Colloids and Surfaces A: Physicochem. Eng.

Aspects 336 (2009) 130–134

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Facile synthesis of magnetic iron oxide nanoparticles using

1-methyl-2-pyrrolidone as a functional solvent
Chen Qin a , Chen Li a , Yizhe Hu a , Jianfeng Shen a , Mingxin Ye a,b,∗
a
Department of Materials Science, Fudan University, Shanghai 200433, PR China
b
The Key Laboratory of Molecular Engineering of Polymer, Ministry of Education, China

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

Article history: Magnetic nanoparticles were generated by thermal decomposition of ferric triacetylacetonate in the
Received 26 September 2008 presence of 1-methyl-2-pyrrolidone, a functional solvent. The particle size and shape could be varied
Received in revised form by altering reaction parameters. For example, with the addition of oleic acid surfactant, smaller parti-
10 November 2008
cles were produced. In addition, step elevation of reaction temperature was in favor of regular particle
Accepted 17 November 2008
morphology. The obtained iron oxide nanoparticles were characterized by X-ray diffraction, transmission
Available online 28 November 2008
electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis and vibrating
sample magnetometer. All of the experimental evidences supported that we succeeded in synthesizing
Keywords:
Facile
monodisperse iron oxide nanoparticles via a facile and effective route. Moreover, when the oleic acid was
Synthesis added, 1-methyl-2-pyrrolidone and oleic acid possibly forms an intercalated monolayer on the particle
Iron oxide nanoparticles surface.
Functional solvent © 2008 Elsevier B.V. All rights reserved.

1. Introduction nanoparticles obtained by above-mentioned approaches may be

Magnetic nanoparticles have been among the appealing
research topics of nanoscience due to their unique properties and
potential applications [1–4]. Although there are several kinds of
interesting magnetic nanoparticles, iron oxide particles – mag-
netite (Fe3 O4 ) and its oxidized form maghemite (␥-Fe2 O3 ) – have
attracted more attention because they are non-toxic and less sus-
ceptible to changes due to oxidation. These facts make this kind
of nanoparticles one of the most studied materials for biomedical
applications.
For all applications, synthetic techniques providing precise con-
trol over nanocrystal grain size are crucial in that they permit
engineering of the magnetic properties. The classical synthetic
techniques of iron oxide nanoparticles have relied on the copre-
cipitation of Fe2+ and Fe3+ ions by a base. The disadvantage of these
aqueous solution syntheses is that the pH value of the reaction
mixture has to be adjusted in both the synthesis and purification
steps, and the process toward monodisperse nanoparticles smaller
than 20 nm has only very limited success [5]. Other techniques such
as microemulsion, ultra sound irradiation and laser pyrolysis, have
been developed for producing iron oxide nanoparticles. However,
∗ Corresponding author at: Department of Materials Science, Fudan University,
No. 220, Hadan Road, Shanghai 200433, China. Tel.: +86 21 55664095;
fax: +86 21 65642622.
E-mail address: mxye@fudan.edu.cn (M. Ye).
poorly crystalline and the size uniformity is hard to control [6]. In
recent years, an alternative method based on the thermal decom-
position of organic iron precursors has been demonstrated to be
very successful in the preparation of iron oxide nanoparticles with
controllable size and high quality. Rockenberger’ group published
a study of ␥-Fe2 O3 nanocrystals prepared by thermal decompo-
sition of pentacarbonyliron [Fe(CO)5 ] in hot surfactants [7]. Sun
and co-workers reported that the thermolysis of ferric triacety-
lacetonate [Fe(acac)3 ] can make monodisperse Fe3 O4 nanoparticles
[8]. Some other research groups demonstrated that FeCup3 [Cup:
C6 H5 N(NO)O− ] could be used as a starting material to form ␥-Fe2 O3
nanoparticles [9–11].
Rather than adopting commonly used nonpolar high-boiling-
point solvents, we have focused our study on 1-methyl-2-
pyrrolidone which can serve as a coordinating solvent in addition
to a high-temperature reaction medium. Moreover, comparing to
different ethers in many cases, 1-methyl-2-pyrrolidone has no per-
oxide formation and is less dangerous. In this work, we report
a one-pot synthesis of monodisperse iron oxide nanoparticles by
thermal decomposition of Fe(acac)3 in the presence of 1-methyl-2-
pyrrolidone. Oleic acid (OA) was added as a competitive surfactant
to find its influence. The heating procedures were also changed
to examine how the temperature affected the formation of mag-
netic nanoparticles. We characterized the products in term of their
magnetic properties, their particle morphology, surfactant coverage
and interaction at the particle surface by vibrating sample mag-
netometer (VSM), X-ray diffraction (XRD), transmission electron

0927-7757/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2008.11.040
 C. Qin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 130–134 131

Table 1
Magnetic nanoparticles synthesized via different processes.

Sample Mass of Fe(acac)3 (g) Mass of OA (g) Total volume of 1-methyl-2-pyrrolidone (ml) Temperature

MN1 1.41 0 50 194 ◦ C, 1 h

MN2 1.41 3.39 50 194 ◦ C, 1 h
MN3 1.41 3.39 50 194 ◦ C, 0.5 h; 204 ◦ C, 1 h

microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy

and thermogravimetric analysis (TGA). With the experimental evi-
dence, our data suggest that the nanoparticles are monodisperse
and the synthetic route does not require a size-selection procedure.
We believe that these well-organized self-assemblies will allow fur-
ther applications in many technological fields such as high area
density data storage.

2. Experimental

In the following, a typical synthesis yielding iron oxide

nanocrystals is described. 30 ml purified 1-methyl-2-pyrrolidone
containing 3.39 g oleic acid was heated to 194 ◦ C. 1.41 g Fe(acac)3
was dissolved in 20 ml purified 1-methyl-2-pyrrolidone and added
dropwise into the 1-methyl-2-pyrrolidone/OA solution under vig-
orous stirring. The process of dropping was completed in 5 min and
the stirring was continued for another 1 h. The whole process was
carried out under a nitrogen atmosphere. During this thermolysis
process, the initial deep red-brown color of the solution changed
to dark brown. After cooled to room temperature, the mixture was Fig. 1. X-ray diffraction patterns of samples with different molar ratios of OA to
Fe(acac)3 : (A) MN1 = 0:1; (B) MN2 = 3:1; (C) MN3 = 3:1 with an additional heating
treated with a 3-fold volume excess of ethanol under air to yield a procedure.
black precipitate, which could be collected either by centrifugation.
The resulting black powder was washed several times by acetone Table 2
and dried in a vacuum oven at 60 ◦ C overnight. For comparison the Comparison of d-spacing values of the synthesized iron oxide nanocrystals with
synthesis was carried out by the similar preparation processes but standard JCPDS Fe3 O4 and ␥-Fe2 O3 data.
with different parameters, such as the addition of oleic acid and
hkl Fe3 O4 MN1 MN2 MN3 ␥-Fe2 O3
the heating procedure, to examine their roles critical to the size-
and shape-guiding processes. Three different samples, labeled MN1, 220 2.967 2.972 2.946 2.967 2.953
311 2.532 2.523 2.527 2.531 2.518
MN2 and MN3, were listed in Table 1. 400 2.099 2.092 2.095 2.092 2.089
Crystal structure information was obtained using a Rigaku 422 1.715 1.696 1.703 1.710 1.705
D/max-␥B X-ray diffract meter with Cu K␣ radiation ( = 1.54056 Å) 511 1.616 1.608 1.612 1.610 1.607
at a scanning rate of 0.02◦ s−1 in the 2 ranging from 25◦ to 75◦ , 440 1.485 1.484 1.478 1.481 1.476
while the morphology of samples was observed by TEM using a
JEOL 2010F. FTIR Spectroscopy data were collected on a NEXUS 670
of these particles, easily oxidized to ␥-Fe2 O3 by the atmospheric O2
spectrometer. At room temperature, the spectra were recorded by
during the washing and drying processes.
signal averaging of 32 scans at a resolution of 2 cm−1 in the range
The crystal domain sizes of magnetic nanocrystals could be cal-
of 4000–500 cm−1 . TGA was conducted with Netzsch TG 209 that
culated from line broadenings by the Scherrer’s formula [12]:
was fitted to a nitrogen purge gas from 30 ◦ C to 600 ◦ C at 10 ◦ C/min
heating rate. Magnetic measurement was operated in air at room 0.89
D≈ (1)
temperature by using a home-made VSM. ˇ cos 
where  is the wavelength (0.154056 nm),  is the diffraction angle,
3. Results and discussion ˇ is the full width at half maximum intensity of the peak and D is
the particle size. The particle size yielding from the above equation
3.1. Composition and microstructure of the thermolysis products in the (3 1 1) reflection was listed in Table 3. By the current synthetic
approach, the particle size and shape would be varied by altering
Both XRD and TEM measurements were performed to obtain different reaction parameters. When there was no addition of OA,
structure information of the resulting magnetic nanoparticles. Fig. 1 larger particle size calculated from the statistical results shown in
shows XRD patterns of nanoparticles synthesized from reaction Fig. 2A was about 16.8 nm with a standard deviation of 1.6 nm. The
mixtures. The positions were assigned to the (2 2 0), (3 1 1), (4 0 0), average size was in close agreement with the value estimated by
(4 2 2), (5 1 1) and (4 4 0) reflections of the inverse spinel structure
of ␥-Fe2 O3 (JCPDS no. 39-1346). However, d-spacing values of all
Table 3
diffraction peaks in Fig. 1 are well consistent with data from the The size of magnetic nanocrystals calculated by Scherrer’s formula.
JCPDS no. 19-0629 for Fe3 O4 (see Table 2). It should be noted that
the standard XRD patterns of ␥-Fe2 O3 and Fe3 O4 are alike. There- Sample  ˇ (rad) D311 (nm)

fore, we concluded that these samples were mixture of ␥-Fe2 O3 MN1 17.78 ◦
0.0086 16.7
and Fe3 O4 , possibly Fe3 O4 in the core and ␥-Fe2 O3 on the surface. In MN2 17.80◦ 0.0152 9.5
MN3 17.72◦ 0.0140 10.3
other words, the initial synthesized Fe3 O4 , especially on the surface
132 C. Qin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 130–134

Fig. 2. TEM images of (A) MN1, (B) MN2, and (C) MN3. The inserted pictures are corresponding particle size histograms.

Scherrer’s formula. It is indicated that each individual particle is

nearly a single crystal. Once the OA surfactant was added, smaller
particles (9.2 ± 2.1 nm) were produced (Fig. 2B), which could be
ascribed to that when the OA surfactant was adsorbed on the iron
oxide particles, the number of accessible sites for further crystal
growth was reduced, leading to termination of crystal growth [13].
Otherwise the shape of nanoparticles was not spheriform but irreg-
ular. The atomic lattice fringes in Fig. 2B could demonstrate that the
particles are also crystalline. Sample MN3 (Fig. 2C) was achieved
by refluxing the reaction mixture at 204 ◦ C for 1 h after an ini-
tial treatment at 194 ◦ C for 30 min. This sample was even larger in
size (11.1 ± 1.2 nm) and possessed more homogeneous shape than
that obtained by simply refluxing the reaction mixture at 194 ◦ C for
1 h. This suggests that step elevation of reaction temperature was
in favor of regular particle morphology. The acquisition of larger
particles was consistent with the Ostwald ripening process dur-
ing which large crystals grow even larger at the expense of smaller
nanocrystals [14].

3.2. Characterization of nanoparticle surfaces

The surface chemical structure of the magnetic nanocrystals Fig. 3. FTIR spectra of purified 1-methyl-2-pyrrolidone, iron oxide nanoparticles and
and their capping were characterized by FTIR spectroscopy and pure oleic acid.
 C. Qin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 130–134
Fig. 4. Heating curves for (A) sample MN1 and (B) sample MN2.
TGA. As depicted in Fig. 3, the characteristic peaks centered at
585 cm−1 in all spectra of magnetic particles can be ascribed to
lattice absorption of magnetite [15]. The band peak at 1710 cm−1 is
attributed to the carbonyl (C O) stretching mode, which is charac-
teristic of the OA dimer form [16]. This band is not observed in
the spectra of magnetic samples, but two additional vibrational
bands appear at around 1530 cm−1 and 1430 cm−1 in both spec-
tra MN2 and MN3. Such changes are assigned to the formation
of either a monodentate or bidentate complex between the car-
boxylic acid and Fe on the surface of the iron oxide nanoparticles
[17,18]. All of these results support that the carboxylic acid from
OA is bound to the particle surface. The FTIR measurements also
reveal that the vibrational band C O shifts from 1680 cm−1 for pure
1-methyl-2-pyrrolidone to 1650 cm−1 for sample MN1, which indi-
cates that the O from C O coordinates with Fe on the surface of the
magnetic nanocrystallites [19]. Since this band remains in spectra
MN2 and MN3, it can be deduced that the 1-methyl-2-pyrrolidone
molecules bound to the particle surface are partially replaced by
OA. This is because 1-methyl-2-pyrrolidone, a coordinating solvent,
was in great excess in comparison with OA under current prepara-
tive condition. We believe that there is some competition between
1-methyl-2-pyrrolidone and OA to coordinate with iron particles, a
scenario which needs further investigation.
Based on TGA measurements, we could determine the relative
composition of iron oxide core, organic shell and solvent residues.
In Fig. 4, curves A and B show the degradation of samples MN1
Fig. 5. Schematic drawing of 1-methyl-2-pyrrolidone, oleic acid, Fe nanoparticles whose surface is capped with 1-methyl-2-pyrrolidone or a monolayer consisting of both
1-methyl-2-pyrrolidone and oleic acid.
133
Fig. 6. Magnetic hysteresis loops measured at room temperature for samples MN1
and MN2.
and MN2, respectively. Both samples display y a similar mass-
loss profile below 260 ◦ C, with initial losses for water or solvent
residues and subsequently organic shell degradation. In both cases,
the amount of water release corresponds to ∼3.4% at T < 180 ◦ C.
For sample MN1, the mass profile exhibits a well defined decrease
over a temperature range of 260–400 ◦ C. For sample MN2, sig-
nificant mass losses were detected in the heating from 270 ◦ C to
430 ◦ C, and the mass loss decreased more intensely as the tem-
perature above 270 ◦ C, revealing a different pattern from that
observed for MN1. During the temperature range of 180–700 ◦ C,
sample MN1 and sample MN2 have 11.0% and 14.8% mass loss for
organic shell, respectively. For the sample MN1, the weight losses
were due to the desorption and subsequent evaporation of the 1-
methyl-2-pyrrolidone. For the sample MN2, the weight reductions
are attributed to quantitative mass loss of OA and 1-methyl-2-
pyrrolidone, according to FTIR results. For OA coated iron oxide
nanoparticles, more than 20% mass losses were observed by other
research groups [20,21]. Therefore, it further supports that the OA
does not completely displace 1-methyl-2-pyrrolidone and possibly
forms an intercalated layer on the particle surface (Fig. 5).
3.3. Magnetic properties
In a preliminary investigation of magnetic properties of these
nanoparticles, hysteresis loops were recorded at room tempera-
ture. Fig. 6 shows the room-temperature magnetization curves
134 C. Qin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 336 (2009) 130–134
of samples MN1 and MN2. The two samples present ferromag- References
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[22]. In the case of 1-methyl-2-pyrrolidone coated nanoparticles, [1]
[2]
described as magnetization curve MN1, the saturation magnetiza- [3]
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[6]
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[11]
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[13]
4. Conclusions
[14]
In summary, size-controlled synthesis of monodisperse iron [15]
oxide nanoparticles are performed by the high-temperature reac- [16]
tion of Fe(acac)3 in the presence of 1-methyl-2-pyrrolidone. The
addition of OA as a competitive surfactant could change the size and [17]
[18]
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allows highly crystalline and monodisperse nanoparticles to be
[20]
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particle size can be easily altered by changing the experimental [21]
parameters. Third, this synthetic process can be readily scaled up for
[22]
mass production. In addition, the low cost of reagents and the high
yields make this reliable way economic, and the reaction medium
is environmentally friendly.
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