J Mater Sci: Mater Electron
DOI 10.1007/s10854-015-3622-y
Sonochemical synthesis of Fe3O4/ZnO magnetic nanocomposites
and their application in photo-catalytic degradation of various
organic dyes
Jilla Saffari1 • Noshin Mir2 • Davood Ghanbari3 • Khatereh Khandan-Barani1
Alireza Hassanabadi1 • Mohammad Reza Hosseini-Tabatabaei1
Received: 15 July 2015 / Accepted: 10 August 2015
Ó Springer Science+Business Media New York 2015
Abstract In this work, Fe3O4/ZnO nanocomposite was
synthesized via a surfactant-free sonochemical method in
aqueous solution. The effect of sonication time and power
on the morphology and particle size of the magnetic seeds
were investigated. The prepared product were character-
ized by X-ray diffraction pattern, scanning electron
microscope, energy dispersive spectroscopy and Fourier
transform infrared spectroscopy. Alternating gradient force
magnetometer showed superparamagnetic behaviour of
Fe3O4 nanoparticles as well as nanocomposites containing
10 % ZnO. The photocatalytic behaviour of Fe3O4–ZnO
nanocomposites was evaluated using the degradation of
eight organic dyes under ultraviolet light irradiation. The
results show that Fe3O4–ZnO nanocomposites have appli-
cable magnetic and photocatalytic performance.
1 Introduction
The growing demand for eliminating pollutants from waste
water in order to provide clean water has urged innovating
various purification methods and among them, the
advanced oxidation processes in which the photo-degra-
dation reactions are included are of great importance. In
these processes, organic molecules mainly undergo
& Jilla Saffari
J.saffari@iauzah.ac.ir
1
Department of Chemistry, Zahedan Branch, Islamic Azad
University, P.O. Box 98135-978, Zahedan, Iran
2
Department of Chemistry, University of Zabol,
P.O. Box 98615-538, Zabol, Iran
3
Young Researchers and Elite Club, Arak Branch, Islamic
Azad University, Arak, Iran
•
decomposition reaction by interacting with both UV (or
visible) light and a photo-catalyst material to give CO2 and
H2O as final products [1]. One of the most appealing
materials for this purpose is semiconductor nanomaterials
such as TiO2 (effective and most frequently mentioned)
ZrO2, WO3, ZnO, ZnS, SnO2, Fe2O3, as well as large
number of binary, ternary, and quaternary mixed oxides
[2–6]. Among the mentioned materials, ZnO nanoparticles
with wide band gap, high quantum efficiency, and non-
toxicity exhibit significant photocatalytic activity for the
decomposition of organic contaminants [7]. The wide band
gap of ZnO is very suitable for various applications such as
solar cells, catalysis, optical, electrical, electromagnetic
shielding, biosensors, and gas sensors [8–11]. However,
single semiconductor suffers from some problems includ-
ing high recombination rate of electronic-hole pairs, low
harvest of visible light, poor selective adsorption, photo-
catalyst deactivation, and high cost of photocatalyst. In
order to improve the photocatalytic activity of semicon-
ductor and exploit its advantageous properties, magnetic
magnetite/semiconductor composites have recently been
designed and developed [12, 13]. As one of the most
important magnetic oxides with spinel structure, magnetite
(Fe3O4) has attracted enormous interest due to its unique
electric and magnetic properties based on the transfer of
electrons between Fe2? and Fe3? in the octahedral sites
[14, 15]. The special properties of magnetite nanoparticles
including excellent chemical stability, suitable mechanical
hardness, degradation of organic pollutants, cost-effec-
tiveness as well as the possibility for precise control on the
composition along with its ability to be separated by a
magnet, has made it a very attractive candidate to be used
in nanocomposite photocatalysts [16–18].
In addition to the possibility for precise control on the
composition and structure of Fe3O4, a variety of facile
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chemical and physical synthesis methods such as precipita-
tion, sol–gel, and hydrothermal have been developed for
simple preparation of magnetite. Among the various reported
methods, sonochemical approach is an efficient way for pro-
duction of magnetite powders with different morphologies
and fine nanoparticles. Sonochemical method is well-known
as a rapid synthetic rout to be suitable and efficient for
preparing nanomaterials with extraordinary morphology and
properties. Propagation of ultrasonic waves causes a hetero-
geneous pressure throughout the liquid resulting in continuous
formation, growth and implosive collapse of the bubbles.
Obtaining ultrafine novel materials with desirable properties
in a short period of time is the most significant advantages of
sonochemical method which is the result of physical and
chemical effects of ultrasonic irradiation [19–22].
In the present work, Fe3O4 nanoparticles and Fe3O4–
ZnO nanocomposites were synthesized by a surfactant-free
sonochemical method without using inert atmosphere. The
effect of reaction parameters such as time, sonication
power, and concentration of semiconductor was investi-
gated in order to optimize the reaction condition for
obtaining an efficient photocatalyst.
obtained confirming the synthesis of Fe3O4. The precipitate
of Fe3O4 was then centrifuged and rinsed with distilled
water. Finally the obtained black precipitate was left to dry
at 50 °C. Figure 1a shows the schematic diagram for
experimental setup used in this sono-chemical procedure.
2.3 Synthesis of Fe3O4–ZnO nanostructures
1 g of magnetite nanoparticles were dispersed in water
solution and Zn(CH3COO)2
2H2O was dissolved in the
solution simultaneously. 5 ml of ammonia (1 M) was
added to solution under sonication (100 W, 20 min,
Fig. 1b). The precipitate of Fe3O4–ZnO is then centrifuged
and rinsed with distilled water.
3 Results and discussion
Figure 2 shows XRD patterns for various samples includ-
ing Fe3O4, ZnO, and Fe3O4/ZnO Nanoparticles. The XRD
pattern of Fe3O4 reveals the typical diffraction patterns of

2 Experimental

2.1 Materials and methods

NH3, Zn(CH3COO)2
2H2O, FeCl2
4H2O and acetone were

purchased from Merck and all the chemicals were used as
received without further purifications. A multiwave ultra-
sonic generator (Bandeline MS 73), equipped with a con-
verter/transducer and titanium oscillator, operating at 20 kHz
with a maximum power output of 150 W was used for the
ultrasonic irradiation. Room temperature magnetic properties
were investigated using an alternating gradient force mag-
netometer (AGFM) device, made by Meghnatis Daghigh
Kavir Company in an applied magnetic field sweeping
between ±10,000 Oe. X-ray diffraction (XRD) patterns were
recorded by a Philips, X-ray diffractometer using Ni-filtered
CuKa radiation. Scanning electron microscope (SEM) ima-
ges were obtained using a LEO instrument model 1455VP.
Prior to taking images, the samples were coated by a very
thin layer of Pt (using a BAL-TEC SCD 005 sputter coater)
to make the sample surface conductor and prevent charge
accumulation, and obtaining a better contrast.

2.2 Synthesis of Fe3O4

1 g of FeCl2 4H2O was dissolved in 100 ml of distilled

water. 15 ml of NH3 solution (5 M) was slowly added to
the solution under ultrasonic irradiation 60 W (100, Fig. 1 Schematic of preparation of a Fe3O4 nanoparticles, b Fe3O4–
150 W) and 10 min (30 min). A black precipitate was ZnO nanocomposite

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J Mater Sci: Mater Electron
Fig. 2 XRD pattern of Fe3O4,
ZnO, and Fe3O4/ZnO
nanoparticles
pure substance (JCPDS No. 75-0449) with Fd3m space
group which is consistent with previous reports [23–25].
The XRD pattern for ZnO with high intensity shows well-
crystalline sample with JCPDS No. 79-0208 and P63mc
space group. The calculated crystalline sizes from Scherrer
equation, Dc = Kk/bCosh, where b is the width of the
observed diffraction peak at its half maximum intensity
(FWHM), K is the shape factor, which takes a value of
about 0.9, and k is the X-ray wavelength (CuKa radiation,
equals to 0.154 nm) were about 12 and 25 nm for Fe3O4
and ZnO nanoparticles, respectively. The structure and
composition of the Fe3O4/ZnO nanocomposites is also
shown in, in Fig. 2. XRD pattern of the nanocomposites. It
can be observed that both cubic phase of Fe3O4 (JCPDS
No. 75-0449) and hexagonal phase of ZnO JCPDS No.
79-0208 are present in the pattern. The intensities of peaks
related to each counterpart is relatively similar which is
representative of rather equal portion of the shared com-
pounds for in the composite.
In order to investigate effect of time on morphology and
size of Fe3O4 nanoparticles, two different reaction times
were selected. Figure 3a, b illustrate SEM images of the as-
synthesized Fe3O4 nanoparticles obtained after 10 min
irradiation of 60 W ultrasonic waves, nanoparticles with
average diameter size less than 50 nm were prepared. In
sonochemical procedure, chemisorbed –OH are formed on
the surface of the primary nuclei which contain the as-
formed Fe3? atoms. During an ultrasonic treatment, ongo-
ing under O2-excluded atmosphere, the oxidation extent of
the particle surface are related to the time of the ultrasonic
treatment since the˙OH radicals generated by ultrasonic
treatment are responsible for inducing the oxidation of Fe2?
into Fe3?. In this condition, the dispersity of the formed
nanoparticles is tuneable by adjusting the time of ultrasonic
treatment because by generation more hydroxyl groups
higher numbers of Fe3? are produced on the particle surface
and the as-formed Fe3? chemisorb hydroxyl groups, which
their concentration is increasing with ultrasonic time [26].
Recently, Küçük et al. [27] showed that ultrasonic agitation
decreased the size of PMAA-coated Fe3O4 agglomerates
significantly. However, herein, an inverse effect is observed
so that, with increasing the ultrasonic irradiation time from
10 to 30 min, the agglomeration size is increased from
25–60 to 130–350 nm. This result could be attributed to the
different atmosphere in which the experiment is undertaken.
The presence of oxygen accelerate the oxidation of Fe2? to
Fe3? and consequently, the surface oxidation of particle
surface and chemisorption of –OH is not dependant on
ultrasonic duration. As soon as the required –OH is avail-
able in the solution, the already-produced Fe3? becomes
saturated and increasing the ultrasonic time does not help
dispersion of the formed nuclei. In addition, the collapse of
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Fig. 3 SEM images of Fe3O4 a,
b 10 min c, d 30 min
bubbles which generates localized hot spots with transient
temperatures of *5000 K increases the solution tempera-
ture in longer reaction time [28] and the crystal growth is
faster at higher temperatures [29]. Moreover, prolongation
of the reaction up to 30 min causes oxidation of most of the
Fe2?–Fe3? and as a result, brown FeOOH nanoparticles are
also obtained which are more likely to agglomerate.
Figure 4 shows the effect of sonication power on particle
size. A detailed study on this effect is already reported by
Mosivand et al. which shows that the particle size and
morphology of magnetic nanoparticles are easily controlled
by adjusting the power. Moreover, it was shown that ultra-
sonic power had a significant, but rather unpredictable
influence on the mean magnetite particle size [30]. Fig-
ure 4a, b exhibit SEM images of Fe3O4 that achieved at
100 W ultrasonic irradiation, images approve agglomeration
size between 150 and 750 nm. In Fig. 4c and d, it is
observed that with increasing the ultrasonic power, the
agglomeration size decreases to 100–500 nm. The balance
between nucleation rate and growth rate which determines
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J Mater Sci: Mater Electron
final particle size and morphology depends both on the
system and the ultrasonic power [30].
During the ultrasound cycles, the cavitation bubbles
would collapse, forming micro-jets that instantaneously
generate intense local heating and high pressure. The
micro-jet impact can develop pressures of about
2 9 108 Pa, and a local heating and cooling rate above
109 K/s. In fact, cavitation damage is generated by the non-
spherical symmetric collapse of a cavitation bubble, either
at or near a solid surface. Violent collapse of bubbles in
asymmetrical geometries occur in a number of situations of
practical interest including cavitation, shock-wave and
laser lithotripsy [14, 16]. This method proposes easy
manipulation in particle size and so magnetic properties by
a simple change in power, time of irradiation, precursor,
temperature and solvent.
In order to investigate the effect of ZnO concentration
on Fe3O4–ZnO agglomeration size, two nanocomposite
samples with 10 and 50 % of ZnO were prepared under
ultrasonic irradiation for 10 min. Figure 5a–b, c–d show
J Mater Sci: Mater Electron
Fig. 4 SEM images of Fe3O4
nanostructures synthesized at a,
b 100 W, c, d 150 W
SEM images of the prepared samples with 10 and 50 % of
ZnO, respectively. At the first sight to the both images, one
can realize the lower degree of agglomeration in 10 %
sample. The agglomeration size of 10 and 50 % samples
are in the range of 50–150 and 60–300 nm, respectively.
The smaller agglomeration of 10 % sample could be
attributed to thinner ZnO shell around magnetic seeds
which gives rise to less agglomeration.
Figure 6a–c shows the Fourier transform infrared (FT-
IR) spectra of the as-prepared Fe3O4, Fe3O4/ZnO, and ZnO
nanoparticles, respectively. In Fig. 6a, the absorption band
at 567 cm-1 is assigned to the Fe–O stretching mode of the
tetrahedral and octahedral sites for the m1 band and the
band at 426 cm-1 is assigned to the Fe–O stretching mode
of the octahedral sites for the m2 band [31]. In Fig. 6b, the
FT-IR spectrum of nanocomposite clearly shows Fe–O
bond around 565 cm-1. In order to confirm existence of
Zn–O bond in nanocomposite, ZnO nanoparticles were
prepared in absence of Fe3O4 by the same method and its
FT-IR spectrum is shown in Fig. 6c. It can be observed that
the strong absorption band at 435 cm-1 which is ascribed
to phonon absorptions of the ZnO lattice [11] is present
both in Fig. 6b, c. The spectrum exhibits broad absorption
peaks between 3500 and 3600 cm-1, corresponding to the
stretching mode of O–H group of hydroxyl group and the
weak band near 1630 cm-1 is assigned to H–O–H bending
vibration mode due to the adsorption of moisture on the
surface of nanoparticles [32].
Energy dispersive spectroscopy (EDS) analysis was
performed to monitor the average elemental composition of
the as-prepared nanocomposite and confirm the purity of
the product. Figure 7 shows the typical EDS pattern of the
sample that confirmed the presence of Fe, Zn and O ele-
ments and there were no other peaks for impurities.
Room temperature magnetic properties of samples were
studied using AGFM device. Hysteresis loop for Fe3O4
magnetite nanoparticles, Fe3O4/ZnO (10 %), and Fe3O4/
ZnO (50 %) are shown in Fig. 8a–c, respectively. This
shows a sufficient magnetization of these Fe3O4 NP/ZnO
NR composites for being recycled by a magnet, making
them excellent recyclable photocatalyst. Fe3O4 synthesized
nanoparticles show super-paramagnetic behaviour and
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Fig. 5 SEM images of Fe3O4–
ZnO nanocomposite a, b, ZnO-
10 % c, d ZnO-50 %
have a saturation magnetization of 58 emu/g and very low
coercivity. Figure 8b shows magnetization curve of Fe3O4–
ZnO 10 % nanocomposites that also exhibits super-para-
magnetic behavior with a very low coercivity and a satu-
ration magnetization of 47 emu/g. This magnetization
indicates that Fe3O4–ZnO 10 % nanocomposites inherit the
magnetic property from the Fe3O4 NPs; however, the
magnetization is lessen due to presence of zinc oxide. This
reduction in saturation magnetization is due to the inter-
facial effect of the typical core–shell nanostructures [33].
The super-paramagnetic property of the prepared
nanocomposites is an essential characteristic of a regener-
able and reusable smart magnetic heterogeneous catalyst
since materials with this magnetic behaviour have low
tendency in interparticles agglomeration caused by dipole–
dipole interaction in comparison with ferromagnetic
nanocomposites. Moreover, better dispersion of the super-
paramagnetic naocomposites provide more surface area
which is a key factor in superior performance of a good
catalyst [23]. As ca be observed in Fig. 8c, increasing ZnO
content to 50 % results in a switch from super-
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J Mater Sci: Mater Electron
paramagnetic to ferromagnetic behaviour with a coercivity
around 100 and a saturation magnetization of 32 emu/g.
The results also indicate that nanocomposite formation
give rise to coercivity enhancement. This could be attrib-
uted to the addition of ZnO on the surface of magnetic
nanostructure which changes its magnetic features [33]. A
possible explanation for this result could be as follow: The
magnetic moments of magnetic nanoparticles are pined by
the ZnO, so that a higher magnetic field is requires to align
the single domain nanoparticles in the field direction [19].
The photo-catalytic activity of the Fe3O4/ZnO-10 %
nanocomposite was evaluated by monitoring the degrada-
tion of organic dyes in an aqueous solution, under irradi-
ation with UV light. The changes in the concentration of
dye are illustrated in Fig. 9. In 60 min, the degradation of
Methyl orange, Eriochromschwarz T, Eosin Y, Rhodamin-
B and Methylene-blue was about 94, 57, 42, 38, and 18 %,
respectively. The degradation after 60 min for various azo
dyes including Acid brown 14, Acid violet 7, Acid blue 92,
and Acid red 151 were about 70, 45, 40, and 23 %,
respectively. Considering the mentioned results, the best
J Mater Sci: Mater Electron
Fig. 6 FT-IR images of a Fe3O4 nanoparticles, b Fe3O4–ZnO
nanocomposite, c ZnO nanoparticles
Fig. 7 EDS spectrum of Fe3O4–ZnO nanocomposite
degradation efficiency of the prepared nanocomposite is for
Methyl Orange dye which has been degraded about 94 %
after 60 min and it was completely depredated after 65 min
and after that, Acid brown 14 with complete degradation
after about 80 min gave a satisfactory result. Organic dyes
decompose to carbon dioxide, water and other less toxic or
nontoxic residuals [6]. Figure 9c, d show complete degra-
dation of the Acid brown 14 and Methyl orange dyes after
80 and 60 min exposure to the nanocomposite.
Fig. 8 Room temperature hysteresis loop of a Fe3O4 nanoparticles,
b Fe3O4–ZnO nanocomposite 10 % ZnO, c Fe3O4–ZnO nanocom-
posite 50 %
4 Conclusions
In conclusion, synthesis, characterization, and photocat-
alytic activity of Fe3O4/ZnO nanocomposite was reported.
First, magnetite nanoparticles were synthesized via a sono-
chemical method and the procedure was followed by syn-
thesis of ZnO shell on the surface of the prepared magnetite.
Effect of sonication time, power, and ZnO concentration was
investigated on morphology and particle size of the products.
AGFM confirmed that nanoparticles and nanocomposite
with 10 % of ZnO exhibit super-paramagnetic behaviour.
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Fig. 9 Photocatalytic activity
of Fe3O4/ZnO (10 %)
nanocomposites on degradation
of various dyes with time a acid
dyes, b azo dyes, c complete
degradation of Acid brown 14
after 80 min, d complete
degradation of Methyl orange
after 60 min
However, by addition of 50 % of ZnO, the paramagnetic
behaviour switched to ferromagnetism. The photocatalytic
behaviour of Fe3O4–ZnO nanocomposite was evaluated
using the degradation of eight various organic and azo dyes
aqueous solution under UV light irradiation. The results
show that sonochemical method is a suitable approach for
preparation of Fe3O4–ZnO nanocomposites as promising
candidate for photocatalytic applications.
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