Materials Chemistry and Physics xxx (2016) 1e10

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Materials Chemistry and Physics

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

Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for

the degradation of organic pollutants
R. Rameshbabu a, Niraj Kumar a, b, A. Karthigeyan b, *, B. Neppolian a, **
a
SRM Research Institute, SRM University, Kattankulathur, Kanchipuram 603203, Tamil Nadu, India
b
Centre for Materials Science and Nano Devices, Department of Physics and Nanotechnology, SRM University Kattankulathur, Kanchipuram 603203, Tamil
Nadu, India

h i g h l i g h t s

Co-precipitation method is proposed to synthesize magnetic nanoparticles.

Modifications in the molar concentration lead to the shift in absorption edge.

Superparamagnetic property is demonstrated for the nanoparticles.

Two dye pollutants are utilized to demonstrate the photocatalytic activity.

a r t i c l e i n f o a b s t r a c t

Article history: ZnFe2O4/ZnO nanoparticles have been synthesized by co-precipitation method using polyvinyl alcohol
Received 9 May 2015 (PVA) as surfactant. The phase formation of synthesized products was systematically investigated from
Received in revised form powder X-ray diffraction. Cubic ZnFe2O4 and hexagonal ZnO were identified in accordance with different
9 May 2016
molar concentrations of Fe3þ ions. The morphology and functionality were analyzed using field emission
Accepted 7 June 2016
scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transform
Available online xxx
infrared (FTIR) spectroscopy. The optical properties and change in the band gap from UV to visible region
upon increasing molar concentration of Fe3þ ions were analyzed from diffuse reflectance spectra (DRS).
Keywords:
Magnetic materials
Superparamagnetic property was observed for synthesized ZnFe2O4/ZnO nanoparticles using vibrating
Annealing sample magnetometer (VSM). The methylene blue and methyl orange were taken as model dyes to
X-ray diffraction illustrate the photocatalytic activity of synthesized products under visible light irradiation. Maximum
Catalytic properties degradation of 99% for methyl orange (MO) was achieved by the use of 13 nm sized ZnFe2O4/ZnO
nanoparticles as catalyst and a minutely less activity was observed for the methylene blue (MB)
degradation (98%), when the photocatalytic processes were carried out for 5 h and 6 h, respectively.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction However, the major drawback is that their photocatalytic activity

Methylene blue (MB) and Methyl orange (MO) are frequently
used dyes in textile industries, which are highly hazardous in na-
ture. Expulsion of these dyes to water bodies (lakes, rivers, oceans,
groundwater etc.) by industries causes severe health issues [1,2].
These textile dyes are very complex in structures, which creates
difficulties in their degradation [3e5]. In recent times, various
semiconductor based photocatalysts have been designed to achieve
high photocatalytic efficiency for the degradation of these dyes [6].
* Corresponding author.
** Corresponding author.
E-mail addresses: karthigeyan.a@ktr.srmuniv.ac.in (A. Karthigeyan), neppolian.
b@res.srmuniv.ac.in (B. Neppolian).
requires irradiation/activation in the UV region. Accounting, the
low availability of UV light in the solar spectrum, various catalysts
have been developed to exhibit photocatalytic activity in visible
region of the electromagnetic spectrum. The improvement of
visible light induced photocatalysts, to counter global energy crisis
and environmental problems, has become one of the most signifi-
cant topics in current photocatalysis research [7e9].
For the remediation of hazardous wastes under stimulated light
condition many efforts have been taken in recent times by the use
of semiconductor materials like TiO2 and ZnO as catalyst for the
photodegradation of toxic dye pollutants [10e13]. ZnO and TiO2
having band gaps of 3.37 eV and 3.2 eV, respectively at room
temperature offer several advantages over other catalytic materials
such as higher quantum efficiency, environmental friendly, low cost

http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
0254-0584/© 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
2 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10
and superior photocatalytic activity [14,15], but unfortunately they
have no effective absorption in the visible light region (l > 420 nm).
They can only operate within the UV light region of solar radiations
due to their wide band gap. Since the photocatalytic activity of TiO2
is influenced by the crystal size, crystal structure and crystallinity.
Synthesis of pure nanocrystalline anatase TiO2 is challenging [2].
The major hindrances for enhancing the photocatalytic efficiency of
pure semiconductor photocatalysts are the fast recombination of
photo generated electron-hole pairs [16]. In order to improve the
photocatalytic efficiency of these materials, doping with rare and/
or transition metals [17] and hetero structures have been reported
[18]. Electron tends to trap inside the quasi-stable energy states
(active sites) created due to doping which significantly increases
the photocatalytic efficiency even when the electron-hole pair
recombination rate is lower than the rate of electron transfer to
adsorbed molecule [19].
Some spinel materials including ZnFe2O4 form a class of semi-
conductors with narrow band gaps and exhibit characteristics of
excellent visible-light response and good photochemical stability.
Zhang et al., reported the magnetic composite photocatalyst
ZnFe2O4/BiVO4 under visible-light and demonstrated that the
photocatalytic activity of BiVO4 is improved by adding a narrow
band gap ZnFe2O4 [20]. Fan et al. [21], reported the synthesis of
cobalt-doped zinc ferrite nanocrystals acting as visible light pho-
tocatalyst. Fu et al., reported about the synthesis and photocatalytic
analysis of magnetically separable ZnFe2O4-graphene catalyst [22].
Magnetic materials have an added advantage that it can be easily
separated and recovered from the medium with the help of
external magnetic field.
Nanomaterials have large surface area to volume ratio, which
results in high surface reactivity, thus increasing the chemical re-
action dynamics and photon absorption efficiency. Several methods
have been proposed to synthesize ZnFe2O4 nanoparticles such as
sol-gel [23], hydrothermal [24], combustion [25], ball milling [26],
microemulsion [27], spray pyrolysis [28], sol-gel auto combustion
[29], electrospinning [30], solid-state combustion [31] and co-
precipitation technique [32]. Among the above mentioned tech-
niques, co-precipitation technique is very simple, cost effective and
non toxic. Furthermore, it offers the possibility to deal with a great
number of experimental strategies by the modification of param-
eters such as solvent, precipitant agent concentration or tempera-
ture. For example, Jadhav et al., investigated the effect of sintering
at different temperatures on photocatalytic degradation of methyl
orange under UV-light irradiation using zinc ferrite prepared by co-
precipitation method [33]. Harish et al., have reported about the
synthesis of Cd-eZn ferrites nanoparticles by co-precipitation
method and its enhanced photocatalytic activity under solar light
irradiation [34].
In the present work, ZnFe2O4/ZnO nanoparticles are synthesized
by co-precipitation method using polyvinyl alcohol (PVA) as sur-
factant. The structural, vibrational, morphological, optical and
magnetic studies are carried out by X-ray diffraction (XRD), fourier
transform infrared spectroscopy (FTIR), field emission scanning
electron microscopy (FESEM), transmission electron microscopy
(TEM), diffuse reflectance spectra (DRS) and vibrating sample
magnetometer (VSM) techniques. The photocatalytic activity is
investigated by the degradation of methylene blue and methyl or-
ange under visible light irradiation.
2. Materials and method
2.1. Materials
Zinc nitrate [Zn (NO3)2 6H2O], ferric nitrate [Fe (NO3)3 9H2O],
sodium hydroxide [NaOH], polyvinyl alcohol (PVA), methylene blue
Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
(MB) and methyl orange (MO) were purchased from Sigma-Aldrich
chemical reagent Co. (MO, USA) and were used without further
purification. The De-ionized water was used in all the experiments.
2.2. Preparation of ZnFe2O4/ZnO nanoparticles
ZnFe2O4/ZnO nanoparticles were prepared by co-precipitation
method using PVA as surfactant. In a typical synthesis, zinc ni-
trate (0.1 M) and PVA (2 g) were dissolved in 200 ml de-ionized
water (DI) under magnetic stirring to form a clear solution at
room temperature. The pH of the mixed solution was adjusted
slowly to 11 by NaOH solution. The precipitated solution was
continuously stirred for 1 h and the precipitate was collected by
centrifugation, washed with de-ionized water and absolute ethanol
for three times and dried in hot air oven at 100  C for 12 h. Then, the
final product was crushed using mortar and pestle and the particles
were subsequently heat treated at 600  C for 6 h and the sample
was named as S1. Then ferric nitrate was added in the reaction
medium with different molar concentration varying from 0.02 M to
0.2 M (in steps of 0.02 M) and the final products were named as S2
(0.02 M), S3 (0.04 M), S4 (0.06 M), S5 (0.08 M), S6 (0.10 M), S7
(0.12 M), S8 (0.14 M), S9 (0.16 M), S10 (0.18 M) and S11 (0.20 M)
respectively. The concentration of zinc nitrate (0.1 M) and PVA (2 g)
was maintained constant in all the experiments.
2.3. Materials characterization
Phase purity of synthesized products was analyzed by powder
X-ray diffraction (XRD) measurement using a PAN analytical X0 Pert
PRO diffractometer employing Cu-Ka rays of wavelength 1.5406 Å
with a tube current of 30 mA at 40 kV in the 2q range of 20 e80 .
The functional groups of the materials were studied using Fourier
transform infrared spectroscopy (FTIR) using Perkin Elmer Spec-
trophotometer by the KBr pellet technique in the range of
4000 cm1e400 cm1. The morphological characterizations of the
samples were observed by Field emission scanning electron mi-
croscopy (Quanta 200 FEG FE-SEM). Particle size measurements
were observed using Transmission electron microscope (TEM). One
drop of the magnetic fluid was placed on a carbon coated copper
grid, dried in vacuum and the TEM image was taken with a ZEISS
EM 900 TEM with an accelerating voltage of 200 kV. The optical
properties were analyzed by UVeVisible Diffuse reflectance spec-
troscopy (DRS) using [PG instruments-Model T90þ. (2009), Japan]
in the wavelength range 200e800 nm. The raw data was further
analyzed using Tauc analysis. The magnetic properties were
investigated using a vibrating sample magnetometer (VSM,
lakeshore-7404) with a maximum field of 1.2 T at room
temperature.
2.4. Measurement of photocatalytic activity
The photocatalytic activities of the ZnFe2O4/ZnO nanoparticles
were evaluated by measuring the degradation of methylene blue
(MB) and methylene orange (MO) under visible light irradiation.
Typically, an aqueous MB solution (20 mg/L, 100 ml) containing
0.05 g of the catalyst is added into 50 ml DI water. The solution was
vigorously stirred for 0.5 h in the dark at room temperature, and
then the solution was irradiated under visible light source using a
500 W halogen lamp for all the samples (S1eS11). During irradia-
tion, stirring was maintained to keep the mixture in suspension. At
the given time interval of 1 h, 3 ml of suspension was collected and
centrifuged to remove the catalyst nanoparticles. Same procedures
were followed with methyl orange (MO) as dye for a comparative
study. The irradiation process of each degraded MB and MO solu-
tions were determined by measuring the characteristic absorption
 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10 3

Fig. 2. Elastic strain of ZnFe2O4/ZnO nanoparticles measured from powder X-ray

diffraction patterns.

Fig. 1. Powder XRD patterns of (a) S1, (b) S2, (c) S3, (d) S4, (e) S5, (f) S6, (g) S7, (h) S8, (i)
S9, (j) S10 and (k) S1.

at 664 nm and 464 nm, respectively, using a UVeVisible Spectro-

photometer (LAB India, UV 3000þ) in the wavelength range of
200e800 nm. Distilled water was used as the reference sample.

3. Results and discussion

3.1. Structural analysis

Powder XRD patterns of the synthesized eleven samples

(S1eS11) are shown in Fig. 1 (a-k). The diffraction peaks in Fig. 1 (a),
of the sample S1 are indexed and consistent with standard JCPDS
card no. (75-0576) of ZnO hexagonal wurtzite nanoparticles. In this
experiment, the reaction medium does not contain ferric nitrate
component. Fig. 1 [(b)-(k)] are the powder XRD patterns of ten
samples (S2eS11). Compared to diffraction patterns of S1 the po-
sitions of the diffraction peaks of samples with different molar
concentrations of Fe3þ gradually changes towards the formation of
ZnFe2O4 phase. The predominant (1 0 0) peak of ZnO partially
disappears for all the molar concentration. As Fe3þ ions molar ratio
increases, the peaks become sharper and their intensity gradually Fig. 3. FTIR spectra of the samples (a) S1, (b) S2, (c) S3, (d) S4, (e) S5, (f) S6, (g) S7, (h)
increases because of the enhanced crystallinity and formation of S8, (i) S9, (j) S10 and (k) S11.
ZnFe2O4 nanoparticles that are of high purity and good crystallinity.
The change in the crystallite size of ZnFe2O4/ZnO nanoparticles

Table 1
Summary of the structural, magnetic, optical and photocatalytic properties of the synthesized ZnFe2O4/ZnO nanoparticles.

Sample name (FWHM) b Crystallite size D (nm) Strain (ε) 103 Magnetic saturation Ms (emu/g) Band gap (eV) Degradation (%) Kinetic value (k)
(h1)

MB 6 h MO 5 h MB 6 h MO 5 h

S1 0.00526 30.00 3.042 0.006 3.21 79 78 0.19 0.18

S2 0.00624 25.19 1.401 0.96 2.73 83 82 0.21 0.20
S3 0.00813 18.87 1.840 2.73 2.20 88 89 0.24 0.25
S4 0.01256 13.00 2.811 3.18 2.19 98 99 0.35 0.36
S5 0.01073 16.00 2.399 4.07 2.18 96 95 0.30 0.29
S6 0.00956 16.94 2.133 4.46 2.10 93 93 0.27 0.26
S7 0.00921 17.03 2.066 4.97 2.09 90 91 0.25 0.25
S8 0.00899 17.36 2.018 5.92 2.06 75 76 0.17 0.17
S9 0.00737 21.91 1.666 7.72 2.05 70 73 0.15 0.16
S10 0.00700 22.49 1.571 9.65 2.00 66 69 0.15 0.15
S11 0.00529 29.42 1.207 12.65 2.00 57 59 0.12 0.13

Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
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4 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10

Fig. 4. FESEM micrographs of samples (a) S1, (b) S2, (c) S3, (d) S4, (e) S5, (f) S6, (g) S7, (h) S8, (i) S9, (j) S10 and (k) S11.

Fig. 5. TEM images of the as prepared samples of different Fe3þ molar Concentrations (a) S4 (0.06 M) and (b) S5 (0.08 M).

Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10
Fig. 6. Magnetization curves of S1, S2, S3, S4, S5, S6, S7, S8, S9, S10 and S11 at room
temperature.
for all the samples was calculated by Debye-Scherrer’s formula:
Kl
DðhklÞ ¼
b cos q
where D is the mean crystallite dimension, K is the shape factor; l is
the X-ray wavelength, b line broadening at half the maximum in-
tensity (FWHM) in radians and q Bragg angle. The calculated crys-
tallite sizes of all the prepared samples (S1eS11) are tabulated in
Table 1. Smallest crystallite size was obtained for sample S4.
The elastic strain induced in the powders due to crystal
imperfection and distortion is calculated using the formula for
cubic structure [35] and hexagonal structure [36] the following
relation are
b cos q
ε¼
4 change the direction of magnetization of the entire crystallite [39].
bhkl
ε¼
4 tan q
Fig. 2 shows the effect of Fe3þ molar concentration on crystallite
size and strain. It can be seen that, increase in Fe3þ molar con-
centration produces increase in strain and decrease in crystallite
size. It can also be seen that there is increase in crystallite size with
increasing Fe3þ ions and decrease in strain.
3.2. Functional group analysis
The FTIR spectroscopy is an appropriate technique to under-
stand the chemical adsorption or functionalization on the synthe-
sized products. Functional groups for the samples (S1eS11) were
analyzed using the characteristic absorption peaks observed in the
FTIR spectra in the wave number range of 400 cm1 to 4000 cm1.
FTIR spectra of the samples are presented in Fig. 3 (a-k). The
characteristic absorption peaks are observed between 542 and
549 cm1 due to the stretching vibrations of the FeeO bonds in
octahedral positions. Furthermore, the characteristic peaks
observed between 401 and 415 cm1 are due to the stretching vi-
brations of the ZneO bonds in tetrahedral positions [37]. FTIR
spectroscopy clearly illustrates a small shift in the stretching vi-
brations of the ZneO frequency with the increase of crystallite size.
It was reported that with the decrease in crystallite size of ZnFe2O4,
more number of Zn2þ cations move to octahedral sites [38]. But,
Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
5
with the increase in crystallite size, the Zn2þ cations mostly occupy
the tetrahedral sites due to its higher affinity towards tetrahedral
sites. The tetrahedrally coordinated ZneO distance is smaller than
octahedrally coordinated ZneO in the crystallite structure. Hence,
with the decrease in the crystallite size, the number of octahedrally
coordinated ZneO bonds increases gradually resulting in the
observed shift in the FTIR spectrum.
3.3. Morphology and microstructure
The surface morphology and microstructures of the all synthe-
sized products were analyzed by FESEM technique. The FESEM
images of ZnFe2O4/ZnO nanostructures are shown in Fig. 4 (a-k).
From Fig. 4 (a), it is seen that S1 exhibited rice like structure. Adding
different ferric nitrate molar concentrations, sphere-like nano-
structures were obtained with agglomeration. The samples S4 and
S5 showed high photocatalytic activity as compared to the other
samples. Therefore, TEM measurements were carried out only for
the samples S4 and S5. Fig. 5 (a, b) shows the TEM image of the
ZnFe2O4 nanoparticles of the samples S4 and S5, respectively. The
average sizes of the particles of S4 and S5 are 13 nm and 16 nm,
respectively and the sizes are in consistent with the particles sizes
determined from the XRD investigation.
(1)
3.4. Magnetic properties
The room temperature magnetic properties of all the synthe-
sized samples (S1eS11) were investigated by VSM measurement.
Fig. 6 shows the magnetization curve of all the samples which
exhibited super paramagnetic behaviors except the sample S1.
Table 1 presents the values of magnetic saturation (Ms) of all syn-
thesized products. The super paramagnetic particle has negligible
coercivity and remanent magnetization for the maximum applied
magnetic field. Generally, in the super paramagnetic materials, the
magnetic spins are relaxed back to give the zero net magnetic
moment in the absence of external magnetic field and thermal
energy is sufficient to overcome the magnetic anisotropy and
(2)
The magnetic saturation (Ms) values obtained for the samples (S1 to
S11) were in the range of 0.006e12.65 emu/g. These samples
(3)
showed enhancement of the magnetic properties with the incre-
ment of Fe3þ molar concentration. This can be attributed to spin
canting effect and surface spin disorder that occurred in these
nanoparticles [40]. Sample S11 showed highest saturation magne-
tization (12.65 emu/g), which is much lower than that reported for
multi-domain bulk zinc ferrite (65.4 emu/g) [41]. Moreover, the
bulk ZnFe2O4 has normal spinel phase in which tetrahedral sites are
exclusively occupied by Zn2þ ions and octahedral sites by Fe3þ ions.
It shows a very low Neel temperature about 10 K due to BeB
interaction and above this temperature, it exhibits the para-
magnetic properties. In the nano form, zinc ferrite becomes a mixed
spinel that may increase the magnetic moments. Furthermore, in-
crease in the saturation magnetization may be due to the strong A-
B interaction between Fe3þ ions in B sites and Fe3þ ions which are
forced into A sites in nanoscale ZnFe2O4 [42]. Normally, the dis-
persibility of magnetic materials and non magnetic materials in a
solution are equal. A magnetic material can be attracted by a
magnet, but a non-magnetic material cannot be. Magnetic mate-
rials have an added advantage that it can be easily separated and
recovered from its suspension solutions with the help of an
external magnetic field.
3.5. UVevisible DRS analysis
The UVeVis diffuse reflectance spectra (DRS) were recorded to
6 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10

Fig. 7. UVeVis diffuse reflectance spectra of (a) S1, (b) S2, (c) S3, (d) S4, (e) S5, (f) S6, (g) S7, (h) S8, (i) S9, (j). S10 and (k) S11. Inset shows the corresponding plots of (ahn)2 vs the
incident photon energy.

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 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10 7

Fig. 8. The temporal evolution of the absorption spectra during the photo degradation (a) MB, (b) MO for the. sample S4, Photocatalytic degradation ratio of (c) MB and (d) MO.

Fig. 9. Fitted pseudo first-order kinetics for the degradation of (a) MB and (b) MO for the sample S4.

understand the optical properties and energy gap of the synthe-
sized products. The optical properties of the samples (S1eS11) are
presented in Fig. 7 (a-k). A strong absorption in the UV range was
observed for the ZnO nanoparticles (sample S1), whereas for
increasing Fe3þ molar concentration in the reaction medium the
absorption range gradually moved from UV to visible region
showing red shift. This indicates that ZnFe2O4/ZnO nanoparticles
have stronger absorption in visible light region than the sample S1
ie., pure ZnO nanoparticles. The optical absorptions can be esti-
mated from the optical reflectance data using the Kubelka-Munk
function,

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8 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10
ð1  RÞ2
a¼
2R
where, a is the absorption coefficient and R is the diffuse reflec-
tance [43].
The bandgap energy (Eg) of a semiconductor can be calculated
using the formula [44].
ðahyÞ2 ¼ Aðhy  EgÞ
where Eg represents the optical band gap, hn is the photon energy
and A is a constant. The band gap of all the synthesized samples
(S1eS11) was determined from (ahy)2 versus hy plots, as shown
(inset) in Fig. 7 (a-k). The band gaps calculated for the samples
(S1eS11) are shown in Table 1. From the above calculated data, it
can be predicted that the band gap value decreases gradually with
increase in the ferric nitrate molar concentration. This possibly
indicates that more photons can be absorbed and then more photo-
produced electron hole pairs can be generated in the composite
than for pure ZnFe2O4 under identical visible light irradiation [45].
3.6. Photocatalytic activities
The photocatalytic activities of the samples (S1eS11) under
visible light irradiation were evaluated by MB and MO degradation.
The changes in the absorption spectra of MB and MO aqueous so-
lutions during their visible light photocatalytic degradation using
sample S4 are shown Fig. 8 (a, b). It can be seen that the intensity of
the absorption peaks at 664 nm and 464 nm are gradually
decreased with irradiation time during MB and MO degradation,
respectively. It was observed that the peaks completely dis-
appeared when the photocatalytic degradation processes for MB
and MO dyes were carried out for 6 h and 5 h, respectively.
The degradation ratios (C/Co) of MB and MO for all the samples
are presented in Fig. 8 (c, d). Here, Co is the initial concentration of
dye and C is the concentration of dye at different reaction times.
The degradation percentages of MB and MO for the samples
(S1eS11) under visible light are listed in Table 1. The photocatalytic
ability of sample S4 was found to be superior among all the syn-
thesized samples. The highest degradation percentages of 98% for
MB and 99% for MO were achieved by using sample S4 as photo-
catalyst, when the degradation processes were carried out for 6 h
and 5 h, respectively. It was found that MO dye was degraded 1%
Fig. 10. A proposed visible light photo degradation mechanism of ZnFe2O4/ZnO catalysis.
Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040
higher, while taking 1 h lesser time than MB. The results suggest
that MO dye is more prone to photocatalytic degradation in
(4)
contrast to MB dye.
Fig. 9 (a, b) shows the first order reaction kinetics plots for
photocatalytic degradation of MB and MO using sample S4,
respectively. The kinetics are represented as 1n(C/Co) ¼ kt, where k
is the apparent reaction constant and is determined by linear fit of
the plot of 1n(C/Co) versus reaction time t. The calculated kinetic
values (k) of the samples (S1eS11) after the degradations of MB and
(5) MO dyes for 6 h and 5 h respectively are listed in Table 1. The
degradation percentage is observed to be directly proportional to
the kinetic value. Highest kinetic values of 0.35 h1 and 0.36 h1
observed during MB and MO degradations, respectively for sample
S4 are due to its higher photocatalytic activity than all other sam-
ples. In the case of MB degradation, the k value using sample S4 is
higher than that of the samples S11, S10, S9, S8, S1, S2, S3, S7, S6, S5
by 2.87, 2.33, 2.29, 2.03, 1.84, 1.67, 1.46, 1.41, 1.29, and 1.17 times,
respectively and in the case of MO degradation the k value for
sample S4 is higher than that of the samples S11, S10, S9, S8, S1, S2,
S3, S7, S6, S5 by 2.76, 2.4, 2.25, 2.11, 2.00, 1.8, 1.44, 1.44, 1.38, and 1.24
times, respectively. This can be seen from Fig. 8 (c, d).
3.7. Mechanism of ZnFe2O4/ZnO catalysis
Photocatalytic activity is essentially depended on surface area
and electron-holes separation efficiency of the catalyst. A schematic
of photocatalytic mechanism is shown in Fig. 10. Nanoparticles
having high surface area are capable for exhibiting higher activity
than their bulk counterpart as nanoparticles can support easy
transition of electron from valence to conduction band generating
electron-hole pair, when exposed to visible light. This generated
electron-hole pairs are favorable for the degradation of dye. In
ZnFe2O4/ZnO nanoparticle, the excited electrons from ZnFe2O4 are
easily transferrable to ZnO due it’s smaller band gap of 2 eV than
ZnO which has a band gap of 3.2 eV. This transfer of electrons can
create cascade connection between these two semiconductors
which tends to reduce the electric pressure generated due to the
formation of electron-hole pairs and may prohibits the recombi-
nation of these electrons and holes increasing their stability. Hence,
the formation of this binary nanostructure can results in significant
improvement of catalytic activity by forming stable electron-hole
pairs, which cannot be recombine easily. The holes oxidizes the
water molecules present in the solution generating highly reactive

OH radicals, whereas the excited electrons reduce the oxygen
 R. Rameshbabu et al. / Materials Chemistry and Physics xxx (2016) 1e10
molecules to oxygen radicals
O2. These oppositely charged radicals
tend to accumulate over the surface of dyes and works actively in
degrading these dyes.
4. Conclusions
ZnFe2O4/ZnO nanoparticles were successfully synthesized by
co-precipitation method. Crystalline phase and optical absorption
of the nanoparticles were strongly influenced by the molar ratio of
Fe3þ and Zn2þ. A shift in absorption edge from UV to Visible region
was achieved by increasing ferric nitrate molar concentration in the
synthesized nanoparticles. The increased photocatalytic activity of
ZnFe2O4/ZnO could be ascribed to the increase in electronehole
separation due to interparticle charge transfer between ZnFe2O4
and ZnO and also to the reduction in size of nanoparticles.
Dependence of photocatalytic activity on the size of catalyst was
well demonstrated by showcasing the maximum degradation
percents of 98% and 99% for MB and MO degradations, respectively
through the use of smallest sized (13 nm) nanoparticles (S4). All of
the synthesized ZnFe2O4/ZnO nanoparticles showed the super-
paramagnetic property except the pure ZnO nanoparticles. The
highest activity was recorded for the MO degradation, as it showed
one percent higher degradation while taking 1 h lesser time during
the degradation process compared to the MB degradation.
Acknowledgements
One of the authors, R.Rameshbabu, wishes to thank grateful for
the financial support from SRM University and also thanks
Department of Physics & Nanotechnology, Nanotechnology
Research Centre (NRC), and SRM College of Pharmacy for XRD,
UVeVis spectrophotometer, FESEM and FTIR measurements.
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Please cite this article in press as: R. Rameshbabu, et al., Visible light photocatalytic activities of ZnFe2O4/ZnO nanoparticles for the degradation
of organic pollutants, Materials Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.06.040