This article was downloaded by: [Universiteit Twente]

On: 29 November 2014, At: 23:59

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Fullerenes, Nanotubes and Carbon Nanostructures

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lfnn20

Monodisperse Iron Oxide Nanoparticle-Reduced

Graphene Oxide Composites Formed by Self-Assembly
in Aqueous Phase
a

Hu Guoxin & Zhengxia Xu

ab

School of Mechanical and Power Engineering, Shanghai Jiaotong University, Shanghai

200240, PR China
b

School of Civil Engineering and Mechanics, Yanshan University, Qinhuangdao 066004, China
Accepted author version posted online: 09 Jan 2014.Published online: 10 Sep 2014.

To cite this article: Hu Guoxin & Zhengxia Xu (2015) Monodisperse Iron Oxide Nanoparticle-Reduced Graphene Oxide
Composites Formed by Self-Assembly in Aqueous Phase, Fullerenes, Nanotubes and Carbon Nanostructures, 23:4, 283-289,
DOI: 10.1080/1536383X.2013.812633
To link to this article: http://dx.doi.org/10.1080/1536383X.2013.812633

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Fullerenes, Nanotubes and Carbon Nanostructures (2014) 23, 283289

Copyright Taylor & Francis Group, LLC
ISSN: 1536-383X print / 1536-4046 online
DOI: 10.1080/1536383X.2013.812633

Monodisperse Iron Oxide Nanoparticle-Reduced

Graphene Oxide Composites Formed by
Self-Assembly in Aqueous Phase
HU GUOXIN1 and ZHENGXIA XU1,2
1

School of Mechanical and Power Engineering, Shanghai Jiaotong University, Shanghai 200240, PR China
School of Civil Engineering and Mechanics, Yanshan University, Qinhuangdao 066004, China

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

Received 9 November 2012; accepted 29 May 2013

Monodisperse iron oxide nanoparticle-reduced graphene oxide composites were prepared by self-assembly in aqueous phase. Presynthesized iron oxide nanoparticles were transferred to aqueous phase and then mixed with graphene oxide dispersion. The iron
oxide nanoparticles, with a diameter of around 10 nm, were self-assembled on the reduced graphene oxide sheets through
electrostatic attraction during the reduction of graphene oxide. The magnetization curves indicated that all samples exhibited
ferromagnetic behavior at room temperature with small coercivity. The values of specic saturated magnetization of composites with
different densities of iron oxide nanoparticles are 38.3, 19.5, and 7.7 emu/g. Permittivity and permeability of composites exhibit
obvious uctuations, which are ascribed to the multiple magnetic resonances. The multiple resonances involve exchange resonances
(the consequence of small size effect, surface effect, and spin wave excitations) and natural resonance.
Keywords: magnetic properties, composites, nanostructures, graphene, self-assembly

1. Introduction
Magnetic nanoparticles have attracted great interest for their
various potential applications in magnetic uids, catalysis,
biomedicine, magnetic resonance imaging, data storage, and
environmental remediation (13). Among various magnetic
nanoparticles, ferromagnetic nanoparticles have been widely
investigated owing to their strong magnetic susceptibility and
superparamagnetism (4, 5). The synthesis of monodisperse
ferromagnetic nanoparticles is of key importance, because
the properties of these nanoparticles are determined by their
uniformity. Recent studies indicate that composites containing ferromagnetic nanoparticles can be useful in electromagnetic wave absorbers, since nanoparticles exhibit distinct
magnetic properties in comparison with bulk ferromagnetic
materials (6, 7). The ferromagnetic resonance, essential for
enhanced absorption, is determined by a few physical parameters, namely, anisotropy coefcient, damping parameter,
saturation magnetization, and particle shape (8, 9). With
diminishing diameter of particles, the surface effects become
increasingly important, affecting primarily the anisotropy
coefcient and damping parameter. The diameter of

Address correspondence to Hu Guoxin, School of Mechanical

and Power Engineering, Shanghai Jiaotong University, Shanghai
200240, PR China. E-mail: hugx@sjtu.edu.cn
Color versions of one or more of the gures in this article can be
found online at www.tandfonline.com/lfnn.

ferromagnetic particles affects the absorption properties

through surface effects.
Thanks to the distinguished properties and promising
applications (1012), graphene has attracted more and more
attention since the discovery in 2004 (10). Three main methods, namely, micromechanical exfoliation of graphite (10),
chemical vapor deposition (epitaxial growth) (13), and the
creation of colloidal suspensions through chemical method
(14), have been used to prepare the graphene. Due to the disadvantage of the small yield by micromechanical exfoliation
and chemical vapor deposition, a combination of oxidation,
sonication, and reduction became a promising large-scale
approach to obtain chemically modied graphene in colloidal
suspensions. This approach is well suited to versatile chemical
functionalization and heterogenous integration. The graphene-metal nanoparticle composites acquire catalytic and
electrochemical properties and can be potentially used as in
the elds of catalysis, electrochemical sensors, and biosensors
(15, 16). Recently, chemically modied graphene materials
have been used to form composites with magnetite in
attempts to improve the reversible capacity and cyclic stability for lithium ion batteries (17, 18). A recent study indicates
that chemically reduced graphene oxide can enhance microwave absorption compared with graphite and carbon nanotube, which makes it a promising candidate as microwave
absorbing material (19). The combination of reduced graphene oxide and ferromagnetic nanoparticles is thus of great
signicance in the development of new microwave absorption
materials.

284

Guoxin and Xu

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

2.2 Preparation of Monodisperse FeONP-RGO Composites

Fig. 1. Scheme showing the self-assembly route for synthesis of

FeONP-RGO composites in aqueous phase.

In this work, we prepared monodisperse iron oxide

nanoparticle-reduced graphene oxide (FeONP-RGO) composites by self-assembly in aqueous phase. The formation
route to obtain FeONP-RGO composites is schematically
illustrated in Figure 1. The monodisperse iron oxide stabilized in hexane was synthesized in large scale without a
size-sorting process, according to previous studies (20, 21).
After pre-synthesized, iron oxide nanoparticles dissolved
in chloroform (Figure 1(A)) were transferred to aqueous
phase, the solution was mixed with graphene oxide dispersion. The graphene oxide in mixed solution was reduced
by hydrazine at 98 C for 1 hour to remove the oxygencontaining functionalities (hydroxyl, carbonyl, and carboxyl groups) and restore the sp2 network. After reduction, the solution can stabilize for more than 4 months
without aggregation. The FeONP-RGO composites can
be precipitated by adding salt and collected by magnet.
Composites with different densities of iron oxide nanoparticles exhibited the ferromagnetic property with changing
specic saturation magnetization. The obvious multi-resonance peaks of FeONP-RGO composites were observed.

2. Experimental
2.1 Materials
Natural graphite powder, iron (III) chloride hexahydrate
(FeCl36H2O, 99.0%, analytical grade), sodium oleate
(NaOL, chemically pure), and cetyltrimethylammonium bromide (CTAB, analytical grade) were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). Oleic
acid (OA, analytical grade) and 1-octadecene (90%) were purchased from Aladdin reagent Co., Ltd. (Shanghai, China).
Other reagents were of analytical grade or better and
obtained from various sources. Organic solvents like ethanol,
hexane, chloroform, and acetone were of analytical grade
or better and all chemicals were used as received. Deionized water obtained from a Nanopure system (resistivity
18 MV cm) was utilized to prepare all aqueous solution.

Preparation of the iron oleate precursor: Two methods have

been used to synthesize the iron oleate precursor. In the rst
method, 4.32 g of FeCl36H2O (16 mmol) and 14.6 g of
NaOL (48 mmol) were dissolved in a mixture solvent composed of 24 ml of water, 32 ml of ethanol, and 56 ml of hexane. The obtained solution was heated to 70 C and
maintained at this temperature with stirring for 4 hours. The
products were washed three times with copious water. In the
second method, 6.49 g of FeCl36H2O (24 mmol) and 26 ml
of OA (72 mmol) were dissolved in 60 ml of methanol and
then 180 ml of 0.4 M NaOH in methanol was slowly added
with stirring using a dropping funnel. The brown precipitate
of iron oleate was washed three times with methanol.
Synthesis of iron oxide nanoparticles: The iron oxide nanoparticles were synthesized by thermal decomposition of iron
oleate in a mixture of OA surfactant and 1-octadecene solvent (20, 21). The obtained iron oxide nanoparticles were dissolved in chloroform in the concentration of 2030 mg/ml.
2 ml of the nanoparticles solution was slowly added to
100 ml of CTAB solution (2 g/l in water) with sonication
and stirring for 10 min. The chloroform can be boiled off
from the solution in water bath at 65 C for 30 min. The aqueous CTAB-capped iron oxide nanoparticle solution was ltered through the commercial mixed cellulose ester
membrane with an average pore size of 0.22 mm to remove
any large aggregates or contaminants. Figure 1(B) shows the
photograph of the ltrated iron oxide solution.
Preparation of graphene oxide: Graphite oxide was prepared from natural graphite using the modied Hummers
method (22). The synthesized graphite oxide (100 mg) was
dispersed in water (100 ml) and then exfoliated by ultrasonication for 2 hours using a DS-3510 ultrasonic cleaner
(150 W, 40 kHz). The obtained brown dispersion was centrifuged at 3000 rpm for 20 min to remove any unexfoliated
graphite oxide using Anke TGL-16C centrifuge.
Synthesis of FeONP-RGO composites: The graphene oxide
dispersion (100 ml) was mixed with 100 ml hydrazine monohydrate. After being stirred for a few minutes, the solution
was added to a certain amount of iron oxide nanoparticle
solution. The volume ratios of the iron oxide nanoparticle
solution to the graphene oxide dispersion are 1:4, 1:1, and 4:1
(the corresponding mass ratios are around 5:28, 5:7, 20:7,
respectively). Then, the mixture was put in a water bath
(98 C) for 1 hour to yield black stable homogenous dispersion. The salt, such as sodium chloride and potassium nitrate,
was added to the mixture (around 5 g/l) to make the
FeONP-RGO composites precipitate. The precipitated composites were collected with magnet, further washed with copious water three times and dried in vacuum (30 C for
24 hours). The dried composites were washed three times
with chloroform in ultrasonication for 5 min to remove the
OA.

2.3 Characterization
Fourier transform infrared (FTIR) spectrum of iron oleate
was recorded with Equinox 55 (Bruker Co., Germany) in the

wave number range from 400 cm1 to 4000 cm1 at

0.44 cm1 resolution. X-ray diffraction (XRD) measurements were carried out using a D8 Advance diffractometer
(Bruker Co., Germany) with Ka copper radiation. The transmission electron microscopy (TEM) images were acquired
using a JEM-2100F transmission electron microscope
(JEOL, Japan) operated at 200 kV. The Raman spectra were
obtained by a confocal Raman spectrometer (Senterra R200L, Bruker Co., Germany), using the 633 nm line of an He-Ne
laser as the excitation source. Magnetization curves of
FeONP-RGO composites were measured using an MPMS
XL-7 superconducting quantum interference device (SQUID)
magnetometer (Quantum Design, USA). The FeONP-RGO
composites (60 mg) were uniformly mixed with parafn
(200 mg), and then the mixtures were compressed into a
toroidal shape (outer diameter: 7 mm, inner diameter: 3 mm,
thickness: 4 mm). The complex permittivity and permeability
of mixtures were measured using the coaxial method in frequency range from 2 GHz to 18 GHz using HP8722ES vector network analyzer (Agilent, USA).

3. Results and Discussion

FTIR spectra of the iron oleate complexes (Figure 2) showed
the characteristic peaks of carboxylate at 1444, 1529, and
1595 cm1 for the rst method, and at 1438 and 1562 cm1
for the second method. The peak at 1710 cm1 can be
assigned to the carbonyl group (-COOH), indicating that the
products contain some OA due to side reaction. The by-product, namely, OA, has no inuence on the formation of iron
oxide nanoparticles, because OA is needed as a stabilizer in
obtaining the iron oxide nanoparticles using thermal decomposition of iron oleate precursor.
The monodisperse iron oxide nanoparticles were prepared
by thermal decomposition of a mixture of equimolar
amount of iron oleate precursor and OA stabilizer in 1-octadecene solvent (20, 21). This procedure utilized non-toxic
and inexpensive reagents and yielded monodisperse magnetic

285

Fig. 3. Typical tapping-mode atomic force microscopy images of

graphene sheets on a mica substrate with a height prole.

nanoparticles without a size-sorting process. The as-prepared

nanoparticles dissolved in chloroform were transferred to
aqueous solution of surfactant such as CTAB. Using this
simple method, the primary alkane of stabilizing ligand
(OA) on the surface of the nanoparticles interacts with the
secondary alkane of the surfactant (CTAB) through van der
Waals force, and the hydrophilic charged head group of
CTAB makes nanoparticles water soluble (Figure 1(C)). It is
an effective method to transfer the hydrophobic nanoparticles into aqueous solution since the solution is stable and
has no sign of precipitation and aggregation for more than 4
months.
A single layer of graphene sheets can be spin coated onto
mica from the dilute graphene dispersion. Tapping-mode
atomic force microscopy images (Figure 3) indicate that the
thickness of graphene sheet is 1.0 nm, which is in good agreement with the previous study (14). Figure 4 shows the Raman
spectra of the FeONP-RGO composite and the reduced graphene oxide. The typical peaks of the D and G bands from
the reduced graphene oxide exhibit at around 1335 cm1 and
1590 cm1, respectively. The D-band is a breathing mode of
k-point phonons of A1g symmetry, which is attributed to
local defects and disorders, particularly the defects located at

1.0
1712
1739

0.8
0.6

-OH
stretching

3005, =CH
0.4 stretching
2925, -CH
0.2

2856, -CH

1438

1444
First method
Second method

0.0
3000

symmetrical
1710
stretching
1562
1595
1529

asymmetrical
stretching
3500

1335 cm

2500

2000

1500

1000

-1

Wavenumbers (cm )
Fig. 2. FTIR spectra of iron oleate with different synthesis
methods.

Intensity (a.u.)

Transmiance (%)

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

Monodisperse Iron Oxide Nanoparticle-Reduced Graphene Oxide Composites

-1

1590 cm

650 cm

-1

500

1000

FeONP-RGO
Reduced
graphene oxide

1500

-1

2000

2500

3000

-1

Raman shi (cm )

Fig. 4. Raman spectra of the FeONP-RGO composite and the
reduced graphene oxide.

286

Guoxin and Xu

(A)

120

Fe 3 O 4 (JCPDS19-0629)
Fe O (JCPDS25-1402)
2 3

Iron oxide

Intensity (A.U.)

80
40
0
(311)
(220)

-40

(400)

(511) (440)
(422)

(222)
-80
20

30

40

50

60

70

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

2Theta (degree)
Fig. 5. XRD pattern of the FeONP-RGO composite.

the edges of graphene and graphite platelets, while G-band

corresponds to the E2g phonon of sp2 bonds of carbon atoms
and is sensitive to the conguration of sp2 sites (16). The characteristic peak at 650 cm1 for iron oxide nanoparticles is

observed in Raman scattering spectrum of FeONP-RGO

composite, corresponding to the A1g vibration mode (23, 24).
XRD pattern of the FeONP-RGO composite is shown in
Figure 5. This pattern conrms the inverse spinel structure of
nanoparticles in composites. XRD pattern of maghemite
(Fe2O3, JCPDS 25-1402) is similar to that of magnetite
(Fe3O4, JCPDS 19-0629), so it is difcult to differentiate
them by XRD pattern (25, 26). The measurements using Xray absorption spectroscopy and X-ray magnetic circular
dichroism spectroscopy in previous studies indicate that the
composition for the iron oxide nanocrystals is in the form of
(g-Fe2O3)1x(Fe3O4)x with different x at different synthesis
conditions (21).
The morphology and microstructure of the FeONP-RGO
composites were characterized using TEM. Figure 6 shows
the TEM images of the FeONP-RGO composites with the
initial volume ratios of CTAB-stabilized iron oxide nanoparticle solution to graphene oxide dispersion in 1:4, 1:1, and
4:1. The morphology and microstructure of the FeONPRGO composites are found to be dependent on the volume
ratio of CTAB-stabilized iron oxide nanoparticle solution to
graphene oxide dispersion. For the composites with low density of iron oxide (FeONP:RGO D 1:4, volume ratio), the

Fig. 6. TEM images of the FeONP-RGO composites with the initial volume ratio of CTAB-stabilized iron oxide nanoparticle solution to graphene oxide dispersion in (A) 1:4, (B) 1:1, and (C, D) 4:1.

40

FeONP:RGO=1:4
FeONP:RGO=1:1
FeONP:RGO=4:1

saturaon
point

20

Moment (emu/g)

-20

-40
-10000

2
0
-2
-160 -80

80

160

Magnec Field (Oe)

-5000

5000

10000

Magnec Field (Oe)

Fig. 7. Magnetization curves of FeONP-RGO composites measured at 300 K with different densities of iron oxide nanoparticles. Inset is the corresponding zoom of the magnetization
curves.

(REAL)

287

12
10
8
6
4
2
0

FeONP:RGO=4:1
FeONP:RGO=1:1
FeONP:RGO=1:4

3.0G

(IMAG)

iron oxide nanoparticles with a little aggregation are electrostatically self-assembled on the crumpled silk-like reduced
graphene oxide sheets. The TEM image (Figure 6(A)) reveals
that iron oxide nanoparticles are rmly attached on the
reduced graphene oxide sheets, even after the ultrasonication
used to remove the OA and to disperse the FeONP-RGO
composites for TEM characterization. When the ratio
increases to 1:1, the coverage density of the iron oxide nanoparticles on reduced graphene oxide sheets increases and the
iron oxide nanoparticles are distributed more uniformly on
the at reduced graphene oxide sheets, as shown in Figure 6
(B). The size of nanoparticles is around 10 nm with narrow
size distribution. The TEM image of composite with high
density of iron oxide (FeONP:RGO D 4:1, volume ratio) is
given in Figure 6(C). Compared with composite with low
density of iron oxide in which the iron oxide nanoparticles
are scattering on wrinkled reduced graphene oxide sheets,
composites with high density of iron oxide show that iron
oxide nanoparticles are uniformly distributed on the reduced
graphene oxide. The lattice fringes of iron oxide are clearly
observed in the high-resolution TEM image in Figure 6(D).
The lattice spacing between two adjacent crystal planes of
nanoparticle is measured to be 0.29 nm, a value that corresponds to the (2 2 0) interplanar distance for iron oxide nanoparticles (27). The lattice fringes with a spacing of 0.25 nm, a
value that corresponds to the (3 1 1) interplanar distance for
iron oxide nanoparticles, are also observed in other high-resolution TEM images (17).
Furthermore, the iron oxide nanoparticles endow the composites the properties of electromagnetic, such as superparamagnetism and single-domain. A vibrating sample
magnetometer study indicates that all the composites at
room temperature exhibit very small remnant magnetization.
Figure 7 shows the magnetization hysteresis loops measured at 300 K in the eld range from 10 kOe to 10 kOe for
the three FeONP-RGO composites with different iron oxide
densities. The higher densities of iron oxide nanoparticles in

Moment (emu/g)

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

Monodisperse Iron Oxide Nanoparticle-Reduced Graphene Oxide Composites

6.0G

9.0G

12.0G

15.0G

18.0G

Frequency (Hz)

1.0
0.8
0.6
0.4
0.2
0.0

FeONP:RGO=4:1
FeONP:RGO=1:1
FeONP:RGO=1:4

3.0G

6.0G

9.0G

12.0G

15.0G

18.0G

Frequency (Hz)
Fig. 8. Real and imaginary value of complex permittivity of
FeONP-RGO composites with different density of iron oxide
blended in parafn.

the composites lead naturally to bigger value of specic saturation magnetization. The values of specic saturation magnetization are 38.3, 19.5, and 7.7 emu/g, which are
corresponding to the composites prepared with the initial volume ratios of CTAB-stabilized iron oxide nanoparticle solution to graphene oxide dispersion at 4:1, 1:1, and 1:4,
respectively. The magnetization for all composites is almost
saturated in a low magnetic eld (1500 Oe), indicating that
the magnetocrystalline anisotropy energy is small (28). It has
been shown that iron oxide nanoparticles would change from
ferromagnetism to superparamagnetism when the size of particle was smaller than 25 nm (29). However, the expanded
plot of hysteresis loop (inset in Figure 7) exhibits small remnant magnetization. The ferromagnetic behavior of the
FeONP-RGO composites correlates with the various interactions (exchange interactions, dipolar interparticle interactions, and interfacial cross-grain-boundary interactions)
between iron oxide nanoparticles and reduced graphene
oxide (30). This phenomenon has been observed in the heterostructure in previous studies (31, 32).
We show the frequency dependence on the real and imaginary value of the complex permittivity for the FeONP-RGO
composites blended with parafn in Figure 8. The real values
decrease rapidly from 12 to 2 with frequency below 3 GHz
and then uctuate around 3 for composites with low and high
densities of iron oxide (FeONP:RGO D 1:4 and 4:1, volume
ratio). The real value for composite with medium density of
iron oxide (FeONP:RGO D 1:1, volume ratio) declines gradually from 5 to 1 with frequency increased from 2 to 18 GHz.
The imaginary values for all spectra uctuate around 0.3.
The uctuation observed in Figure 8 is magnetic resonance
phenomena, which can be ascribed to the surface effect, small
size effect, and spin wave excitations. These multi-resonance
phenomena have been analyzed in detail in previous studies
(3335). The surface effect causes the lag of electrical displacement behind the electrical eld at the interfaces (34, 36).
After the size of the magnetic particles decreased, multi-resonance peaks were observed. The anisotropy energy of

288

Guoxin and Xu

(REAL)

4
2
1
0

3.0G

6.0G

0.4

(IMAG)

graphene oxide sheets. The multiple resonance peaks

appeared in permittivity and permeability curves involve natural resonance and exchange resonances. The exchange resonances are dependent on small size effect, surface effect, and
spin wave excitations.

FeONP:RGO=4:1
FeONP:RGO=1:1
FeONP:RGO=1:4

9.0G

12.0G

Frequency (Hz)

15.0G

18.0G

Acknowledgments

FeONP:RGO=4:1
FeONP:RGO=1:1
FeONP:RGO=1:4

0.3
0.2

The authors thank Instrumental Analysis Center of SJTU for

Raman spectra measurements.

0.1
0.0

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

3.0G

6.0G

9.0G

12.0G

Frequency (Hz)

15.0G

18.0G

Fig. 9. Real and imaginary value of complex permeability of

FeONP-RGO composites with different density of iron oxide
blended in parafn.

nanometer scale particles may be remarkably arisen because

the surface anisotropic eld was affected by the very small
size effect.
Figure 9 shows the real and imaginary value of complex
permeability for the FeONP-RGO composites blended with
parafn as a function of frequency in the range from 2 to
18 GHz. Similar to the complex permittivity, several resonance peaks also appear on the complex permeability spectra,
but the shape of these multi-resonance peaks becomes irregular. The cause of the multi-resonance peaks for complex permeability is the same as that for complex permittivity, so the
position shift of these peaks does not occur. The multi-resonance peaks for complex permeability comprise several
minor peaks and a major peak with a maximum value of 3.2
at 3.7 GHz for the real value and 0.36 at 3.1 GHz for the
imaginary value. The natural resonance frequency estimated
by Kittel equation (6, 35) may be located at a lower frequency
band around several megahertz, so it is reasonable to consider that the major peak is natural resonance peak. Multiresonances are observed when the size of magnetic nanoparticles is reduced (11). The multi-resonance peaks in Figure 9,
dened as exchange resonances, are a consequence of small
size effect, surface effect, and spin wave excitations, according to the analysis in previous investigation (34, 36).

4. Conclusions
In conclusion, we prepared FeONP-RGO composites by selfassembly in aqueous phase. Iron oxide nanoparticles were
synthesized using FeCl3 as iron source and then self-assembled on reduced graphene oxide sheets through electrostatic
attraction. The composites can be precipitated from the stable aqueous solution by adding salt and be collected by magnet. The reduced graphene oxide sheets were uniformly
covered by iron oxide nanoparticles with a diameter of
around 10 nm. The values of specic saturated magnetization
of composites are 38.3, 19.5, and 7.7 emu/g by controlling
the coverage densities of iron oxide nanoparticles on reduced

Funding
This work was supported by the National Natural Science
Foundation of China (No. 51076094, No. 51176113).

References
1. Pankhurst, Q. A., Connolly, J., Jones, S. K., and Dobson, J. (2003)
Applications of magnetic nanoparticles in biomedicine. J. Phys. DAppl. Phys., 36: R167R181.
2. Rangheard, C., de Julian Fernandez, C., Phua, P.-H., Hoorn, J.,
Lefort, L., and de Vries, J. G. (2010) At the frontier between heterogeneous and homogeneous catalysis: Hydrogenation of olens and
alkynes with soluble iron nanoparticles. Dalton Trans., 39:
84648471.
3. Reiss, G. and Hutten, A. (2005) Magnetic nanoparticles: Applications beyond data storage. Nat. Mater., 4: 725726.
4. Bulte, J. W. M. and Kraitchman, D. L. (2004) Iron oxide MR contrast agents for molecular and cellular imaging. NMR Biomed., 17:
484499.
5. Koenig, S. H. and Kellar, K. E. (1995) Theory of 1/T1 and 1/T2
NMRD proles of solutions of magnetic nanoparticles. Magn.
Reson. Med., 34: 227233.
6. Zhan, Y., Meng, F., Lei, Y., Zhao, R., Zhong, J., and Liu, X.
(2011) One-pot solvothermal synthesis of sandwich-like graphene
nanosheets/Fe3O4 hybrid material and its microwave electromagnetic properties. Mater. Lett., 65: 17371740.
7. Azadmanjiri, J., Hojati-Talemi, P., Simon, G. P., Suzuki, K., and
Selomulya, C. (2011) Synthesis and electromagnetic interference
shielding properties of iron oxide/polypyrrole nanocomposites.
Polym. Eng. Sci., 51: 247253.
8. Bregar, V. B. (2004) Advantages of ferromagnetic nanoparticle
composites in microwave absorbers. IEEE Trans. Magn., 40:
16791684.
9. Lamba, S. and Annapoorni, S. (2004) Single domain magnetic
arrays: Role of disorder and interactions. Eur. Phys. J. B, 39: 1925.
10. Novoselov, K. S., Geim, A. K., Morozov, S. V., Jiang, D., Zhang,
Y., Dubonos, S. V., Grigorieva, I. V., and Firsov, A. A. (2004)
Electric eld effect in atomically thin carbon lms. Science, 306:
666669.
11. Liu, C., Hu, G., and Gao, H. (2012) Preparation of few-layer and
single-layer graphene by exfoliation of expandable graphite in
supercritical N,N-dimethylformamide. J. Supercrit. Fluids, 63:
99104.
12. Wang, X., Zhi, L., and Mullen, K. (2007) Transparent, conductive
graphene electrodes for dye-sensitized solar cells. Nano Lett., 8:
323327.
13. Park, H. J., Meyer, J., Roth, S., and Sk

akalov

a, V. (2010) Growth
and properties of few-layer graphene prepared by chemical vapor
deposition. Carbon, 48: 10881094.

Downloaded by [Universiteit Twente] at 23:59 29 November 2014

Monodisperse Iron Oxide Nanoparticle-Reduced Graphene Oxide Composites

14. Li, D., Muller, M. B., Gilje, S., Kaner, R. B., and Wallace, G. G.
(2008) Processable aqueous dispersions of graphene nanosheets.
Nat. Nanotechnol., 3: 101105.
15. He, F.-A., Fan, J.-T., Song, F., Zhang, L.-M., and Lai-Wa Chan,
H. (2011) Fabrication of hybrids based on graphene and metal
nanoparticles by in situ and self-assembled methods. Nanoscale, 3:
11821188.
16. Xu, Z., Gao, H., and Guoxin, H. (2011) Solution-based synthesis
and characterization of a silver nanoparticlegraphene hybrid lm.
Carbon, 49: 47314738.
17. Zhu, X., Zhu, Y., Murali, S., Stoller, M. D., and Ruoff, R. S. (2011)
Nanostructured reduced graphene oxide/Fe2O3 composite as a
high-performance anode material for lithium ion batteries. ACS
Nano, 5: 33333338.
18. Zhou, G., Wang, D.-W., Li, F., Zhang, L., Li, N., Wu, Z.-S., Wen,
L., Lu, G. Q., and Cheng, H.-M. (2010) Graphene-wrapped Fe3O4
anode material with improved reversible capacity and cyclic stability for lithium ion batteries. Chem. Mat., 22: 53065313.
19. Wang, C., Han, X., Xu, P., Zhang, X., Du, Y., Hu, S., Wang, J.,
and Wang, X. (2011) The electromagnetic property of chemically
reduced graphene oxide and its application as microwave absorbing
material. Appl. Phys. Lett., 98: 072906.
20. Bronstein, L. M., Huang, X., Retrum, J., Schmucker, A., Pink, M.,
Stein, B. D., and Dragnea, B. (2007) Inuence of iron oleate complex structure on iron oxide nanoparticle formation. Chem. Mat.,
19: 36243632.
21. Park, J., An, K., Hwang, Y., Park, J.-G., Noh, H.-J., Kim, J.Y., Park, J.-H., Hwang, N.-M., and Hyeon, T. (2004) Ultralarge-scale syntheses of monodisperse nanocrystals. Nat. Mater.,
3: 891895.
22. Hummers, W. S. and Offeman, R. E. (1958) Preparation of graphitic oxide. J. Am. Chem. Soc., 80: 13391339.
23. de Faria, D. L. A., Ven^
ancio Silva, S., and de Oliveira, M. T. (1997)
Raman microspectroscopy of some iron oxides and oxyhydroxides.
J. Raman Spectrosc., 28: 873878.
24. Shebanova, O. N. and Lazor, P. (2003) Raman spectroscopic study
of magnetite (FeFe2O4): A new assignment for the vibrational spectrum. J. Solid State Chem., 174: 424430.
25. Jung, C. W. and Jacobs, P. (1995) Physical and chemical properties of superparamagnetic iron oxide MR contrast agents: Ferumoxides, ferumoxtran, ferumoxsil. Magn. Reson. Imaging, 13:
661674.

289

26. Park, Y. I., Piao, Y., Lee, N., Yoo, B., Kim, B. H., Choi, S. H., and
Hyeon, T. (2011) Transformation of hydrophobic iron oxide nanoparticles to hydrophilic and biocompatible maghemite nanocrystals
for use as highly efcient MRI contrast agent. J. Mater. Chem., 21:
1147211477.
27. Cong, H.-P., He, J.-J., Lu, Y., and Yu, S.-H. (2010) Water-soluble
magnetic-functionalized reduced graphene oxide sheets: In situ synthesis and magnetic resonance imaging applications. Small, 6:
169173.
28. Kusakari, Y., Kanomata, T., Fukushima, K., and Nishihara, H.
(2007) Magnetic properties of Heusler alloys Ru2xFexCrGe. J.
Magn. Magn. Mater., 310: e607e609.
29. Lee, J. W., Viswan, R., Choi, Y. J., Lee, Y., Kim, S. Y., Cho, J., Jo,
Y., and Kang, J. K. (2009) Facile fabrication and superparamagnetism of silica-shielded magnetite nanoparticles on carbon nitride
nanotubes. Adv. Funct. Mater., 19: 22132218.
30. Tromsdorf, U. I., Bigall, N. C., Kaul, M. G., Bruns, O. T., Nikolic,
M. S., Mollwitz, B., Sperling, R. A., et al. (2007) Size and surface
effects on the MRI relaxivity of manganese ferrite nanoparticle contrast agents. Nano Lett., 7: 24222427.
31. Ji, Z., Shen, X., Song, Y., and Zhu, G. (2011) In situ synthesis of
graphene/cobalt nanocomposites and their magnetic properties.
Mater. Sci. Eng. B, 176: 711715.
32. Zhan, Y., Meng, F., Yang, X., Zhao, R., and Liu, X. (2011) Solvothermal synthesis and characterization of functionalized graphene
sheets (FGSs)/magnetite hybrids. Mater. Sci. Eng. B, 176:
13331339.
33. Liu, X. G., Geng, D. Y., Meng, H., Shang, P. J., and Zhang, Z. D.
(2008) Microwave-absorption properties of ZnO-coated iron nanocapsules. Appl. Phys. Lett., 92: 173117.
34. Zhang, Q., Li, C., Chen, Y., Han, Z., Wang, H., Wang, Z., Geng,
D., Liu, W., and Zhang, Z. (2010) Effect of metal grain size on multiple microwave resonances of Fe/TiO2 metal-semiconductor composite. Appl. Phys. Lett., 97: 133115.
35. Zhang, X. F., Dong, X. L., Huang, H., Lv, B., Lei, J. P., and Choi,
C. J. (2007) Microstructure and microwave absorption properties of
carbon-coated iron nanocapsules. J. Phys. D-Appl. Phys., 40:
53835387.
36. Zhang, X. F., Dong, X. L., Huang, H., Liu, Y. Y., Wang, W. N.,
Zhu, X. G., Lv, B., Lei, J. P., and Lee, C. G. (2006) Microwave
absorption properties of the carbon-coated nickel nanocapsules.
Appl. Phys. Lett., 89: 53835387.