Materials Letters 61 (2007) 2204 – 2207

www.elsevier.com/locate/matlet

Ultrasonic-assisted preparation of monodisperse iron oxide nanoparticles

G.Q. Zhang a , H.P. Wu a,b,⁎, M.Y. Ge b , Q.K. Jiang b , L.Y. Chen b , J.M. Yao a
a
Key Laboratory of Advanced Textile materials and Manufacturing Technology (Zhejiang Sci-Tech University), Ministry of Education,
Hangzhou 310018, P.R. China
b
Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, P.R. China
Received 22 April 2006; accepted 24 August 2006
Available online 12 September 2006

Abstract

Monodisperse iron oxide nanoparticles with 5–20 nm can be synthesized by an inexpensive and simple ultrasonic-assisted method at low
temperature. This is based on the decomposition of iron pentacarbonyl in cis–trans decalin. The high energy emitted by ultrasonic irradiation at a
short time can promote the crystallization process simultaneously. At low temperature, these crystalline nucleuses can grow to monodisperse
nanoparticles. Effects of ultrasonic treatment, the concentration of surfactant and the refluxing time on the size and size distribution of iron oxide
nanoparticles were investigated. The morphology and crystal structure of iron oxide nanoparticles obtained at different conditions were
characterized by high-resolution transmission electron microscope, X-ray diffraction and selected area electron diffraction.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Iron oxide nanoparticles; Ultrasonic; Monodisperse; Magnetic materials

1. Introduction 1 MHz, has been widely used in chemical synthesis because it

The synthesis of nanoparticles with controlled size and
composition is of fundamental and technological interest. The
synthesis of monodisperse nanocrystals (size variation b 5%) is
of key importance, because the properties of these nanocrystals
depend strongly on their dimensions [1–3]. For example, the
semiconductor nanocrystals showing size-tunable optical prop-
erties have been integrated into exploratory optical and elec-
tronic devices [3–6]. The study of nanoscale magnetic materials
domains is of both fundamental and pressing technical interest
as the grain size of advanced recording media is rapidly
shrinking to dimensions where magnetic properties depend
strongly on nanocrystal size [7–10]. In recent years, various
synthetic methods have been reported to prepare monodisperse
magnetic nanomaterials, including Fe [11,12], Co [13,14], γ-
Fe2O3 [15,16], Fe3O4 [17] and ferrimagnetism [17]. Since the
1980s, ultrasound, in the frequency range from 20 kHz to
leads to an increase in the rate of many chemical reactions:
organic, inorganic, organic composite, etc [18]. The value of
ultrasonic irradiation to organic chemists lies in its ability not
only to accelerate known reactions, particularly those that are
heterogeneous in the solvent systems of interest, but also in its
ability to generate new chemistry that is not available using
existing methodologies because an ultrasonic wave can gene-
rate a very extreme reaction environment as it passes through a
liquid [19]. Many research groups have used ultrasound in the
synthesis of polymers and composites, and have obtained
striking results [20,21]. In the present work, we found that
ultrasonic irradiation could greatly enhance the crystallization
of iron oxide nucleus at 190 °C, after the react solution was
refluxed at this temperature, monodisperse γ-Fe2O3 nanocrys-
tals could be obtained.
2. Experimental

⁎ Corresponding author. Laboratory of New-Structured Materials, Department

of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027,
P.R. China. Tel.: +86 571 87953705; fax: +86 571 87951404.
E-mail address: ludwig@zju.edu.cn (H.P. Wu).
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.08.051
In a typical experiment, 15 ml cis–trans decalin and 2.2 ml
oleic acid were mixed in a three-neck round-bottomed flask and
heated to 100 °C at a rate of 5 °C/min, then 0.3 ml iron
pentacarbonyl (Fe(CO)5) was added into the flask quickly. The
 G.Q. Zhang et al. / Materials Letters 61 (2007) 2204–2207 2205

mixture solution was heated at a rate 2 °C/min under an argon

flow, when the temperature reached 190 °C, a probe equipped
on a high-intensity ultrasonic horn (Branson 184 V, 20 kHz,
900 W) was dipped into the solution, ultrasonic irradiation time
was 10 min. The mixture was then refluxed at 190 °C for 30–
90 min under mechanic stirring and argon atmosphere. After
reaction, the solution was placed in air for 12 h, iron oxide
nanoparticles were precipitated by adding ethanol to the re-
action solution. The supernatant was discarded after centrifu-
gation. The precipitate was redispersed in 10 ml hexane with a
few drops of oleic acid. The molar ratio of oleic acid to Fe(CO)5
was changed from 1:1 to 6:1 by increasing oleic acid from
2.2 ml to 13.2 ml in the reaction solution.
Transmission electron microscopy (TEM JEOL-2010)
samples were prepared by dipping the dispersion onto a carbon
coated copper grid. X-ray powder diffraction (XRD) measure-
ments were performed using a Rigaku D/MAX-2550PC X-ray
powder diffractometer with Bragg–Brentano geometry using
Cu Kα irradiation in the range of 25–70°, a step of 0.02° and 2 s
per step. Fourier transform infrared (FTIR) measurements were
carried out with a resolution of 2 cm− 1 and 32 scans.

3. Results and discussions

Iron oxide nanoparticles were prepared by ultrasonic-assisted

method as shown in Fig. 1a. These monodisperse nanoparticles have
an average grain size of 9.6 ± 0.2 nm. Grain size distribution was
estimated by counting about 300 nanoparticles and characterized by a
log-normal function (solid line) (Fig. 1d). SAED pattern of iron oxide
nanoparticles in Fig. 1b is indexed by a cubic γ-Fe2O3 (PCPDF
#872334), the diffraction rings are attributed to the (220), (311), (400),
(422), (511) and (440) planes, respectively. The high-resolution TEM
image in Fig. 1c shows the internal crystallinity for an iron oxide
nanocrystal. The particle appears to be a single crystal and exhibits a
0.24 nm d-spacing for the (311) reflection. The surface of iron oxide
nanoparticles was wrapped by oleic acid, which can be detected from
the FTIR pattern in Fig. 1e. The pattern was obtained from the sample
as shown in Fig. 1a. The peaks that appear at 1565–1487 cm− 1 are
attributed to the characteristic absorption of the –COO– group on the
surface of iron oxide nanoparticles. The effects of surfactants and their
concentrations, ultrasonic irradiation and refluxing time on the size and
size distribution of iron oxide nanoparticles were studied
systematically.
Fig. 1. Iron oxide nanoparticles prepared by ultrasonic-assisted method, the
molar ratio of oleic acid to Fe(CO)5 is 3:1, ultrasonic irradiation time is 10 min,
refluxing time is 30 min. (a) Low magnification TEM image of monodisperse
iron oxide nanoparticles. (b) SAED pattern of iron oxide shown in (a), the
diffraction rings are attributed to the (220), (311), (400), (422), (511) and (440)
planes, respectively. (c) High-resolution TEM image of a single iron oxide
nanoparticle, the d-spacing is 0.24 nm corresponding to the (311) fringes of
cubic γ-Fe2O3. (d) Size distribution of iron oxide nanoparticles obtained from
counting 300 nanoparticles. (e) FTIR pattern of iron oxide nanoparticles shown
in (a).
particles. Keeping on increasing the concentration of oleic acid in the
solution, monodisperse iron oxide particles with smaller size are
obtained, as shown in Fig. 2c, which can be explained that higher
concentration of surfactant can wrap iron oxide particles and can
prevent the growth of nanoparticles more easily.

3.1. Effect of surfactant concentration on size and size distribution of
iron oxide nanoparticles
The concentration of surfactant has a drastic effect on the size
distribution of iron oxide nanoparticles in this work as shown in Fig. 2.
The obtained iron oxide nanoparticles in Fig. 2a, b and c correspond to
the molar ratio (oleic acid to Fe(CO)5) of 1:1, 3:1 and 6:1, respectively.
The average sizes are 9.5 ± 1.2 nm, 9.6 ± 0.2 nm and 5.4 ± 0.1 nm,
respectively. We find that higher concentration of oleic acid can get
smaller size and narrower size distribution of iron oxide nanoparticles
as reported in Ref. [9]. When the molar ratio is 1:1, only polydispersed
nanoparticles can be observed, which suggests that, at low concentra-
tion, oleic acid is ineffective at stabilizing the iron oxide particles.
When the ratio reaches 3:1, monodisperse nanoparticles are obtained as
shown in Fig. 2b, but the size is not smaller than that obtained at 1:1,
the reason is that the size is an average statistic value from 300
3.2. Effect of refluxing time on iron oxide nanoparticles
Fig. 3 shows TEM images of iron oxide nanoparticles obtained with
oleic acid:Fe(CO)5 ratio of 3:1 at 190 °C for a refluxing time that varies
from 30, 60 and 90 min. The average sizes of iron oxide nanoparticles
are 10, 15 and 20 nm, which correspond with XRD patterns (Fig. 3d).
The diffraction peaks are attributed to the (220), (311), (400), (422),
(511) and (440) planes of cubic γ-Fe2O3, the smaller the size of the
nanoparticles, the broader of the peaks. It appears that the larger
nanoparticles have relatively higher crystallinity.
3.3. Effect of ultrasonic irradiation on iron oxide nanoparticles
Many researchers have investigated the effect of ultrasound on
chemical reactions and have suggested some proposed explanations,
such as the “hot spot” explanation [18], the “electrical explanation”
2206 G.Q. Zhang et al. / Materials Letters 61 (2007) 2204–2207

Fig. 2. TEM images of iron oxide nanocrystals obtained from different concentrations of oleic acid. From (a) to (c) the molar ratio of oleic acid to Fe(CO)5 is 1:1, 3:1
and 6:1, respectively. The ultrasonic irradiation time is 10 min, refluxing time is 30 min.

[22], and a proposed model based on plasma discharge [23]. Most
theories imply that the harsh conditions generated upon bubble collapse
lead to the formation of free radicals, mechanical shocks, high shear
gradients, and very rapid and efficient mixing in multiphase systems.
When an ultrasonic wave passes through a liquid medium, a large
number of microbubbles form, grow, and collapse in the very short time
of a few microseconds, an effect that is called ultrasonic cavitation.
Sonochemical theory calculations and the corresponding experiments
suggest that ultrasonic cavitation can generate local temperatures as
high as 5000 K and local pressures as high as 100 MPa, with heating
and cooling rates greater than 109 K/s, which is a very extreme
environment [18]. This considerably changes the physicochemical
parameters of the processed medium. Thus, we believe that acoustic
cavitation holds much promise for controlled change in the
microstructure of powders obtained under solvothermal conditions.
Ultrasonic irradiation has been successfully used to promote the
crystallization of many metal oxide nanocrystals in solution [24–26].
Fig. 4 shows TEM images for iron oxide prepared with and without
ultrasonic irradiation. We can obtain very good crystalline iron oxide
nanocrystals with average grain size of 15.8 ± 0.7 nm and a narrower
size distribution of σ = 4.4% with ultrasonic irradiation (Fig. 4a). Only
amorphous iron oxide colloidal can be obtained without ultrasonic
irradiation as shown in Fig. 4b. In the present work, the process of
nucleation, crystallization and growth was segregated. The nucleation
process occurred at 190 °C when Fe(CO)5 decomposed. The reported
temperature for crystallization of iron oxide nanoparticles is about
220–250 °C [5,6,17], so the crystallization process could not occur at
190 °C. But the solution temperature would increase from 190 °C to
225 °C (even higher in local parts) after ultrasonic irradiation for
10 min. The local high temperature could promote the crystallization of
the iron oxide nucleus. After crystallization, the growth proceeded at
190 °C when the solution was refluxed at this temperature.

Fig. 3. Iron oxide nanoparticles obtained at different refluxing time. From (a) to
(c), TEM images of iron oxide nanoparticles prepared by refluxing in cis–trans
decalin for 30 min, 60 min and 90 min, respectively. (d) is XRD patterns for iron
oxide particles shown in (a) to (c). The molar ratio of oleic acid to Fe(CO)5 is Fig. 4. TEM images of iron oxide obtained under different reaction conditions.
3:1, ultrasonic irradiation time is 10 min. With (a) and without (b) ultrasonic irradiation.
 G.Q. Zhang et al. / Materials Letters 61 (2007) 2204–2207
4. Conclusions
In conclusion, we report here a simple and inexpensive
method to synthesize monodisperse iron oxide nanoparticles of
5–20 nm by ultrasonic-assisted method at low temperature. This
is based on the decomposition of iron pentacarbonyl in cis–trans
decalin. The high energy emitted by ultrasonic in a short time
could promote the crystallization process simultaneously. Then at
relatively lower temperature, these nucleuses could grow to
monodisperse nanoparticles. With increasing surfactant concen-
tration, monodisperse iron oxide nanoparticles with narrower size
distribution could be obtained. The average diameter of iron
oxide nanoparticles was affected by refluxing time.
Acknowledgments
The authors would like to thank the financial support from
the National Natural Science Foundation of China (Grant No.
20404011) and the Key Laboratory of Advanced Textile
Materials and Manufacturing Technology (Zhejiang Sci-Tech
University), Ministry of Education.
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