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Advanced Powder Technology xxx (2011) xxxxxx
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Contents lists available at ScienceDirect

Advanced Powder Technology

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

Original Research Paper

Synthesis of magnetite nanoparticles by surfactant-free electrochemical method

in an aqueous system

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Q1

Fauziatul Fajaroh, Heru Setyawan , W. Widiyastuti, Sugeng Winardi

Department of Chemical Engineering, Faculty of Industrial Technology, Sepuluh Nopember Institute of Technology, Kampus ITS Sukolilo, Surabaya 60111, Indonesia

a r t i c l e

i n f o

Article history:
Received 1 November 2010
Received in revised form 27 March 2011
Accepted 12 April 2011
Available online xxxx
Keywords:
Magnetite nanoparticles
Electrochemical synthesis
Aqueous system
Surfactant-free
Magnetic properties

a b s t r a c t
A simple surfactant-free electrochemical method is proposed for the preparation of magnetite nanoparticles using iron as the anode and plain water as the electrolyte. This study observed the effects of certain
parameters on the formation of magnetite nanoparticles and their mechanism in the system, including
the role of OH ions, the distance between electrodes and current density. We found that OH ions play
an important role in the formation of magnetite nanoparticles. Particle size can be controlled by adjusting
the current density and the distance between electrodes. Particle size increases by increasing the current
density and by decreasing the distance between electrodes. Particle formation cannot be favored when
the distance between electrodes is larger than a critical value. The magnetite nanoparticles produced
by this method are nearly spherical with a mean size ranging from 10 to 30 nm depending on the experimental conditions. They exhibit ferromagnetic properties with a coercivity ranging from 140 to 295 Oe
and a saturation magnetization ranging from 60 to 70 emug1, which is lower than that of the corresponding bulk Fe3O4 (92 emug1). This simple method appears to be promising as a synthetic route to
producing magnetite nanoparticles.
2011 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights
reserved.

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1. Introduction

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Magnetite (Fe3O4) is one of the most important magnetic materials and is widely used in industry. In recent years, monodispersed
magnetite nanoparticles have attracted increasing attention due to
their good biocompatibility, strong superparamagnetic properties,
low toxicity and easy preparation process [1]. They have considerable potential for use in the biomedical industry, such as targeted
drug delivery, hyperthermia treatment, cell separation, magnetic
resonance imaging, immunoassays and the separation of biochemical products [26]. They are also useful for environmental processes, such as the treatment of water and wastewater [79].
Among the methods available for the preparation of magnetite
nanoparticles, the co-precipitation of ferrous and ferric ions in
aqueous solutions is attractive because of its simplicity and low
cost [10]. Producing monodispersed magnetite nanoparticles using
this conventional method is difcult due to instantaneous reactions in the mixture that make it difcult to control the process
of crystallization [11]. Moreover, the size of the generated particle
is typically in the range of 512 nm, which tends to decrease its
magnetic properties [10,12]. Alternatively, solgel and hydrothermal techniques may effectively control the morphology and chem-

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Corresponding author. Tel.: +62 31 5946240; fax: +62 31 5999282.

E-mail address: sheru@chem-eng.its.ac.id (H. Setyawan).

ical composition of the prepared magnetite nanoparticles [13,14].

However, the solgel technique typically requires expensive alkoxide reactants, high temperature calcinations, and a long time to
produce the nal product. The hydrothermal technique requires a
high temperature and a long time period to obtain the nal product
(about 25 h). This method is typically performed in the presence of
a surfactant to avoid the aggregation of particles. The combination
of surfactants with magnetite may not be rm enough, and they
may severely interfere with certain applications, such as biomedical uses [15].
The electrochemical method is beginning to emerge as an option for the preparation of magnetite nanoparticles [1619]. It offers many advantages over the above-mentioned methods for the
production of magnetite nanoparticles. Using this method, the
particle size can be easily controlled by adjusting the imposed
electro-oxidation current density or potential to the system. Marques et al. prepared magnetite nanoparticles with sizes ranging
from 4.4 to 9 nm by the electrochemical method, using Fe(NO3)3
as the iron precursor in ethanol media [16]. However, the purity
of the nal product is quite vulnerable to the synthesis conditions,
i.e., iron concentration and current density. These parameters must
be controlled very carefully to prevent the formation of iron
hydroxide, which contaminates the magnetite particles. Moreover,
this method requires a relatively water-free bath to obtain pure
magnetite particles, which causes the generated particles to be

0921-8831/$ - see front matter 2011 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights reserved.
doi:10.1016/j.apt.2011.04.007

Please cite this article in press as: F. Fajaroh et al., Synthesis of magnetite nanoparticles by surfactant-free electrochemical method in an aqueous system,
Advanced Powder Technology (2011), doi:10.1016/j.apt.2011.04.007

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F. Fajaroh et al. / Advanced Powder Technology xxx (2011) xxxxxx

hydrophobic. A hydrophobic surface does not allow the particles to

be easily dispersed in aqueous solution. Indeed, the efcacy of
many applications might rely upon generating hydrophilic and
well-dispersed nanoparticles in aqueous solution [20]. Franger
et al. prepared magnetite nanoparticles using electrochemical processes from an iron-based electrode in an alkaline aqueous soluQ2 tion (pH 10) containing a complexing agent such as Cl, SO4,
SCN, or S2O3 to enhance the kinetics of the elemental charge
transfer reaction of iron metal [18,19]. The particles produced by
their method had sizes ranging from 74 to 88 nm. Cabrera et al.
used a similar method to produce magnetite nanoparticles of sizes
between 20 and 30 nm in aqueous solution, but they used pure
iron as the anode and an amine surfactant, instead of a complexing
agent, to avoid aggregation [17]. As mentioned above, the use of a
surfactant may strongly interfere with certain applications.
Several studies on surfactant-free method for synthesizing
magnetite nanoparticles using liquid phase reactions have been reported [21,22]. Nishio et al. prepared magnetite nanoparticles by
oxidizing ferrous hydroxide with a weak oxidant in an N2-deaerated aqueous NaOH solution at various temperatures below 37 C
without any surfactant [21]. The particles produced by their method had sizes ranging from 30 to 100 nm depending on the synthesis temperature. Ahniyaz et al. synthesized magnetite nanocrystals
by a surfactant-free thermal decomposition of iron alkoxide precursors at temperatures higher than 320 C resulting nanocrystals
with an average size of about 5.6 nm [22]. Their method involved
the use of organic solvents such as octadecene and ethanol that
may remain on the particle surface and tend to make the particles
to be hydrophobic.
It has been shown that, as illustrated by the Pourbaix diagram,
iron oxides and/or hydroxides (Fe2O3, Fe3O4, Fe(OH)2, Fe(OH)3) can
be in electrochemical equilibrium with water at high potentials in
neutral and basic solutions [23]. Therefore, an iron oxide lm may
be grown electrochemically on the surface of iron-based materials
to produce a blue-black magnetite layer, a light brown oxide, or a
semi-adherent dichroic magnetite layer by varying temperature,
voltage, and electrolyte composition [24,25]. It was assumed that
if a layer of iron lm adheres weakly to an anode surface, iron
oxide would be released from the surface during the electro-oxidation of the iron and would not adhere to the surface as mentioned
above. Under basic conditions, Fe3O4 may be formed by the corrosion process in an aqueous medium [26]. The particle size might be
constrained by controlling the current density to the system, which
controls the oxidation rate.
In the present work, we report on the electrochemical synthesis
of nano-sized particles of magnetite using a sacricial iron anode
and untreated water as the electrolyte without any surfactant.
We also investigated the role of hydroxyl ions on magnetite formation. Moreover, we rst studied various physicochemical parameters to understand the reaction mechanism so that we could
optimize the conditions of the electro-synthesis.

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2. Experimental

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A sacricial iron anode and an iron-based cathode of the same

dimensions (23 mm  13 mm dimension and 0.25 mm thick) were
used for the synthesis of magnetite nanoparticles. To obtain a
highly pure iron layer that was adhered weakly on the anode surface, a steel plate was electroplated in a 0.072 M FeSO4 solution under a current density of 0.167 A/dm2 for 6 h. It was conrmed that
the thickness of the iron coated on the steel was sufcient for all
experiments to synthesize magnetite nanoparticles for the designated period of time. The experiments were carried out in de-ionized water, either with or without the addition of sodium
hydroxide to understand the role of OH ions in the formation of

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magnetite. The distance between electrodes varied from 2 to

6 cm. The current density was varied from 205 to 415 lA/cm2 by
adjusting the potential using a laboratory DC power supply (GW
Instek GPC-M Series). The potential and the current were measured
by a digital multimeter (HewlettPackard Type 3435A). All experiments were conducted at room temperature and had a reaction
time of 12 h unless otherwise stated. The obtained product was
washed with de-ionized water and dried at 60 C for subsequent
analysis. Under the time course of the experiments, about 0.4
0.7 g of dried powders was obtained depending on the current density applied. The progress of the reaction was followed by the
change of electrolyte turbidity (TB 1000 EUTECH) around the anode by sampling a small amount of aliquots periodically. In addition, it was also observed by recording the electrochemical cell
using a video camera for later inspection.
The mean size of the prepared particles was measured indirectly by measuring their BET specic surface area, which was
determined by multi-point nitrogen adsorption at its boiling point
(Nova 1200, Quantachrome). In this measurement, the particles
were assumed to be spherical and dense such that the particle
diameter dp could be calculated using the relation.

6
dp
qAs

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where q is the particle density and As is the specic surface area.

X-ray diffraction (XRD) patterns were detected using an X-ray diffractometer (XPert, Philips). Infrared (IR) spectra were recorded
using an FTIR spectrophotometer (FTIR 8400s, Shimadzu). Magnetic
characterization was conducted using a vibrating sample magnetometer (Type 1.2H VSM, Oxford).

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3. Results and discussion

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3.1. Magnetite nanoparticles

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A black precipitate was obtained by electrochemical synthesis

under the conditions described above, both with and without the
addition of NaOH. The initial pH of the electrolyte with and without the addition of NaOH was about 7 and 10, respectively, and the
current density was kept constant at 205 lA/cm2 for both experiments. The black precipitate was identied as magnetite by XRD.
Fig. 1 shows the XRD patterns of the representative dried powder
for the samples with and without NaOH at a distance between
electrodes of 6 cm. The patterns for both cases have seven charac-

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Fe3O4
FeOOH

Intensity (a.u.)

without NaOH

with NaOH
10

20

30

40

2 (degree)

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60

70

Fig. 1. XRD patterns of the particles prepared by electro-oxidation with and

without NaOH addition at a distance of 6 cm between electrodes and a current
density of 205 lA/cm2.

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10
9

Transmittance (%)

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3176.87

1022.31

OH

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2

580
Fe3O4 442

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0
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3400

2900

2400

1900

1400

900

400

100 nm

Wavenumber (cm -1)

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teristic peaks (indicated by a circle) at 30.5 (2 2 0), 35.9 (3 1 1),

37 (2 2 2), 43.5 (4 0 0), 57.3 (5 1 1) and 63.1 (4 4 0), which
match the standard pattern of Fe3O4 (JCPDS 19-0629) well. The diffraction peaks were indexed in the cubic spinel structure (space
group Fd3m, No. 227). There are still diffraction peaks, indicated
by a square symbol, other than those for Fe3O4 that correspond
to FeOOH (JCPDS 44-1415). It appears that FeOOH is an intermediate product in the formation of Fe3O4 during electrochemical synthesis, which will be discussed in detail later.
The infrared spectrum of the above sample without the addition
of NaOH shown in Fig. 2 conrms that, in addition to Fe3O4, FeOOH
exists in the sample as indicated by the XRD pattern. Two main
bands can be observed in the gure corresponding to Fe3O4. The
bands at 580 and 442 cm1 are metaloxygen bands that correspond to the intrinsic stretching of the tetrahedral and octahedral
sites of the inverse spinel cubic of Fe3O4, respectively. The bands
appearing from 3600 to 3200 cm1 and at 1022 cm1 can be attributed to O-H stretching that probably comes from FeOOH. A scanning electron microscopy (SEM) image of the sample prepared
under the above conditions without the addition of NaOH is shown
in Fig. 3(a), and the corresponding size distribution derived from
the image is shown in Fig. 3(b). The size distribution was deduced
from the SEM image using Feret method with a particle number of
about 200 particles. The particles are quasi-spherical with a mean
particle size of about 18.7 nm with a standard deviation of 1.1 nm.
The mean particle size estimated from the specic surface is about
22.5 nm, which is in agreement with that measured by SEM.
The variation of current density and the distance between electrodes signicantly inuences the mean particle size. As shown in
Fig. 4, the particle size tends to increase with an increase in current
density and a decrease in the distance between electrodes. The results on the effect of current density do not agree with previous results on the electrochemical generation of Fe3O4 in the presence of
an amine surfactant reported by Cabrera et al. [17]. In their study,
mean particle size was observed to be constant even if current density was varied. Cabrera et al. imposed a much higher maximum
current of 200,000 lA/cm2, where the effects of diffusion rate
and the Helmholtz layer can be ignored during the reaction. In
our study, the effect cannot be neglected because the maximum
current used in this work was only 600 lA/cm2, which is much
lower than that of Cabrera et al. These may also be the reason
why the effect of electrode distance on the particle size is slight
at a current density less than 400 lA/cm2. Both charge transfer
and diffusion rate have signicant effect on the overall reaction
of magnetite formation at low current density, i.e., low reaction

0.30
0.25

Fraction/m

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191

0.20
0.15
0.10
0.05
0.00
0

10

15

20

25

30

35

40

Particle size (nm)

Fig. 3. (a) SEM image of particles prepared at a distance of 6 cm between electrode
and a current density of 325 lA/cm2 and (b) the corresponding particle size
distribution (number basis) deduced from SEM images using Feret method.

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Particle size (nm)

Fig. 2. FTIR spectrum of particles prepared under the same conditions as in Fig. 1
without the addition of NaOH.

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2 cm
6 cm

20

15

10
100

200

300

400

500

600

Current density (A/cm )

2

Fig. 4. Effect of current density and distance between electrodes on particle size.

rate, that makes the particle size increases slightly by decreasing

the electrode distance. In addition, when inuencing the particle
size, the distance between electrodes also inuences the crystallin-

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Intensity (a.u.)

6 cm

Fe3O4
FeOOH

2 cm
20

40
2 (degree)

60

Fig. 5. XRD patterns of the particles prepared by electro-oxidation at a current

density of 205 lA/cm2 and two different distances between electrodes.

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ity of the formed magnetite. The crystallinity tends to increase

when the distance between the electrodes is decreased as shown
in Fig. 5. Decreasing the electrode distance would make the hydroxyl ions produced by water reduction at the cathode reach the anode faster. This, in turn, makes the concentration of OH near the
anode is high that favor the formation of magnetite. This may explain why the crystallinity tends to increase with the decrease of
electrode distance.
The magnetic properties of the prepared magnetite nanoparticles were investigated with VSM at room temperature. Fig. 6 shows
the magnetization curve for magnetite nanoparticles prepared at a
distance of 6 cm between electrodes with two different current
densities, namely 205 and 325 lA/cm2. The result indicates that
the magnetite nanoparticles likely possess ferromagnetic properties as indicated by a hysteresis loop, which is typically observed
for ferromagnetic materials of sizes larger than 10 nm. The hysteresis loop is related to the pinning of magnetic domain walls at
impurities or grain boundaries within the material and also to
intrinsic effects, such as the magnetic anisotropy of the crystalline
lattice [27]. The saturation magnetization of the nanoparticles was
dependent on the current density, i.e., the particle size, that takes
the value of about 60 and 70 emug1 for the current densities of
205 and 325 lA/cm2, respectively. The values are less than that
of the Fe3O4 bulk materials (Ms = 92 emug1) [28]. The reduction

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60

Magnetization (emu/g)

238

40

Current
(A/cm 2)
325
205

Ms
(emu/g)
70
60

325 A/cm

Hc
(Oe)
140
295

205 A/cm

20
0
-20
-40
-60
-80
-1.0 -0.8 -0.6 -0.4 -0.2 0.0

0.2

0.4

0.6

0.8

1.0

Applied Field (T)

Fig. 6. Magnetization curve at room temperature of magnetic nanoparticles
prepared under the same conditions as in Fig. 1 without the addition of NaOH.

of saturation magnetization may be attributed partly to the small

particle size and the high surface area, which lead to surface effects, such as spin canting. From the curve, we found that the
coercivities have values of about 295 and 140 Oe, which is in agreement with the expected value for randomly oriented, uniaxial and
non-interacting particles of magnetite.

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3.2. Mechanism of particle formation

268

It has been shown that during the corrosion process of iron in an

aqueous medium, Fe3O4 may be formed by an alkalization reaction
of ferrous ions under a condition of excess OH ions [29]. Therefore, the solution should be sufciently basic, probably around
nine, for the formation of Fe3O4 to occur. To conrm this, some
experiments were carried out with a large distance between electrodes (6 cm) so that OH ions produced by the reduction of H2O
at the cathode had little effect on particle formation around the anode. One experiment occurred without the addition of NaOH, and
the other was performed with the addition of NaOH (pH 10) as
described above. The aim of these experiments was to understand
the role of the OH ion on the formation of Fe3O4. Notably, the
solution for both cases, especially close to the anode, initially displayed several color changes. The solution was colorless at the
beginning of the experiments when neither current nor potential
had yet been imposed. As the reaction took place, yellowbrown
precipitates gradually appeared near the anode. These yellow
brown precipitates indicated the formation of Fe(OH)2, as being
in water with the presence of oxygen produced by anodic reaction,
readily oxidized, upon which the color changes immediately from
green to brownish [30]. The formation of Fe(OH)2 proceeded with
the elapsed time as indicated by the increase in the amount of yellowbrown precipitates. Then, the color of the precipitates gradually changed to reddish-brown indicating the formation of FeOOH.
Finally, the precipitates became black, indicating the formation of
Fe3O4. The color changes occurred faster for the case where NaOH
was added. It is obvious that higher OH concentrations induce a
faster formation rate of Fe3O4 as discussed above. However, the
fact that Fe3O4 can be formed without the external addition of
OH ions is exciting. This result means that OH ions originating
from water reduction at the cathode are sufcient to induce the
formation of Fe3O4 around the anode. Therefore, it could be
expected that the formation rate of F3O4 might be increased by
reducing the distance between electrodes or by increasing the current density. These possibilities will be discussed in the following
section.
As expected, when the distance between electrodes was
reduced to 2 cm, the appearance of yellowbrown, then reddishbrown, and eventually black precipitates occurred at a much shorter time. In addition, the crystallinity of the magnetite increases by
decreasing the distance between electrodes as discussed previously (Fig. 5). The reaction occurring during the electrosynthesis
of magnetite was followed by monitoring the turbidity of the
solution close to the anode. Fig. 7 shows the change of solution turbidity at two different current densities. Turbidity indicates the
formation of particles in the solution. The turbidity increases more
rapidly at a higher current density, indicating a faster formation
rate of Fe3O4. Increasing current density has a similar effect to that
caused by decreasing the distance between electrodes, for which
the formation rate increases by increasing the current density.
From these data, the XRD pattern and the FTIR spectrum, the
route of a particle formation taking place during the electrooxidation of iron can be deduced. This is illustrated schematically in
Fig. 8. At the beginning of the reaction, the iron anode was oxidized
rst to ferrous ions.

269

Fe ! Fe

2e

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4OH ! O2 2H2 O 4e

Turbidity (ntu)

1
3FeOH2 O2 ! FeOH2 2FeOOH H2 O
2

100

205 A/cm
2
415 A/cm

10

10
15
Time (h)

20

FeOH2 FeOOH ! Fe3 O4 2H2 O

25

Fig. 8. Schematic diagram of the Fe3O4 formation process by the electro-oxidation

of iron anode in water.

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329
330

Because the potential imposed was low, further oxidation of ferrous ions to ferric ions did not occur. As mentioned above, the rst
color of precipitates appeared was yellowbrown indicating the
formation of Fe(OH)2 as follows.

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333

Fe2 2OH ! FeOH2

334

342

When NaOH was added, the OH ions required for the formation of Fe(OH)2 were readily available in the region close to the anode. Therefore, the yellowbrown precipitates appeared during the
rst hours of electrosynthesis because the conditions that favor the
precipitation of Fe(OH)2 were met. However, for the case without
the addition of NaOH, the basic media required for the formation
of Fe(OH)2 were not readily available. The OH ions may come
from the cathode. At the cathode, the reduction of water occurs
according to the following reaction.

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2H2 O 2e ! H2 2OH

335
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341

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350
351

The formation of FeOOH was indicated by the appearance of

reddish-brown precipitates as mentioned above. Magnetite is
formed when an appropriate proportion of Fe(OH)2 and FeOOH is
created by the following reaction.

Fig. 7. The change of solution turbidity around the anode at two different current
densities.

327

In the presence of oxygen, ferrous hydroxide can be partially

oxidized to form FeOOH following the reaction [29,31].

1000

The OH ions produced at the cathode arrive at the anode by

diffusion, creating the basic medium necessary for the formation
of Fe(OH)2. The initial pH of the solution near the anode was 7,
and it increased to 9 by the end of process.
The reduction of hydroxyl ions is another reaction that provides
protons near the anode according to the following reaction.

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The formation of FeOOH as intermediate product is also suggested by the XRD pattern of the samples as discussed above (Figs.
1 and 5).
We conclude that the distance between electrodes appears to
be critical to the formation of magnetite by the electrochemical
method. If the distance between electrodes is too great, the region
close to the anode cannot reach the pH value necessary for the precipitation of ferrous hydroxide. Therefore, when the distance between electrodes was greater than 6 cm, the formation of any
precipitate was not observed during the standard reaction time.
It should be noted that the mechanism of magnetite formation
described here is completely different from that of Cabrera et al.
[17]. In their case, magnetite was formed by reduction of ferric
hydroxide at the cathode. They used a supporting electrolyte in
the form of amine salt that probably fastened the diffusion rate
of ions formed to reach the cathode. In our study, we used only
plain water as an electrolyte. In the absence of a supporting electrolyte, the diffusion of ions becomes very slow. Therefore, the
overall reaction rate is controlled by diffusion. Because the mobility of the OH ion is higher than that of the Fe2+ ion [32], OH ions
produced by water reduction at the cathode move faster to reach
the anode region.

367

4. Conclusions

389

This study demonstrated that magnetite nanoparticles can be

prepared using a simple surfactant-free electrochemical method.
The magnetite nanoparticles produced are nearly spherical and
are uniform in size, with mean sizes ranging from about 10 to
30 nm depending on the experimental conditions. Although there
are some impurities in the form of FeOOH, which is a non-magnetic
material, the nanoparticles still exhibit ferromagnetic behavior
with a relatively high saturation magnetism. The formation of
magnetite nanoparticles is favored in the presence of hydroxyl
ions, either from an external source or from water reduction at
the cathode during preparation. The formation of magnetite nanoparticles is inuenced by certain factors, including the distance between electrodes and the current density. An increase in current
density tends to promote the formation of magnetite nanoparticles, and the particle size becomes larger. Moreover, the distance
between electrodes appears to be important for producing magnetite nanoparticles using this electrosynthesis technique. This
arrangement can promote the formation of magnetite by supplying
sufcient OH ions that are necessary for its formation. These preliminary results demonstrate the possibility of using this technique
as an environmentally friendly synthetic route to producing magnetite nanoparticles.

390

Acknowledgements

412

This work was partially supported by a Fundamental Research

Grant provided by the Directorate General of Higher Education,
Ministry of National Education, Indonesia. One of the authors

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Please cite this article in press as: F. Fajaroh et al., Synthesis of magnetite nanoparticles by surfactant-free electrochemical method in an aqueous system,
Advanced Powder Technology (2011), doi:10.1016/j.apt.2011.04.007

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(F.F.) would like to thank DGHE, the Ministry of National Education, Indonesia for a doctoral scholarship through BBPS. We also
thank Ms. Risa Enggawati and Ms. Intan Gita Wardhani for their
assistance with the experiments.

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Please cite this article in press as: F. Fajaroh et al., Synthesis of magnetite nanoparticles by surfactant-free electrochemical method in an aqueous system,
Advanced Powder Technology (2011), doi:10.1016/j.apt.2011.04.007

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