm for ZnS, CoFe2O4 and Ag/CoFe2O4 and
ZnS/Ag/CoFe2O4 nanocomposites, respectively.
The detailed size and structure of ZnS QDs were analyzed through
HRTEM and the results are displayed in Fig. 2 (a). The ZnS QDs exhibit
spherical like morphology with an average particle size of 2.9 nm, which
is in correspondence with the XRD result. The insert of Fig. 2 (a) dem­
onstrates the SAED pattern of the ZnS QDs, from this ring formation
reveals that the particles are in the polycrystalline in nature. The EDAX
spectrum of ZnS QDs presented in Fig. 2 (b) indicate the presence of Zn
and S content and the sample purity as well. The morphologies of
CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposite were
analyzed by FESEM. The bare CoFe2O4 displayed spherical like
morphology (presented in Fig. 3. (a)) in which the larger spheres are the
agglomeration of small spherical nanoparticles. In the case of Ag/
G. Palanisamy et al.
Fig. 5. XPS spectra of ZnS/Ag/CoFe2O4 nanocomposites (a) Zn 2P (b) S 2P (c) Ag 3d (d) Co 2P (e) Fe 2P (f) O 1s.
CoFe2O4 sample, the electron microscopic images show the formation of
micron sized Ag plates (Fig. 3 (c)), which are irregularly covered with
the CoFe2O4 nanoparticles (The elemental mapping analysis presented
in Fig. S1 show the distribution of individual elements across the Ag/
CoFe2O4 sample). The addition of ZnS quantum dots lead to even
coverage of these Ag plates by ZnS and CoFe2O4. As shown in Fig. 3 (e),
the ZnS/Ag/CoFe2O4 nanocomposite is evenly covered with nearly
spherical shaped particles. The elemental mapping analysis (Fig. S2)
indicate the homogeneous distribution of all corresponding elements
across the ZnS/Ag/CoFe2O4 nanocomposite sample. The recorded EDAX
spectra of all the samples demonstrated the purity and the atomic and
weight percentages of the corresponding samples reveal the composition
(Fig. 3 (b, d and e).
FTIR spectroscopy is a useful tool to identify the functional group of
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Journal of Physics and Chemistry of Solids 138 (2020) 109231
organic and inorganic samples. Fig. 4 shows the FTIR spectra of the as-
prepared samples. In all the samples a strong band at 3410 cm 1 and a
broad band at 1621 cm 1 are attributed to O–H stretching and H–O–H
bending vibrations, respectively, arising from the physically adsorbed
water molecules. The strong peaks appearing at 470-670 cm 1 are due to
the characteristic Zn–S stretching vibrations of ZnS QDs [29]. The two
bands observed at 1550 and 1417 cm 1 are due to the asymmetrical and
symmetrical stretching of the zinc carboxylate (COO ), respectively
[30]. The FTIR spectra of pure CoFe2O4 nanoparticles exhibit peaks at
2921 and 2850 cm 1 which are attributed to the asymmetric and sym­
metric stretching vibration of the C–O groups, respectively. Ferrites
exhibited two main metal-oxygen bands in the range of 400–600 cm 1.
The peak corresponding to high frequency band vibrations of the
metal-oxygen at the tetrahedral site (ν1) appeared in the frequency range
G. Palanisamy et al. Journal of Physics and Chemistry of Solids 138 (2020) 109231

Fig. 6. (A) UV–Visible spectra and (B) Band gap energy of (a) ZnS QDs (b) CoFe2O4 NPs (c) Ag/CoFe2O4 and (d) ZnS/Ag/CoFe2O4 nanocomposites.

of 600–500 cm 1 and low frequency band vibrations of metal-oxygen at

Fig. 7. PL spectra of (a) ZnS QDs (b) CoFe2O4 NPs (c) Ag/CoFe2O4 and (d) ZnS/
Ag/CoFe2O4 nanocomposites.
Fig. 8. Magnetic hysteresis loop of as-prepared samples.
the octahedral site (ν2) frequency range appeared at 490–400 cm 1 [31].
The addition of Ag to the CoFe2O4 sample has resulted a shift in the Fe–O
peak position from 587 cm 1 to 583 cm 1. This shift is attributed to the
interaction of Ag nanoparticles with the octahedral lattice of CoFe2O4
[32]. The peak appearing at 1018 cm 1 is attributed to the cobalt ion
alloy vibration, as reported elsewhere [33].
The FTIR spectra of ZnS/Ag/CoFe2O4 nanocomposites showed all the
characteristic peaks of individual samples, thereby indicating the for­
mation of the ZnS/Ag/CoFe2O4 nanocomposites. The strain state the
cation distribution of CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4
nanocomposites are shown in Fig. S3 (The detailed description of the
Raman results are presented in supporting information section).
In order to further confirm the surface composition and chemical
state, the ZnS/Ag/CoFe2O4 nanocomposites were analysis by using XPS
and results are depicted in Fig. 5. The surface of ZnS/Ag/CoFe2O4
nanocomposites consists of Co, Fe, S, Ag, Zn and O, which is in good
agreement with the EDAX analysis results. The survey spectrum of the
ZnS/Ag/CoFe2O4 nanocomposite is displayed in Fig. S4. The Zn 2p
spectrum (Fig. 5 (a)) shows two different peaks at binding energies of
1021.5 and 1045.2 eV corresponding to Zn 2p3/2 and Zn 2p1/2, respec­
tively; the typical binding energies of Zn2þ states in ZnS QDs [22,34].
Further, the peak at 23.0–23.1 eV is attributed for zinc ions binding to
sulphur ions in ZnS lattices [35] are demonstrated in Fig. S4. The S 2p
spectrum (shown in Fig. 5 (b)) displayed two distinct peaks at 160.95
and 162.75 eV, araising from S 2p3/2 and S 2p1/2 of metal-sulphur
binding, as reported elsewhere [22].
As shown in Fig. 5 (c), the two eminent peaks at 368.2 and 374.2 eV
are ascribed to characteristic Ag 3d5/2 and Ag 3d3/2 of Ag0, respectively.
The Ag 3d5/2 peak clearly shows the presence of Ag metal hybrid into the
ferric matrix, which is in good agreement with the other analytical re­
sults. As shown in Fig. 5 (d), the Co 2p XPS spectrum contains four peaks
which can be described as, (i) peaks at 781.5 and 786.4 eV corre­
sponding to Co 2p3/2 and its shakeup satellites, respectively, and (ii) at
796.06 and 803.26 eV corresponding to Co 2p1/2 and its shakeup sat­
ellites, respectively [36]. Based on the above observation, we conclude
that, cobalt mainly exists in the Co2þ state in the sample, since the
intense shakeup Co 2p satellites are derived from the unpaired valence
3d electron orbitals of the high spin Co2þoxidation state. The Fe 2p high
resolution XPS spectrum presented in Fig. 5 (e) displays two major peaks
centered at 712.6 eV and 725.16 eV, which are assigned to Fe 2p3/2 and
Fe 2p1/2, respectively, which indicates the presence of Fe3þ oxidation
state [37]. The peaks at 715.96 and 733.66 eV are ascribed to Fe 2p3/2
and Fe 2p1/2 shakeup satellites, respectively [36]. The O1s spectrum
presented in Fig. 5 (f) was deconvoluted into two peaks at 529.81 and

6
G. Palanisamy et al.
Fig. 9. (a) Concentration changes of RhB as a function of irradiation time. (b) First order kinetics in RhB dye degradation of as prepared photocatalyst (c)
Degradation efficiency of asprepared nanocatalyst (d) Cycling runs for the photocatalytic degradation of RhB over ZnS/Ag/CoFe2O4 nanocomposite under sun light
irradiation.
531.81 eV are attributed to O2 present in the lattices and the chem­
isorbed oxygen species, respectively [38]. Therefore, from the XRD,
FTIR, Raman EDAX and XPS investigation, the analytical results
confirmed the formation of ZnS QDs/Ag metal/CoFe2O4 nanocomposite.
The optical absorption measurement is the powerful tool for under­
standing the absorption behavior and band structure of both crystalline
and non-crystalline materials. The optical properties of the as-prepared
nanoparticles were investigated by UV–Visible spectrometer and the
results are shown in Fig. 6 A. It can be clearly seen that, the pure ZnS
QDs have strong absorption peak at 308 nm, which is in correspondence
with previous reports [39]. Moreover, the reported absorption value of
bulk ZnS is 350 nm and it is blue shifted in our pristine ZnS QDs
(~308 nm). As reported elsewhere, this blue shift is due to quantum
confinement effect that comes into play when the particle is comparable
or less the exciton Bohr radius [40]. Our ZnS QDs have the size value of
2.45 nm, and therefore it is obvious to observe the quantum confinement
effect [41]. The Pure CoFe2O4 sample have strong and broad absorption
peak at 409 nm which indicates strong absorption in the visible light
region (Fig. 6 A (b)) and the incorporation of Ag, further enhanced the
absorption (Fig. 6A (c)). In the case of ZnS/Ag/CoFe2O4 nanocomposite
sample, the ZnS QD incorporation enhanced the absorption in the UV
region and it is clear that the as prepared ZnS/Ag/CoFe2O4 nano­
composite can absorb both visible and UV light. This enhanced optical
absorption lead to improved charge carrier separation, which is dis­
cussed in the application part.
The optical band gap energy (Eg) for the synthesized samples was
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Journal of Physics and Chemistry of Solids 138 (2020) 109231
calculated using the Tauc’s relation [42]. Fig. 6 B shows the plots of
(αhν)2 versus absorption energy hν in eV for all the synthesized samples.
The obtained Eg value of pure ZnS QDs is 3.8 eV, which is larger than the
reported value of the ZnS nanoparticles, indicating the role of quantum
confinement effect [22]. The CoFe2O4 nanoparticles show a direct
bandgap of about 1.62 eV and the addition of Ag content in CoFe2O4
nanoparticles, increased the band gap value from 1.62 to 2.02 eV.
Further, the bandgap of ZnS/Ag/CoFe2O4 nanocomposites is increased
to 2.3 eV. The optical absorption and the measured bandgap values
indicate the electronic interaction between ZnS QDs, Ag and CoFe2O4.
Since, the recombination rate and separation efficiency is an
important tool in the wastewater degradation process, the PL spectra
were recorded at room temperature in order to investigate the charge
carrier trapping and recombination phenomena [43]. Fig. 7(a–d) shows
the PL spectra of the as-prepared samples. The ZnS QDs exhibited a
broad peak around 440 nm with a shoulder-like peak around 360 nm.
While the peak around 360 nm is produced by the band edge recombi­
nation transition, the peak around 440 nm was originated from the
sulphur vacancy trap state mediated radiative recombination process
[44].
The CoFe2O4 and Ag/CoFe2O4 samples display the emission band at
around 355 nm, originating from the radiative defects related to the
interface traps existing at the grain boundaries [45]. In the case of
ZnS/Ag/CoFe2O4 nanocomposite, the emission was similar to that of
ZnS QDs with decreased intensity in the visible region around 440 nm.
This observed decrease indicates the decreased trap state mediated
G. Palanisamy et al. Journal of Physics and Chemistry of Solids 138 (2020) 109231

Fig. 10. (a) Concentration changes of MB as a function of irradiation time. (b) First order kinetics in MB dye degradation of as prepared photocatalyst (c)
Degradation efficiency of asprepared nanocatalyst (d) Cycling runs for the photocatalytic degradation of MB over ZnS/Ag/CoFe2O4 nanocomposite under sun light
irradiation.

Fig. 11. (a) Powder XRD patterns and (b) FTIR spectra for ZnS/Ag/CoFe2O4 nanocomposite before and after 4 cyclic runs.

recombination in ZnS QDs, which means that the photoexcited electrons
trapped at the sulphur vacancies might be transferred to other compo­
nents, thereby creating a charge separated state. Such charge separation
process will have good effect in the photocatalytic degradation process
by enhancing the radical generation.
The room temperature (300 K) magnetic measurements of pure
CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposite were car­
ried out by applying an external magnetic field of 1.5 T. From the hys­
teresis loop, it can be observed that all the as-prepared samples exhibit
ferromagnetic behavior, as shown in Fig. 8. The measured saturation

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G. Palanisamy et al. Journal of Physics and Chemistry of Solids 138 (2020) 109231

Fig. 12. Effects of many active scavengers on the degradation of RhB over ZnS/
Ag/CoFe2O4 nanocomposite under irradiation with sunlight.
magnetization, coercivity and residual magnetization values of Ag/
CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposite (0.5407 emu/g,
1139.6 Oe and 0.17 emu/g and 0.4338 emu/g, 1050.46 Oe, 0.12 emu/
g), are lower than that of the bare CoFe2O4 nanoparticles (0.8670 emu/
g, 1175.1 Oe and 0.22 emu/g). This decrease is ascribed to the incor­
poration of non-magnetic ZnS and Ag nanoparticles to CoFe2O4.
This type of reduction may be due to the quenching of surface
moment and small particle size effect [46,47]. These experimental re­
sults confirm the magnetically recoverable nature of the ZnS/Ag/Co­
Fe2O4 nanocomposite photocatalyst. The widely used MB and RhB dyes
were chosen as model organic pollutants to check photocatalytic
degradation efficiency of the as prepared photocatalysts. The photo­
catalytic degradation of RhB was carried out in the presence of ZnS QDs,
CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposite under the
sunlight irradiation. The treated dye samples were collected at regular
intervals and subjected to optical absorption measurements. The
measured absorption spectra showed the linear decrease in the charac­
teristic absorption of RhB dye (at around 550 nm), which indicates the
photocatalytic degradation under visible light. The ZnS/Ag/CoFe2O4
nanocomposites exhibited the excellent photocatalytic activity for the
degradation of RhB under the sunlight irradiation, which is about
96.54% of RhB photodegraded after 150 min (Fig. 9 (a) & (b)). While,
the control dye sample treated without photocatalysts showed only a 2%
degradation, the other samples exhibited the efficiency of 50–60%.
Therefore, it is clear that the ZnS/Ag/CoFe2O4 nanocomposite pho­
tocatalyst exhibited better performance in degrading the RhB dye under
visible light. To quantitatively study the reaction kinetics, the RhB
degradation was fitted to the first-order kinetic equation [24]. The
fitting model indicates the better photocatalytic activity of ZnS/Ag/­
CoFe2O4 nanocomposite, which was improved by the incorporation of
ZnS QDs and Ag with CoFe2O4 nanoparticles. The bar graph in Fig. 9 (c)
represents the comparative % RhB dye degradation for all prepared
samples.
In Fig. 10 (a), similar behavior was observed for photocatalytic
degradation of MB dye in the presence of as-prepared samples under
direct sunlight irradiation. It was obvious from (Fig. S5, Supporting
Information) that the absorption peak of MB at 664 nm decreased
significantly as time increases, indicating the efficient degradation of
this cationic dye in the presence of the ZnS/Ag/CoFe2O4 nanocomposite.
Fig. 10 (b) shows the high value first-order rate constant (k ¼ 0.0256
min 1) values for ZnS/Ag/CoFe2O4 nanocomposites curves exhibited
good linear performance compared to other prepared samples. The
degradation efficiency (C/C0) of MB over ZnS QDs, CoFe2O4, Ag/
CoFe2O4 and ZnS/Ag/CoFe2O4 nanocomposites was found to be 50,
62.12, 74.19 and 95.78%, respectively, after 90 min sunlight irradiation
(Fig. 10 (c)).
Recyclability of Photocatalysts is a very important parameter of the
catalytic degradation process, because the use of recyclable and reusable
photocatalysts lead to a significant cost reduction of the treatment. The
reusability and photostability of a photocatalyst are shown in Figs. 9 (d)
and 10 (d). The ZnS/Ag/CoFe2O4 nanocomposites were further inves­
tigated through four successive runs under the same experimental con­
ditions. Each run was conducted for 150 and 90 min for RhB and MB dye
respectively, after every run the reaction system was re-evaluated. These
results indicated that the ZnS/Ag/CoFe2O4 nanocomposites remained
effective for first two cycle and later it was slightly decreased due to the
slight inactivation of the photocatalyst caused by surface adsorption of
small fragmented species during the degradation process.
The stability of the ZnS/Ag/CoFe2O4 nanocomposite was examined
by XRD and FTIR [48]. Fig. 11 (a) shows the XRD pattern of ZnS/Ag/­
CoFe2O4 nanocomposite before and after four photocatalytic reactions,
which are very similar, thereby indicating the stability of the photo­
catalysts. Fig. 11 (b) shows the FTIR Spectra of Ag/CoFe2O4
Fig. 13. Schematic illustration of the photocatalytic separation and transfer of
photogenerated charge carriers on the ZnS/Ag/CoFe2O4 nanocomposite under
sun light irradiation.

Table 1
Comparison of degradation efficiency for various photocatalysts.
S.No. Photocatalyst Dye Catalyst amount (mg/L) Irradiation time (min.) Degradation efficiency (%) Ref.

1. AgCl/Ag NPs MB 50 240 ~100 [49]

2. CoFe2O4-graphene composite MB and RhB 20 240 ~93 and 94 [50]
3. Zn0.6Co0.4Fe2O4 MB 10 480 ~90 [51]
4. CuFe2O4- graphene composite MB 25 240 ~96 [52]
5. P25–CoFe2O4-PANI MO 40 420 ~90 [53]
6. CoFe2O4 rGO nanocomposite MB 10 180 ~95 [54]
7. Ag–TiO2 nanofibers. MB 50 260 100 [55]
8. TiO2/CoFe2O4 nanocomposite MO 20 120 ~75 [56]
9. Ag/ZnO nanocomposite MB 20 480 ~93 [57]
10. ZnS/Ag/CoFe2O4 nanocomposite MB and RhB ~40 90 and 150 ~95.78 and 96.54 This work

9
G. Palanisamy et al. Journal of Physics and Chemistry of Solids 138 (2020) 109231

Fig. 14. Inhibition zone formed around the samples disks against E. coli and S. aureus cultures (a) CoFe2O4 NPs (b) Ag/CoFe2O4 and (c) ZnS/Ag/CoFe2O4
nanocomposites.

(O�2 ) for the degradation of dye molecules [60]. The RhB or MB dye
Table 2 pollutant was oxidized (active species) to produce carbon dioxide and
Antibacterial activity of pure CoFe2O4 and Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 water [22]. The photocatalytic separation and transfer of photo­
nanocomposite towards E. coli and S. aureus. generated charge carriers on the ZnS/Ag/CoFe2O4 nanocomposite under
Samples Diameter of Zone of inhibition (mm) sunlight irradiation were schematically represented in Fig. 13.
E. coli S. aureus A possible photocatalytic mechanism of the ZnS/Ag/CoFe2O4
nanocomposite under sunlight irradiation was proposed. The ZnS/Ag/
Positive Control 18 � 0.50 19 � 0.25
CoFe2O4 NPs 6 � 0.25 6 � 0.50
CoFe2O4 nanocomposite absorbs the visible light photons and produce
Ag/CoFe2O4 nanocomposite 11 � 0.80 12 � 0.30 the electron-hole pairs. Silver nanoparticles immigrated (hþ) from the
ZnS/Ag/CoFe2O4 nanocomposite 26 � 0.10 21 � 0.60 VB of CoFe2O4 into VB of ZnS QDs, which reacted with OH or water
molecules to form to � OH radicals. The electrons transferred from CB of
ZnS to CB of CoFe2O4 are available on the ZnS/Ag/CoFe2O4 nano­
nanocomposite before and after four cycling trials. The characteristic
composite surface to get reacted with absorbed oxygen, thereby forming
vibration peaks of ZnS/Ag/CoFe2O4 nanocomposite do not noticeably
the superoxide radicals (O�2 ). The generated active species (O�2 , � OH,
change, indicating that it was stable after recycling.
hþ) react with dye molecule to produce CO2 ; ​ NO3 ; H2 O; etc...
In order to identify which active species played important role in dye
Generally, Ag nanoparticles and Ag based composites have been
degradation when using ZnS/Ag/CoFe2O4 under sunlight irradiation, a
widely used as an effective antibacterial agent [61]. The antibacterial
series of experiments on quenching active species by adding individual
properties of CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4 nano­
scavengers to the photocatalytic reaction system were carried out. The
composite are studied to explore their convenience as a prospective
photodegradation of RhB with the addition of TEOA (hþ quencher), BQ
material for antibacterial applications. The excellent activity of the
(� O2 quencher), and IPA (� OH quencher) were evaluated and the results
antibacterial effect of the as-prepared samples against S. aureus (Gþ) and
are shown in Fig. 12. The extent of decrease caused by scavengers in the
E. coli (G ) shown in Fig. 14. The activity towards the Gþ bacteria are
conversion indicated the importance of the corresponding reactive
more because of G bacteria cell wall is more probable than the Gþ
species. The ZnS/Ag/CoFe2O4 nanocomposite was greatly inhibited
bacteria, and the composite nanoparticles may get trapped into easily
after adding BQ (� O2 quencher), therefore it is clear that the (� O2 ) is the
[62] by the electrostatic interactions between the appreciated ions and
main reactive species in the photocatalytic degradation of RhB under
the bacteria’s. The ZnS/Ag/CoFe2O4 nanocomposite showed better
direct sunlight irradiation. While the � OH, e and hþ reactive species
antibacterial activity against Gþ and G compared to the bare samples.
were playing a minor role, the synergistic effect could have affected the
The ZnS/Ag/CoFe2O4 nanocomposites showed a clear zone of inhi­
overall better photocatalytic degradation of the RhB dye. The photo­
bition around the disc indicating the bacterial inhibition. The zone of
catalytic activity of the as-prepared ZnS/Ag/CoFe2O4 nanocomposites
inhibition exhibited by CoFe2O4, Ag/CoFe2O4 and ZnS/Ag/CoFe2O4
was compared to the previously reported experiments under the visible
nanocomposites are given in Table 2.
light irradiation and presented in Table 1 [49–57].
The zones of inhibition were then evaluated so that their sizes could
The band structure (valance and conduction band) of ZnS/Ag/
be averaged from three small dishes on the same testing plate. The
CoFe2O4 nanocomposite was calculated by using Mulliken electroneg­
catalytic process of ZnS/Ag/CoFe2O4 generates different reactive oxy­
ativity theory [24]. The absolute electronegativity value of ZnS QDs and
gen species including superoxide and hydroxyl radicals. The superoxide
CoFe2O4 nanoparticles were 5.26 [58] and 5.47 eV [21]. The calculated
radical’s directly involved and damage to the outer surface of the bac­
valance band (VB) and conduction band (CB) edge positions of ZnS and
teria. The electromagnetic attraction between the positive charge of the
CoFe2O4 are 2.66, 1.14 eV and 1.78, 0.16 eV, respectively. When the
ZnS/Ag/CoFe2O4 nanocomposite and the negative charge of the bacteria
photocatalyst was irradiated, the sunlight generates electron-hole pairs.
cell wall lead to the detriment of the microorganism. It is clear that, the
The CB edge position of ZnS QDs is more negative than that of CoFe2O4
ZnS/Ag/CoFe2O4 nanocomposite is more effective against Gram-
NPs. Thus the electrons were transferred from CB of ZnS QDs into the CB
positive bacteria; so the zone of inhibition was larger for S. aureus
of CoFe2O4 NPs, while the holes are transferred into VB of ZnS QDs.
than that for E. coli. The above study showed that the antibacterial ac­
Silver nanoplates might have worked as an electron emitter to send out
tivity of the ZnS/Ag/CoFe2O4 nanocomposite is better than those of the
electrons (e ) to the CB of CoFe2O4 NPs [59]. These electrons react with
bare samples.
oxygen molecules in water to generate the superoxide radical anions

10
G. Palanisamy et al.
4. Conclusion
In summary, pure ZnS QDs, CoFe2O4 NPs, Ag/CoFe2O4 and ZnS/Ag/
CoFe2O4 nanocomposite samples have been successfully fabricated via a
simple precipitation method. The crystal structure, functional group,
morphology, chemical composition, and photophysical properties were
revealed by XRD, FTIR, FESEM, EDAX with mapping, UV, and PL ana­
lyses. The ZnS/Ag/CoFe2O4 nanocomposite exhibited superior photo­
catalytic activity for the degradation of MB and RhB under sunlight
irradiation. The added Ag content provided the visible light absorption
capability and the CoFe2O4 provided ferromagnetic behavior to the ZnS/
Ag/CoFe2O4 nanocomposite sample. The enhanced visible light ab­
sorption resulted the efficient photocatalytic degradation and the
ferromagnetic behavior helped to recover the sample with ease. The
antibacterial activity of the nanocomposite was examined against both
Gþ and G bacteria’s. The ZnS/Ag/CoFe2O4nanocomposite showed
better antibacterial activity as compared to other samples. With all the
experimental results, we conclude that, the ZnS/Ag/CoFe2O4 nano­
composite serves as an overall better candidate in terms of degradation
efficiency as well as recyclability.
Declaration of competing interest
No Conflict of Interest form.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpcs.2019.109231.
References
[1] P.V. Kamat, J. Bisquert, Solar fuels. photocatalytic hydrogen generation, J. Phys.
Chem. C 117 (2013) 14873–14875.
[2] M.A. Nguyen, E.M. Zahran, A.S. Wilbon, A.V. Besmer, V.J. Cendan, W.A. Ranson,
R.L. Lawrence, J.L. Cohn, L.G. Bachas, M.R. Knecht, Converting light energy to
chemical energy: a new catalytic approach for sustainable environmental
remediation, ACS Omega 1 (2016) 41–51.
[3] X. Chen, S. Shen, L. Guo, S.S. Mao, Semiconductor-based photocatalytic hydrogen
generation, Chem. Rev. 110 (2010) 6503–6570.
[4] S. Kumar, S. Tonda, A. Baruah, B. Kumar, V. Shanker, Synthesis of novel and stable
g-C3N4/N-doped SrTiO3 hybrid nanocomposites with improved photocurrent and
photocatalytic activity under visible light irradiation, Dalton Trans. 43 (2014)
16105–16114.
[5] K.K. Senapati, C. Borgohain, P. Phukan, CoFe2O4-ZnS nanocomposite: a
magnetically recyclable photocatalyst, Catal. Sci. Technol. 2 (2012) 2361–2366.
[6] X. Chen, Z. Zheng, X. Ke, E. Jaatinen, T. Xie, D. Wang, C. Guo, J. Zhao, H. Zhu,
Supported silver nanoparticles as photocatalysts under ultraviolet and visible light
irradiation, Green Chem. 12 (2010) 414–419.
[7] P. Dong, B. Yang, C. Liu, F. Xu, X. Xi, G. Hou, R. Shao, Highly enhanced
photocatalytic activity of WO3 thin films loaded with Pt–Ag bimetallic alloy
nanoparticles, RSC Adv. 7 (2017) 947–956.
[8] D. Zhang, X. Pu, K. Du, Y.M. Yu, J.J. Shim, P. Cai, S. Il Kim, H.J. Seo, Combustion
synthesis of magnetic Ag/NiFe2O4 composites with enhanced visible-light
photocatalytic properties, Separ. Purif. Technol. 137 (2014) 82–85.
[9] H. Katsumata, Y. Oda, S. Kaneco, T. Suzuki, Photocatalytic activity of Ag/CuO/
WO3 under visible-light irradiation, RSC Adv. 3 (2013) 5028.
[10] Y. Chen, W. Huang, D. He, Y. Situ, H. Huang, Construction of heterostructured g-
C3N4/Ag/TiO2 microspheres with enhanced photocatalysis performance under
visible-light irradiation, ACS Appl. Mater. Interfaces 6 (2014) 14405–14414.
[11] V.S. Kumbhar, A.D. Jagadale, N.M. Shinde, C.D. Lokhande, Chemical synthesis of
spinel cobalt ferrite (CoFe2O4 ) nano-flakes for supercapacitor application, Appl.
Surf. Sci. 259 (2012) 39–43.
[12] Z. Jia, L. Yang, Q. Wang, J. Liu, M. Ye, R. Zhu, Synthesis of hierarchical CoFe2O4
nanorod-assembled superstructures and its catalytic application, Mater. Chem.
Phys. 145 (2014) 116–124.
[13] D.H. Kim, D.E. Nikles, D.T. Johnson, C.S. Brazel, Heat generation of aqueously
dispersed CoFe2O4 nanoparticles as heating agents for magnetically activated drug
delivery and hyperthermia, J. Magn. Magn. Mater. 320 (2008) 2390–2396.
[14] H.J. Zhang, L.Z. Liu, X.R. Zhang, S. Zhang, F.N. Meng, Microwave-assisted
solvothermal synthesis of shape-controlled CoFe2O4 nanoparticles for acetone
sensor, J. Alloy. Comp. 788 (2019) 1103–1112.
[15] K.L. Routray, S. Saha, D. Behera, N. Tripathy, S.P. Ghosh, High dielectric constant,
low loss and efficient visible photoluminescence properties of porous rose- flower
shaped CoFe2O4 for photovoltaic application, Mater. Lett. 242 (2019) 62–65.
11
Journal of Physics and Chemistry of Solids 138 (2020) 109231
[16] M. Atif, M. Idrees, M. Nadeem, M. Siddique, M.W. Ashraf, Investigation on the
structural, dielectric and impedance analysis of manganese substituted cobalt
ferrite i.e., Co1-xMnxFe2O4 (0.0 � x � 0.4), RSC Adv. 6 (2016) 20876–20885.
[17] D.S. Nikam, S.V. Jadhav, V.M. Khot, R.A. Bohara, C.K. Hong, S.S. Mali, S.H. Pawar,
Cation distribution, structural, morphological and magnetic properties of Co1 xZn
xFe2O4 (x ¼ 0–1) nanoparticles, RSC Adv. 5 (2015) 2338–2345.
[18] N.J. Ashbolt, Microbial contamination of drinking water and disease outcomes in
developing regions, Toxicology 198 (2004) 229–238.
[19] M. Madhukara Naik, H.S. Bhojya Naik, G. Nagaraju, M. Vinuth, K. Vinu,
R. Viswanath, Green synthesis of zinc doped cobalt ferrite nanoparticles: structural,
optical, photocatalytic and antibacterial studies, Nano Struct. Nano Objects 19
(2019) 100322.
[20] J. Xu, Q. Gao, X. Bai, Z. Wang, Y. Zhu, Enhanced visible-light-induced
photocatalytic degradation and disinfection activities of oxidized porous g-C3N4 by
loading Ag nanoparticles, Catal. Today 332 (2019) 227–235.
[21] E. Abroushan, S. Farhadi, A. Zabardasti, Ag3PO4/CoFe2O4 magnetic
nanocomposite: synthesis, characterization and applications in catalytic reduction
of nitrophenols and sunlight-assisted photocatalytic degradation of organic dye
pollutants, RSC Adv. 7 (2017) 18293–18304.
[22] G. Palanisamy, K. Bhuvaneswari, G. Bharathi, D. Nataraj, T. Pazhanivel, Enhanced
photocatalytic properties of ZnS-WO3 nanosheet hybrid under visible light
irradiation, ChemistrySelect 3 (2018) 9422–9430.
[23] M. Nasr, L. Soussan, R. Viter, C. Eid, R. Habchi, P. Miele, M. Bechelany, High
photodegradation and antibacterial activity of BN-Ag/TiO2 composite nanofibers
under visible light, New J. Chem. 42 (2018) 1250–1259.
[24] X. Chen, B. Zhou, S. Yang, H. Wu, Y. Wu, L. Wu, J. Pan, X. Xiong, In situ
construction of an SnO2/g-C3N4 heterojunction for enhanced visible-light
photocatalytic activity, RSC Adv. 5 (2015) 68953–68963.
[25] E. Albert, P.A. Albouy, A. Ayral, P. Basa, G. Csík, N. Nagy, S. Rouald� es,
V. Rouessac, G. S� afr�
an, A.
� Suhajda, Z. Zolnai, Z. H�
orv€
olgyi, Antibacterial properties
of Ag–TiO2 composite sol–gel coatings, RSC Adv. 5 (2015) 59070–59081.
[26] S. Liu, J. Xie, C. Fang, G. Cao, T. Zhu, X. Zhao, Self-assembly of a CoFe2O4/
graphene sandwich by a controllable and general route: towards a high-
performance anode for Li-ion batteries, J. Mater. Chem. 22 (2012) 19738.
[27] S. Feng, M. Wang, Y. Zhou, P. Li, W. Tu, Z. Zou, Double-shelled plasmonic Ag-TiO2
hollow spheres toward visible light-active photocatalytic conversion of CO2 into
solar fuel, Apl. Mater. 3 (2015) 104416.
[28] P. Wang, B. Huang, Q. Zhang, X. Zhang, X. Qin, Y. Dai, J. Zhan, J. Yu, H. Liu,
Z. Lou, Highly efficient visible light plasmonic photocatalyst Ag@Ag(Br,I), Chem.
Eur J. 16 (2010) 10042–10047.
[29] M.M. Hasan Farooqi, R.K. Srivastava, Structural, optical and photoconductivity
study of ZnS nanoparticles synthesized by a low temperature solid state reaction
method, Mater. Sci. Semicond. Process. 20 (2014) 61–67.
[30] H. Labiadh, K. Lahbib, S. Hidouri, S. Touil, T. BEN Chaabane, Insight of ZnS
nanoparticles contribution in different biological uses, Asian Pac. J. Trop. Med. 9
(2016) 757–762.
[31] A.J. Rondinone, A.C.S. Samia, Z.J. Zhang, Characterizing the magnetic anisotropy
constant of spinel cobalt ferrite nanoparticles, Appl. Phys. Lett. 76 (2000)
3624–3626.
[32] M. Vadivel, R. Ramesh Babu, K. Sethuraman, K. Ramamurthi, M. Arivanandhan,
Synthesis, structural, dielectric, magnetic and optical properties of Cr substituted
CoFe2O4 nanoparticles by co-precipitation method, J. Magn. Magn. Mater. 362
(2014) 122–129.
[33] M.V. Limaye, S.B. Singh, S.K. Date, D. Kothari, V.R. Reddy, A. Gupta, V. Sathe, R.
J. Choudhary, S.K. Kulkarni, High coercivity of oleic acid capped CoFe2O4
nanoparticles at room temperature, J. Phys. Chem. B 113 (2009) 9070–9076.
[34] G. Bharathi, D. Nataraj, S. Premkumar, M. Sowmiya, K. Senthilkumar, T.
D. Thangadurai, O.Y. Khyzhun, M. Gupta, D. Phase, N. Patra, S.N. Jha,
D. Bhattacharyya, Graphene quantum dot solid sheets: strong blue-light-emitting &
photocurrent-producing band-gap-opened nanostructures, Sci. Rep. 7 (1–17)
(2017) 10850.
[35] Y.C. Liang, C.C. Wang, Surface crystal feature-dependent photoactivity of ZnO-ZnS
composite rods: via hydrothermal sulfidation, RSC Adv. 8 (2018) 5063–5070.
[36] Z. Zhang, W. Li, R. Zou, W. Kang, Y. San Chui, M.F. Yuen, C.S. Lee, W. Zhang,
Layer-stacked cobalt ferrite (CoFe2O4) mesoporous platelets for high-performance
lithium ion battery anodes, J. Mater. Chem. A. 3 (2015) 6990–6997.
[37] A.E. Reddy, T. Anitha, C.V.V. Muralee Gopi, S.S. Rao, B. Naresh, H.J. Kim,
Construction of novel nanocomposite ZnO@CoFe2O4 microspheres grown on
nickel foam for high performance electrochemical supercapacitors, Anal. Methods
10 (2018) 223–229.
[38] W.P. Wang, H. Yang, T. Xian, J.L. Jiang, XPS and magnetic properties of CoFe2O4
nanoparticles synthesized by a polyacrylamide gel route, Mater. Trans. 53 (2012)
1586–1589.
[39] S. Horoz, B. Yakami, U. Poudyal, J.M. Pikal, W. Wang, J. Tang, Controlled
synthesis of Eu2þ and Eu3þ doped ZnS quantum dots and their photovoltaic and
magnetic properties, AIP Adv. 6 (2016) 45119.
[40] S. Dhara, P. Giri, Size-dependent visible absorption and fast photoluminescence
decay dynamics from freestanding strained silicon nanocrystals, Nanoscale Res.
Lett. 6 (2011) 320.
[41] O. Khani, H.R. Rajabi, M.H. Yousefi, A.A. Khosravi, M. Jannesari, M. Shamsipur,
Synthesis and characterizations of ultra-small ZnS and Zn(1-x)FexS quantum dots in
aqueous media and spectroscopic study of their interactions with bovine serum
albumin, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 79 (2011) 361–369.
[42] D. Jiang, L. Chen, J. Xie, M. Chen, Ag2S/g-C3N4 composite photocatalysts for
efficient Pt-free hydrogen production. the co-catalyst function of Ag/Ag2S formed
by simultaneous photodeposition, Dalton Trans. 43 (2014) 4878–4885.
G. Palanisamy et al.
[43] D. Ayodhya, G. Veerabhadram, Ternary semiconductor ZnxAg1 xS nanocomposites
for efficient photocatalytic degradation of organophosphorus pesticides,
Photochem. Photobiol. Sci. 17 (2018) 1429–1442.
[44] A. Sarkar, G.G. Khan, The formation and detection techniques of oxygen vacancies
in titanium oxide-based nanostructures, Nanoscale 11 (2019) 3414–3444.
[45] L.J. Zhuge, X.M. Wu, Z.F. Wu, X.M. Yang, X.M. Chen, Q. Chen, Structure and deep
ultraviolet emission of Co-doped ZnO films with Co3O4 nano-clusters, Mater.
Chem. Phys. 120 (2010) 480–483.
[46] J. Kaur, M. Kaur, Facile fabrication of ternary nanocomposite of MgFe2O4 -TiO2@
GO for synergistic adsorption and photocatalytic degradation studies, Ceram. Int.
45 (2019) 8646–8659.
[47] Y. Meng, D. Chen, X. Jiao, Synthesis and characterization of CoFe2O4 hollow
spheres, Eur. J. Inorg. Chem. 2008 (2008) 4019–4023.
[48] P.K. Boruah, P. Borthakur, G. Darabdhara, C.K. Kamaja, I. Karbhal, M.V. Shelke,
P. Phukan, D. Saikia, M.R. Das, Sunlight assisted degradation of dye molecules and
reduction of toxic Cr(VI) in aqueous medium using magnetically recoverable
Fe3O4/reduced graphene oxide nanocomposite, RSC Adv. 6 (2016) 11049–11063.
[49] M. Choi, K.H. Shin, J. Jang, Plasmonic photocatalytic system using silver chloride/
silver nanostructures under visible light, J. Colloid Interface Sci. 341 (2010) 83–87.
[50] Y. Fu, H. Chen, X. Sun, X. Wang, Combination of cobalt ferrite and graphene: high-
performance and recyclable visible-light photocatalysis, Appl. Catal. B Environ.
111–112 (2012) 280–287.
[51] G. Fan, J. Tong, F. Li, Visible-light-induced photocatalyst based on cobalt-doped
zinc ferrite nanocrystals, Ind. Eng. Chem. Res. 51 (2012) 13639–13647.
[52] Y. Fu, Q. Chen, M. He, Y. Wan, X. Sun, H. Xia, X. Wang, Copper ferrite-graphene
hybrid: a multifunctional heteroarchitecture for photocatalysis and energy storage,
Ind. Eng. Chem. Res. 51 (2012) 11700–11709.
[53] P. Xiong, L. Wang, X. Sun, B. Xu, X. Wang, Ternary titania-cobalt ferrite-
polyaniline nanocomposite: a magnetically recyclable hybrid for adsorption and
12
Journal of Physics and Chemistry of Solids 138 (2020) 109231
photodegradation of dyes under visible light, Ind. Eng. Chem. Res. 52 (2013)
10105–10113.
[54] G. He, J. Ding, J. Zhang, Q. Hao, H. Chen, One-step ball-milling preparation of
highly photocatalytic active CoFe2O4-reduced graphene oxide heterojunctions for
organic dye removal, Ind. Eng. Chem. Res. 54 (2015) 2862–2867.
[55] M.A. Kanjwal, N.A.M. Barakat, F.A. Sheikh, M.S. Khil, H.Y. Kim, Functionalization
of electrospun titanium oxide nanofibers with silver nanoparticles: strongly
effective photocatalyst, Int. J. Appl. Ceram. Technol. 7 (2010) 54–63.
[56] D. Sun, Y. Han, S. Gao, X. Zhang, Surface modification of titania-coated cobalt
ferrite magnetic photocatalyst by cold plasma, Surf. Coat. Technol. 228 (2013)
516–519.
[57] T.J. Whang, M.T. Hsieh, H.H. Chen, Visible-light photocatalytic degradation of
methylene blue with laser-induced Ag/ZnO nanoparticles, Appl. Surf. Sci. 258
(2012) 2796–2801.
[58] Y. Xu, M.A.A. Schoonen, The absolute energy positions of conduction and valence
bands of selected semiconducting minerals, Am. Mineral. 85 (2000) 543–556.
[59] H. Tian, C. Wan, X. Xue, X. Hu, X. Wang, Effective electron transfer pathway of the
ternary TiO2/RGO/Ag nanocomposite with enhanced photocatalytic activity under
visible light, Catalysts 7 (2017) 156.
[60] W. Cao, L. Chen, Z. Qi, Microwave-assisted synthesis of Ag/Ag2SO4/ZnO
nanostructures for efficient visible-light-driven photocatalysis, J. Mol. Catal. A
Chem. 401 (2015) 81–89.
[61] K.J. Woo, C.K. Hye, W.K. Ki, S. Shin, H.K. So, H.P. Yong, Antibacterial activity and
mechanism of action of the silver ion in Staphylococcus aureus and Escherichia
coli, Appl. Environ. Microbiol. 74 (2008) 2171–2178.
[62] J.K. Rajput, G. Kaur, Synthesis and applications of CoFe2O4 nanoparticles for
multicomponent reactions, Catal. Sci. Technol. 4 (2014) 142–151.