ORI GI NAL PAPER

Synthesis of Iron Nanoclusters by Pulsed Current

Method
Hassan Karami Ozra Rostami-Ostadkalayeh
Received: 3 January 2009 / Published online: 28 July 2009
Springer Science+Business Media, LLC 2009
Abstract The main objective of this research is to prepare iron nanoclusters with
more porous structure by the pulsed current electrochemical method. In this method,
there are some effective parameters including; pulse amplitude (current amount),
pulse frequency, iron salt concentration, sulfuric acid concentration and synthesis
temperature, which were optimized by the one at a time method. An iron optimized
nanopowder was synthesized by using iron sulfate (0.005 M) as precursor and silver
nitrate as a nucleation agent (at 0.5% mole of iron sulfate in the starting solution) by
pulsed current of 20 mA cm
-2
with a frequency of 14 Hz. The relative gravimetrical
density was used as an optimizing parameter for iron nanoparticles synthesis. The
morphology and particle size of each synthesized sample was studied by SEM, TEM
and XRD. The iron nanopowder synthesized in the optimum conditions has excellent
uniform and a more porous structure including nanoclusters with a particle size of
approximately 2040 nm. The obtained results indicate that the pulsed current elec-
trochemical method can be used as a condent and controllable method for the
preparation of iron nanoparticles. XRD, EDX and ICP-AES results showed that the
iron nanoclusters can be synthesized with high purity by the proposed method.
Keywords Pulsed current Nanoclusters Iron Electrochemical
Nanoparticle Nanopowder
Introduction
Small metal particles in the nanometer range display different chemical and
physical properties from bulk materials, and play an important role as a
H. Karami (&) O. Rostami-Ostadkalayeh
Electrochemistry Laboratory, Department of chemistry, Payame Noor University (PNU),
P.O. Box 97, Abhar, Iran
e-mail: [email protected]
1 3
J Clust Sci (2009) 20:587600
DOI 10.1007/s10876-009-0262-5
heterogeneous catalyst. The reactivity of the nanosized catalyst particle is associated
with their high ratio of surface to bulk atoms [1]. The metal nanoparticles display
unique properties that differ from the bulk substances, i.e., a different heat capacity,
vapor pressure, and melting point. Moreover, when decreasing the metal particle
size sufciently enough, there occurs a transition of the electronic state from a
metallic to non-metallic one. Additionally, metal nanoparticles exhibit a large
surface-to-volume ratio and an increased number of edges, corners and faces leading
to altered catalytic activity and selectivity [2]. Nanometre-sized particles of
magnetic metals have been attracting substantial interest in basic and applied
research for many years [36]. This activity is mainly driven by the envisaged
application of such nanoparticles in high-density data storage [7], in magnetic
resonance imaging [8, 9], catalysts [10, 11] and especially for soil remediation [12].
In many cases they show improved or even new properties due to their size in the
nanometre range [13]. State-of-the-art production methods of metal nanoparticles
include arc discharge [4], colloidal chemistry [14], sputtering or laser ablation [15],
and ripening from gel-like lms [10]. Each method has its specic advantages and
disadvantages. Critical issues are the stability of the particles with time, their
protection against oxidation [16], and the control of their size and shape [17].
Magnetic nanoparticles have received much attention because of their applica-
tions in various elds, and thus, a lot of methods for synthesis of magnetic
nanoparticles have been developed and reported. As for the metal nanoparticles,
methods through decomposition or chemical reduction of organometallic com-
pounds at high temperature are investigated extensively. In the present study, we
focus on a two-phase liquidliquid system, which has been established for the
synthesis of gold nanoparticles [18], as a novel approach to the synthesis of
magnetic nanoparticles containing iron. Because the two-phase liquidliquid system
has been applied to the synthesis of gold-alloys including goldplatinum and gold
palladium [19], it is expected to be useful for its application to the magnetic iron-
alloy nanoparticles if the synthesis of iron nanoparticles is conveniently achieved. In
addition, the oxidation of iron nanoparticles has been reported to bring about the
formation of monodisperse iron-oxide nanoparticles [2022]. Magnetic nanoparti-
cles can be used for many applications, including magnetic recording media,
catalysis, MRI contrast enhancement, drug delivery and hyperthermia [23, 24].
Hyperthermia is a promising form of cancer therapy that locally heats tissue to
greater than 42 C for to destroy tissue, particularly tumors. The difculty of this
therapy lies in selectively heating cancer tumors [23]. By localizing magnetic
nanoparticles to the desired area and applying an alternating magnetic eld (AMF),
the particles can generate heat by hysteresis loss, thus killing cancer cells with
minimal injury to normal tissues. Highly hysteretic particles are desirable because
they will give off the most heat with the lowest dose to a patient. Iron, which has a
very high magnetic saturation value (220 emu/g), is ideal for hyperthermia
application [23, 24].
The preparation methods inuence the properties of nanoscale iron particles.
Mostly chemical and physical methods are used to generate iron nanoparticles in the
form of colloids as well as powders. From the preparation point of view, one of the
important subjects in the study of magnetic nanoparticles is the preparation of stable
588 H. Karami, O. Rostami-Ostadkalayeh
1 3
nanoparticles with novel properties. In the present study we report a simple way to
synthesis iron nanoclusters. Iron nanoclusters were electrodeposited by applying a
pulsed current technique from an iron salt acidic solution containing sulfuric acid.
The synthesized samples were characterized by relative gravimetrical density
(RGD), scanning electron microscopy (SEM), X-ray diffraction (XRD) and
determination of magnetic momentum.
Experiment
Materials
All materials and reagents used in these experiments were of reagent grade and were
produced in the Loba Chemie Co. (India). Double-distilled water was used in all the
experiments.
Instrumentals
A power source of the MPS-3010L model, made by the Taiwan Matrix Company
was used for producing the constant current. A home-made electrical pulse
apparatus was applied to make the reproducible current pulses. Figure 1 shows the
used laboratory systems, including the power supply, pulse apparatus, and
electrochemical cell. The solution temperature was kept constant with usage of a
water bath (Optima, Tokyo, Japan).
A scanning electron microscope with EDX instrument from Philips Co. (XL30)
was used for studying of morphology, particle size and surface analysis of the
prepared iron nanopowders. X-ray diffraction (XRD) studies were performed by a
Fig. 1 Laboratory system used to synthesis the lead dioxide nanoparticles, including power supply, pulse
maker apparatus, and electrochemical cell
Synthesis of Iron Nanoclusters by Pulsed Current Method 589
1 3
Decker D8 instrument. Bulk analysis of the sample was performed by inductively
coupled plasma atomic emission spectroscopy (ICP-AES) from Varian Co.
Procedure
Reagent grade iron sulfate (FeSO
4
) was used as the precursor and, silver nitrate
(AgNO
3
) was chosen as the source of Ag as a nucleation agent for iron synthesis. The
appropriate amounts of iron sulfate (0.005 M) and AgNO
3
(at 0.5% mole of iron in
the starting solution) were rst dissolved in low acidic water (pH = 5), which was
then heated to the desired temperature for the reaction. The obtained solution was
used in the electrochemical synthesis cell with two stainless steel (316L) electrodes as
anodes and one stainless steel (316L) as a cathode. In theses cases, the precipitate was
separated from the solution, washed with water and ethanol, and dried at room
temperature in inert atmosphere. After milling, RGD of the obtained powder was
determined by a simple gravimetrical method. For this concept; a glass vessel was
made with constant volume (0.5 cm
3
); the powder sample was pressed into this vessel
under constant pressure (1.0 bar). RGD was calculated from powder weight and
vessel volume. The morphology, dimension size, and structure of iron nanoparticles
were studied by scanning electron microscopy and XRD. The magnetic saturation and
coercivity of the nanoparticles were determined by examining the hysteresis loop
produced by the vibrating sample magnetometer (VSM).
At this method, there are effective parameters which include pulse amplitude
(current amount or pulse height), pulse frequency, iron salt concentration, solution
pH, and temperature of synthesis solution which were optimized by the one at a time
method.
Results and Discussion
In this procedure, a pulse current is exerted on the electrochemical solution
containing a stainless steel (316L) cathode and two stainless steel (316L) anodes by
the electrical pulse instrumentation. Experimental observations showed that the
synthesized iron nanoclusters do not stick to the electrode surface in this method. The
synthesized particles immediately leave the electrode surface. Therefore, electrode
surface is not completely covered by the synthesized particles. In this method, there
are some effective parameters which include, pulse amplitude (current amount or
pulse height), pulse frequency, iron salt concentration, solution pH, and temperature
of synthesis solution which were optimized by the one at a time method.
Before optimizing of pulse parameters, the effect of pH was studied. Initial
studies showed that the pH range of 2.83.8 is suitable for iron synthesis by this
method.
Determination of RGD
Our initial studies showed that RGD can be used as an easy and cheep optimizing
parameter when phase composition is constant. For this propose, many iron powder
590 H. Karami, O. Rostami-Ostadkalayeh
1 3
samples with different porosity were synthesized and then, their porosity were
determined by mercury adsorption method and then, RGD of all samples were
determined by the proposed method. Figure 2 shows the experimental correlation
between RGD and porosity of iron powder. The presented results show good
correlation between RGD and porosity so that, RGD can be used as an optimizing
parameter to obtain a more porous powder.
Pulse Frequency Optimization
In the pulsed current method, the current vs. time was applied as shown in Fig. 3. As
it can be seen in Fig. 3, the used current pulse has four variable parameters: pulse
0.7
0.9
1.1
1.3
1.5
1.7
1.9
2.1
30 40 50 60 70 80 90 100 110 120 130 140 150
Porosity (m
2
.g
-1
)
R
G
D

(
g
.
c
m
2
-
)
Fig. 2 Correlation between RGD and porosity of iron powder
Fig. 3 Used pulse diagram, including pulse time, relaxation time, and pulse height
Synthesis of Iron Nanoclusters by Pulsed Current Method 591
1 3
height (current amplitude), pulse time, relaxation time, and pulse frequency. Our
initial studies show that the relaxation time/pulse time ratio of three is suitable and
optimum to obtain a suitable synthesis, thus the ratio of three was selected for later
studies. At constant ratio of relaxation time to pulse time, a pulse system has three
variable parameters: pulse height, pulse time, and pulse frequency. The effect of all
effective parameters was optimized by the one at a time method.
Our initial studies showed that the pulse current method is more effective than
the simple constant voltage and simple constant current methods. The pulsed current
electrochemical method can be used as a condent and controllable method for the
production of nanoparticles. Each current pulse contains an on time (pulse time)
and an off time (relaxation time), so that the pulse frequency can be related to the
sum of current pulses which can be applied in to the system at one unit of time. At
constant ratio of relaxation time/pulse time (which is equal to 3), any variation in
pulse frequency makes a new pulse and relaxation time.
In order to investigate the effect of pulse frequency on particle size, the pulse
frequency was varied from 0 to 18 Hz. The SEM results showed that at a frequency
of 14 Hz, the synthesized iron nanopowder is more uniform, it has smaller particles
and more porous, exceptional nanostructures. Figure 4 shows the effect of pulse
frequency on the relative gravimetrical density (RGD) of yield powder. As it was
shown in Fig. 4, RGD is decreased when the pulse frequency increased from 0 to
14 Hz. Applying the synthesis current in pulse form decreases the nuclear growth,
thus the uniform and more porous powder with low RGD is synthesized. At higher
pulse frequencies (more than 14 Hz), the relaxation time between two successive
pulses is very short so that the new synthesis cycle (according to the new pulse)
starts before the nishing of the previous synthesis cycle (according to the previous
pulse). It should be mentioned that the nuclear growth has little hindrance time with
respect to pulse time (reduction of iron ion). At lower frequencies, the nuclear
growth kinetic is faster than the nuclear production. For the pulse frequency of
14 Hz, the on and off durations were 18 and 54 ms, respectively. All samples
of frequency optimizing experiments also studied with SEM. The obtained results
by SEM were conrmed those of RGD experiments. Figure 5 shows the SEM image
Fig. 4 Effect of the pulse frequency on relative gravimetrical density (RGD) of iron nanoparticles
592 H. Karami, O. Rostami-Ostadkalayeh
1 3
of the sample which synthesized at pulse frequency of 14 Hz. The sample has a
more porous structure in nanometric scale.
Optimization of Pulsed Current Amplitude
In order to investigate the effect of pulse current amplitude (pulse height) on the
RGD, morphology and particle size, the pulse height varied from 10 to 70 mA/cm
2
was exerted on the electrochemical solution while the other parameters were kept
constant. Figure 6 shows the effect of pulse height (current density) on the relative
Fig. 5 SEM image of the sample which synthesized at pulse frequency of 14 Hz
Fig. 6 Effect of pulse height on the relative gravimetrical density (RGD) of yield powder
Synthesis of Iron Nanoclusters by Pulsed Current Method 593
1 3
gravimetrical density (RGD) of yield powder. As it was shown in Fig. 6, RGD is
increased when the pulse height increased from 20 to 70 mA cm
-2
. This result can
be related to this fact that in the electrochemical pulse system, particle growth and
agglomeration rates increases making the pulse height increase, which therefore
causes a decrease in that porosity and consequently an increase in RGD. The
obtained results showed that the current density (pulse height) of 20 mA cm
-2
and
or lower cause to more porous structure and smaller and more uniform structures.
Use of lower current density not only makes to increase the experiment time but
also, makes no considerably improvement in the structure so that the amount of
20 mA cm
-2
was select as optimum pulse height. Figure 7 shows the SEM image
of the sample with porous and uniform structure which synthesized under optimum
current density.
Temperature Optimization
For investigation of the synthesis temperature effect on the morphology and
particle size of iron nanopowder, ve synthesizes were carried out at temperatures
of 0, 30, 50, 75 and 95 C. RGD and SEM studies showed that samples
synthesized at higher temperature have uniform nanoparticles with smaller
diameters. Therefore, temperature of 95 C was chosen as an optimum temperature
for further studies. All samples which synthesized at different temperatures were
studied by XRD. XRD results showed that the temperature has not any effect on
the composition of samples. All analyzed sample at these series of experiments had
only a-Fe form.
Fig. 7 SEM image of iron nanopowder which were synthesized at current density of 20 mA cm
-2
594 H. Karami, O. Rostami-Ostadkalayeh
1 3
Optimization of the Initial Iron Sulfate Concentration
The effect of the initial iron sulfate concentration on the RGD, particle size and
morphology of iron nanopowder was investigated by varying the iron salt
concentration from 0.005 to 0.1 M. RGD and SEM studies showed that the lower
concentrations of iron salts create a uniform structure and the smallest particle size
for the nal iron nanopowder. As the initial concentration of iron sulfate in the
synthesis solution decreases from 0.1 to 0.005 M, the average particle size of iron
nanopowder also decreases from 150 nm to 40 nm. The obtained results can
probably be related to the reduction of particle growth and the agglomeration rate at
lower concentrations. At initial iron sulfate concentrations which are lower than
0.005 M, the amount of iron nanoparticles precipitation is very low, thus it can not
be ltered and collected. Therefore, the initial concentration of 0.005 M was
selected for the optimization of other parameters.
Optimized Iron Nanoclusters
The excellent uniform nanoclusters of iron in nanopowder form can be synthesized
at the optimum conditions as followings:
(1) Pulse frequency of 14 Hz
(2) Pulse height (current amplitude) of 20 mA cm
-2
(3) Synthesis solution temperature of 95 C
(4) Initial iron ion concentration of 0.005 M in sulfate salt form
When a synthesis is carried out under the above-mentioned conditions, iron
nanoclusters can be obtained in powder form. Figure 8 shows the nal SEM
images of the obtained iron powder samples for the optimization of the effective
parameters (See Determination of RGD, Pulse Frequency Optimization, Optimi-
zation of Pulsed Current Amplitude and Temperature Optimization sections). In
Fig. 8, for each effective parameter (pulse frequency, pulse height, temperature,
and initial concentration of iron ion) the nal SEM image of the sample which
synthesized in the optimum value of the proposed parameter has been presented.
As observed in Fig. 8, in the duration of the optimization steps, the morphology
and particle size of the synthesized iron change from agglomerated particles to
perfect uniform nanoclusters. For more clarication, TEM images of the
optimized sample were shown in Fig. 9. As it can be seen in Fig. 8e and
Fig. 9, the sample synthesized at optimum conditions has excellent uniform
nanoclusters. Figure 10 shows the particle size distribution in the optimum
condition. Based the obtained results, major of the synthesized iron nanoparticles
was 20 to 40 nm in diameter.
For the determination of sample purity, the optimum sample was analyzed by
EDX, XRD and ICP-AES. EDX peaks and XRD patterns for the optimum iron
nanoclusters were shown in Fig. 11. As it is obvious in Fig. 11, the sample is very
pure and the EDX and XRD could not detect any impurity in the sample. It should
be mentioned that the EDX and XRD can be used only for surface analysis, but
Synthesis of Iron Nanoclusters by Pulsed Current Method 595
1 3
ICP-AES can reveals bulk analysis with more precision. EDX and ICP-AES
analysis showed that the Silver content of each sample is very small and negligible
(lower than 0.01 %wt). Silver is a starting agent for iron crystallization so that, iron
synthesis in the absence of silver ion is very slow. The silver impurity was not
detected by XRD and EDX, because there is this element only in the center of each
iron nanoparticle.
Fig. 8 Final SEM images (with magnication of 150009) of the obtained iron nanopowder at the
different optimization steps: a optimized pulse frequency, b optimized current amplitude, c optimized
solution temperature, d optimized initial concentration of iron salt, and e sample synthesized in the
optimum conditions with magnication of 300009
596 H. Karami, O. Rostami-Ostadkalayeh
1 3
Magnetization Studies
The present study focuses on the magnetic properties of these novel iron
nanoclusters. Figure 12 shows the magnetization measurements of iron nanoclusters
and bulk iron. The measurements were performed on powder samples. It is observed
that the saturation magnetization is about 110 and 100 emu/g for iron nanoclusters
and bulk iron powders, respectively. The obtained result showed that the
synthesized iron nanoclusters exhibit saturation magnetization 10% more than bulk
iron.
Fig. 9 TEM images of the iron nanoclusters synthesized in the optimum conditions
Fig. 10 Size distribution histogram for the iron nanoparticles
Synthesis of Iron Nanoclusters by Pulsed Current Method 597
1 3
Conclusion
The experimental results indicate which pulse current electrochemical method can
be used as a condent and controllable method for the preparation of iron
nanoclusters. When a synthesis is carried out under a pulse frequency of 14 Hz, a
pulse height (current amplitude) of 20 mA cm
-2
, a synthesis solution temperature
of 95 C, and an initial iron ion concentration of 0.005 M in sulfate salt form, iron
nanopowder can be obtained in the perfect uniform structures in nanocluster form
with an average particle size of 20 to 40 nm.
Fig. 11 EDX and XRD patterns for the iron nanoclusters; all indexed and non-indexed peaks are related
to different atomic lines of Iron
598 H. Karami, O. Rostami-Ostadkalayeh
1 3
Acknowledgments We gratefully acknowledge the support of Abhar Payame Noor University
Research Council, throughout these research experiments.
References
1. G. Schmid Clusters and Colloids, from Theory to Application (VCH, Weinheim, 1994).
2. D. Y. Murzin Nanocatalysis (Research Signpost, Kerala, India, 2006).
3. J. E. Wegrowe, O. Fruchart, J. P. Nozieres, D. Givord, F. Rousseaux, D. Decanini, and J. P. H.
Ansermet (1999). J. Appl. Phys. 86, 1028.
4. J. M. Bonard, S. Seraphin, J. E. Wegrowe, J. Jiao, and A. Chatelain (2001). Chem. Phys. Lett. 343,
251.
5. F. M. Brunsman (1994). J. Appl. Phys. 75, 5882.
6. H. Zeng, J. Li, J. P. Liu, Z. L. Wang, and S. Sun (2002). Nature 420, 395.
7. B. Warne, O. I. Kasyutich, E. L. Mayes, J. A. Wiggins, and K. K. W. Wong (2000). IEEE Trans.
Magn. 36, 3009.
8. C. H. Cunningham, T. Arai, P. C. Yang, M. V. McConnell, J. M. Pauly, and S. M. Conolly (2005).
Magn. Reson. Med. 53, 999.
9. Q. A. Pankhurst, J. Connolly, S. K. Jones, and J. Dobson (2003). J. Phys. D: Appl. Phys. 36, R167.
10. C. Klinke, J. M. Bonard, and K. Kern (2004). J. Phys. Chem. B 108, 11357.
11. K. Hernadi, E. Couteau, P. Umek, C. Miko, J. W. Seo, L. Forro, M. Croci, C. Klinke, P. Chauvin, and
P. J. M. Bonard (2002). Chimia 56, 547.
12. W. X. Zhang (2003). J. Nanopart. Res. 5, 323.
13. X. Batlle and A. Labarta (2002). J. Phys. D: Appl. Phys. 35, R15.
14. E. V. Shevchenko, D. V. Talapin, H. Schnablegger, A. Kornowski, O. Festin, P. Svedlindh, M. Haase,
and H. Weller (2003). J. Am. Chem. Soc. 125, 9090.
15. P. Ayyub, R. Chandra, P. Taneja, A. K. Sharma, and R. Pinto (2001). Appl. Phys. A 73, 67.
16. H. Zeng, M. Zheng, R. Skomski, D. J. Sellmyer, Y. Liu, L. Menon, and S. Bandyopadhyay (2000).
J. Appl. Phys. 87, 4718.
17. R. P. Cowburn, D. K. Koltsov, A. O. Adeyeye, and M. E. Welland (2000). J. Appl. Phys. 87, 7067.
Fig. 12 Magnetization measurements of iron nanoclusters and bulk iron at different magnetic elds
Synthesis of Iron Nanoclusters by Pulsed Current Method 599
1 3
18. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, and R. Whyman (1994). J. Chem. Soc. Chem.
Commun. 801.
19. M. J. Hostetler, C.-J. Zhong, B. K. H. Yen, J. Anderegg, S. M. Gross, N. D. Evans, M. Porter, and R.
W. Murray (1998). J. Am. Chem. Soc. 120, 9396.
20. T. Hyeon, S. S. Lee, J. Park, Y. Chung, and H. B. Na (2001). J. Am. Chem. Soc. 123, 12798.
21. X. Teng and H. Yang (2004). J. Mater. Chem. 14, 774.
22. T. Nakanishi, H. Iida, and T. Osaka (2003). Chem. Lett. 32, 1166.
23. L. Dale (2005). Huber. Small 5, 482.
24. A. H. Lu, E. L. Salabas, and F. Schuth (2007). Angew. Chem. Int. Ed. 46, 1222.
600 H. Karami, O. Rostami-Ostadkalayeh
1 3