Materials Letters 67 (2012) 358–361

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Fe3O4 nanoparticles: Microwave-assisted Synthesis and Mechanism

Zhenlong Liu 1, Fei Miao 1, Wei Hua ⁎, Feng Zhao
School of Electronics and Information Engineering, Sichuan University, Chengdu, 610064, China

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

Article history: The chemical mechanism for the microwave-assisted formation of Fe3O4 was clarified in present work. Micro-
Received 4 July 2011 wave irradiation supplied sufficient energy for the formation of Fe3O4 because of its uneven distribution within
Accepted 24 September 2011 the raw materials, as determined via the comparative heating experiment and numerical analysis (finite ele-
Available online 1 October 2011
ment method). Quantitative analysis and oil (dimethyl silicone fluid) bath comparative experiment revealed
that H2O supplied an appropriate reaction environment. The Fe/Fe2O3 stoichiometric ratio in the synthetic reac-
Keywords:
Magnetic materials
tion was 1:4, as determined via quantitative analysis and in accordance with the electronic conservation theory.
Nanoparticles Therefore, the mechanism for the microwave-assisted formation of Fe3O4 is Fe+ 4Fe2O3 → 3Fe3O4.
Microwave method © 2011 Elsevier B.V. All rights reserved.
Finite element method

1. Introduction 2. Experimental

Magnetite (Fe3O4), which has a cubic inverse spinel structure, has 2.1. Materials
attracted considerable attention because of its unique properties [1]
and wide applications in biotechnology, medicine, and microwave ab- Two pieces of rusted scrap iron foils (3 cm × 3 cm), analytical
sorption materials [2–4]. With the rapid expansion of its applications, grade Fe powder, and deionized, deoxygenated H2O.
various synthetic techniques such as hydrothermal synthesis [5],
micro-emulsion [6], γ-ray irradiation [7], and co-precipitation [8]
2.2. Experiment
have been developed. Khollam et al. [9] fabricated Fe3O4 nanoparti-
cles via a microwave-hydrothermal reaction of FeSO4 and NaOH.
Two pieces of rusted iron foils were submerged in 500 mL deio-
However, in their report, rigid requirements in equipment and/or
nized deoxygenated H2O. One was irradiated under 2.45 GHz micro-
chemicals must first be satisfied before the synthesis can proceed.
wave radiation in a 700 W transformational household microwave
Furthermore, the chemicals used in the preparation should be desired
oven for 30 min, whereas the other was heated using an alcohol
to be removed from the suspension containing Fe3O4 nanoparticles
blast burner for 30 min, which guaranteed that the mixture's rising
[10].
temperature was basically consistent with that of the microwave ra-
To effectively solve the aforementioned problem, a facile and
diation. The precipitates were then filtered and dried under vacuum
green microwave method without rigid reaction conditions (i.e., alka-
at 45 °C for 2 h. The product from the microwave irradiation was
li, acid, or high temperature) was proposed by Miao et al. [11] to pre-
marked as sample 1 and the other was marked as sample 2. Similarly,
pare Fe3O4 nanoparticles using scrap iron (Fe and Fe2O3) and
Fe powder (5.6 g) was rusted and dried under vacuum at 45 °C for
deionized water. Therefore, understanding the reaction mechanism
12 h to ensure that sample 3 does not contain H2O. The resulting
is essential in designing an environmentally friendly method of nano-
powder was then weighed and treated in the same way as sample 1
material preparation. However, no such studies have been conducted
under N2 protection. Finally, the precipitates (sample 3) were filtered
to date.
and dried under vacuum at 45 °C for 12 h.
The purpose of the current paper is to study the mechanism of a
microwave-assisted synthesis of Fe3O4. The effects of the microwave,
H2O, and the Fe/Fe2O3 molar ratio on the reaction mechanism were 2.3. Characterization
investigated. The particle size, morphology, and magnetization prop-
erties of Fe3O4 were also determined. The samples were weighed using an accurate electronic balance
(JA2103, Shanghai Minqiao Precision Scientific Instrument Co.Ltd.
China) and characterized via X-ray diffraction (XRD, DX-1000)
⁎ Corresponding author. Tel.: + 86 28 85403882; fax: + 86 28 85408779.
E-mail addresses: scu_liuzhenlong@hotmail.com (Z. Liu), boymf123@163.com
under a 40 kV potential and 25 mA current. The morphologies of the
(F. Miao), huaw@scu.edu.cn (W. Hua), mydear_S101853@126.com (F. Zhao). samples were examined via transmission electron microscopy (TEM,
1
These authors contributed equally to this work. JEM-100CX) and scanning electron microscopy (SEM, JSM-5900LV).

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.09.095
 Z. Liu et al. / Materials Letters 67 (2012) 358–361
The magnetic properties were measured on a BHV-55 vibrating sam-
ple magnetometer at room temperature.
3. Results and discussion
XRD pattern (Fig.1(a)) of the purified sample 1 can be indexed to
the face-centered cubic spinel structure of Fe3O4 (JCPDS card no. 75-
0033). No diffraction peaks of any other phases were detected, indi-
cating the high purity of main product. The average crystallite size
of Fe3O4 nanoparticles was 20 nm which was calculated from the
full-width at half-maximum of the Fe3O4 (311) diffraction peak at
2θ = 35.6° using Scherrer's equation.
The morphologies of the Fe3O4 particles amassed with one magnet
and dispersed by ultrasound in ethanol were respectively character-
ized by SEM and TEM (shown in Fig.1(b) and (c)), which revealed
that the Fe3O4 particles exhibited cube-like morphology with the av-
erage crystallite size of 20 nm.
The hysteresis loop (Fig.1(d)) measured at room temperature
shows a superparamagnetic behavior with saturation magnetization,
coercivity values of 51.4 emu/g and 2.21 Oe, respectively. The satura-
tion magnetization of the nanoparticles obtained in the present work
is 51.4 emu/g at room temperature, which is much lower than the
corresponding bulk materials and consistent with that in the litera-
tures [6].
Fig. 1. Characteristics of purified Fe3O4 nanoparticles. (a) XRD pattern of Fe3O4; (b) SEM image of Fe3O4 particles; (c) TEM image of Fe3O4 particles; (d) Magnetic hysteresis curves
measured at room temperature for Fe3O4.
359
Results of the series of experiments show that microwave radia-
tion, H2O, and the Fe/Fe2O3 ratio significantly affected the formation
of Fe3O4. Thus, these parameters were selected for the investigation
of the mechanism of Fe3O4 formation.
3.1. Microwave
Fig. 2(a) and (b) show that the color of sample 1 turned black after
microwave irradiation. However, that of sample 2 remained
unchanged, indicating that no Fe3O4 was generated under conven-
tional heating. The XRD patterns of sample 2 (Fig. 2(b)) also show
no Fe3O4 peaks(Fe2O3 JCPDS card no. 89-0596). Therefore, Fe3O4
was not produced in the reaction system without microwave.
As an indispensable reaction condition, microwave irradiation
produces thermal effects that result from the inverted heat transfer,
inhomogeneities of the microwave field within the raw materials,
and selective absorption of radiation by polar compounds [12].
These effects, in turn, result in higher temperatures in certain zones
within the materials compared with the macroscopic temperature.
The thermal effects can be used efficiently to improve the reaction,
modify the selectivity, or even perform reactions that do not occur
under classical conditions [12]. The finite element method (FEM)
[13] is a powerful numerical analytical tool that analyzes the distribu-
tion of the microwave field. Modeling and FEM results (Fig. 2(c))
show the distinct inhomogeneities of the microwave field within
360 Z. Liu et al. / Materials Letters 67 (2012) 358–361

Fig. 2. (a) XRD pattern of sample 1. Inset: the optical photographs of rust iron foil after microwave irradiation. (b) XRD pattern of sample 2. Inset: the optical photographs of rust
iron foil after conventional heating. (c) Distribution of the microwave field within raw materials. (d) XRD pattern of resultant precipitates using dimethyl silicone fluid.

raw materials. Therefore, microwave was indispensable in the current
reaction system and provided sufficient energy for Fe3O4 formation.
Fe powder was used to synthetize Fe3O4 nanoparticles instead of
iron foils to obtain the accurate mass ratio of the components in the
mixture via XRD. Table 1 summarizes the composition of sample 3
and the weight of each component before and after reaction. Data
are representative of at least five repeat experiments.
3.2. H2O
The difference in the mass of the mixture before and after the reac-
tion was 0.001 g (Table 1). According to the law of conservation of
mass and element, the absence of a significant increase in mass implies
that all the oxygen of Fe3O4 came from Fe2O3 rather than from H2O.
To provide direct proof for the role of H2O in the reaction, a typical
solvent, dimethyl silicone fluid, was used instead of H2O. The synthe-
sis of sample 1 was repeated, and the resultant precipitates were
washed with ethanol and deionized water. Pure Fe3O4 (JCPDS card
no. 75-0033) was acquired, as shown in the XRD pattern in Fig. 2
(d). In addition, a clear arc was observed for the rusted iron foils heat-
ed via microwave without any solvent. Thus, H2O was chosen as the
solvent mainly to prevent the overheating of raw materials as well
as arc generation in a microwave environment. Moreover, H2O may
also have provided an appropriate chemical potential, because the
synthesis of inorganic materials via solvothermal processing requires
substantially lower temperatures than conventional solid-state
methods [14] and H2O may have provided high diffusivity to facilitate
mass transport [15].

Table 1 3.3. Fe/Fe2O3 molar ratio

Summary of the composition of sample 3 and the weight of each component.
The aforementioned discussion suggests that only Fe and Fe2O3 were
Materials Mass (g)
involved in Fe3O4 formation and that the product is purely Fe3O4. In
Before reaction After reaction

Fe 3.990 3.791
Fe2O3 2.299 0
Fe3O4 0 2.499
Mixture 6.289 6.290
Scheme 1. Mechanism of formation of Fe3O4.
 Z. Liu et al. / Materials Letters 67 (2012) 358–361 361

accordance with the electronic conservation theory, a mechanism of for- References

mation of Fe3O4 nanocrystals is proposed for the first time in Scheme 1.
According to Table 1, the amount of Fe, Fe2O3, and Fe3O4 used in
the reaction were 0.199, 2.299, and 2.499 g, respectively. Thus, the
experimental stoichiometric molar ratio in the synthesis of Fe3O4 is
1.000:4.040:3.031, which is in good agreement with that in Scheme 1.
4. Conclusion
Microwave, as a crucial reaction condition, led to higher tempera-
tures in certain zones within the samples because of the inhomogene-
ities of the microwave field, which determined whether the reaction
would occur. H2O provided a relatively stable reaction environment,
which prevented the overheating of raw materials as well as arc gen-
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reaction was determined as 1:4. These results suggest that the mech-
anism for the microwave-assisted formation of Fe3O4 nanocrystals is
Fe + 4Fe2O3 → 3Fe3O4.
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