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Journal of Physics and Chemistry of Solids 71 (2010) 673676

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Fabrication and characterization of magnetic Fe3O4CNT composites

Xuzhen Wang, Zongbin Zhao, Jiangying Qu, Zhiyu Wang, Jieshan Qiu n,1
Carbon Research Laboratory, Center for Nano Materials and Science, State Key Laboratory of Fine Chemicals, School of Chemical Engineering, and Key Laboratory for Micro/Nano
Technology of Liaoning Province, Dalian University of Technology, Dalian 116012, China

a r t i c l e in fo abstract

Article history: Carbon nanotubes (CNTs) decorated with magnetite nanoparticles on their external surface have been
Received 20 May 2009 fabricated by in situ solvothermal method, which was conducted in benzene at 500 1C with ferrocene
Received in revised form and CNTs as starting reagents. The as-prepared composites were characterized using XRD, FTIR, SEM
2 November 2009
and TEM. It has been found that the amount of magnetite nanoparticles deposited on the CNTs can be
Accepted 10 November 2009
controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe3O4CNT composites display
good ferromagnetic property at room temperature, with a saturation magnetization value (Ms) of
Keywords: 32.5 emu g 1 and a coercivity (Hc) of 110 Oe.
A. Magnetic materials & 2009 Elsevier Ltd. All rights reserved.
B. Chemical synthesis
D. Magnetic properties

1. Introduction morphology and size of nanoparticles deposited on the CNTs.

Since their discovery in 1991 [1], carbon nanotubes (CNTs)
have attracted considerable attention due to their unique
structural, electrical and mechanical properties [2]. In recent
years, much attention has been paid to the decoration of CNTs, i.e.
lled inside [36] or supported on the outside of CNTs [79] by
foreign materials, in order to further improve their properties and
functions with the aim of extending their applications in various
technology elds. Under this driving force, numerous ways have
been developed to fabricate CNT-based nanocomposites, includ-
ing the conventional impregnation method [10], solgel techni-
que [11], hydrothermal and solvothermal process [12,13],
chemical vapor deposition [14,15] and electron-beam evaporation
[16]. With these methods, many types of active inorganic
components such as noble metals [7,17], transition metals,
and their oxides and suldes [8,18,19] were introduced into
CNT-based composites. Among them, magnetic CNT composites
were suggested to be of great importance because of their
potential uses in magnetic data storage, xerography and in
magnetic force microscopy as nanoprobes [2023].
Magnetic iron oxides (magnetite Fe3O4 or maghemite g-Fe2O3)
have long been the focus of basic research and practical
applications. Various techniques such as wet-chemistry methods
have been used for loading iron oxide nanoparticles on the outer
surface of CNTs [2427]. However, these methods are normally
tedious and complicated, and it is difcult to control the
n
Corresponding author. Tel.: + 86 411 39893994; fax: + 86 411 39893991.
E-mail address: jqiu@dlut.edu.cn (J. Qiu).
1
Current address: Zhongshan Road 158, Dalian 116012, PR China.
Alternatively, in situ synthesis approaches provide a more
promising way. Jiang and Gao [21] have prepared CNTmagnetite
composites by solvothermal method from a mixture of Feurea
coordination complex and CNTs in an ethylenediamine medium.
Wan et al. [22] reported the decoration of CNTs with Fe3O4
nanoparticles by high-temperature treatment of iron (III) acet-
ylacetonate and CNTs in liquid polyols. Here, we describe a one-
step solvothermal approach to the production of magnetiteCNT
nanocomposites, in which ferrocene was used as iron source, and
benzene was used as solvent. It is shown that when the reaction
was conducted at 500 1C, the as-formed magnetite nanoparticles
were efciently assembled on the sidewalls of carbon nanotubes.
The resulting composites exhibit ferromagnetic property at room
temperature (RT).
2. Experimental
2.1. Synthesis
Multi-wall CNTs, with a purity of about 95% and an outer
diameters of 4060 nm (from Shenzhen Nanotech Port Co. Ltd),
were puried with 1 M HNO3 solution for 6 h at room tempera-
ture (RT), and then washed several times with distilled water and
dried at 100 1C. These treatments helped remove residual
catalysts in the CNTs, but cannot decorate COOH and C= O
groups on the surface of CNTs, as conrmed by FTIR analysis
(Fig. 1B). The pretreated CNTs are sinuous and highly entangled.
Their lengths are several tens of micrometer (see Fig. 2a). For a
typical procedure to fabricate the magnetic CNT nanocomposites,

0022-3697/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2009.12.063
 ARTICLE IN PRESS
674 X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676

* graphite a CNTs
1000 b Fe3O4-CNTs
311
a

Transmittance %
800 1630
Intensity /a.u.

* 3430
220
600 b
111 400 440
511 1630
3430
400 422
570
200

10 20 30 40 50 60 70 80 4000 3500 3000 2500 2000 1500 1000 500

2 theta /degree Wavenumbers /cm-1

Fig. 1. (A) XRD pattern of Fe3O4CNT composites; (B) FTIR spectra of (a) puried CNTs and (b) Fe3O4CNT composites. (The composites were prepared in benzene at 500 1C
and an initial mass ratio 2:1 of ferrocene to CNTs.)

O Fe
Fe Cu

Cu Fe Cu

0 2 4 6 8 10

Fig. 2. TEM images of (a) pristine multi-wall CNTs and Fe3O4CNT composites prepared in benzene at 500 1C and an initial mass ratio of ferrocene to CNTs of (b) 1:1 and
(c) 2:1; (d) detailed view of the composites in (c); the inset is ED patterns of the composites; (e) HRTEM image of the boxed area in (d) and (f) EDX spectrum of the
composites, in which the Cu signals are from the grid used for TEM examination.

30 mg of ferrocene [Fe(C5H5)2] was dissolved in 3 mL benzene.
Then, 15 mg of CNTs was dispersed into the above solution under
sonication, and the mixture was transferred into a 10 mL
stainless-steel autoclave. The autoclave was sealed without
removing air, and maintained at 500 1C for 12 h before being
cooled back to RT. The black precipitates formed in the reactor
were collected using a magnet, and washed with absolute ethanol
3 times. Finally, the products were dried at RT in a vacuum oven.
By changing the solvent and the reaction temperature, different
products can be obtained.
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X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676
2.2. Characterization
The crystal phases of the as-prepared products were examined
using Rigaku D/MAX-2400 diffractometer (XRD) equipped with a
rotating anode and a CuKa radiation source (l =0.15418 nm). The
morphology and the size of the products were characterized by
scanning electron microscopy (SEM, JSM-5600LV) and transmis-
sion electron microscopy (TEM, JEM-2000EX). FTIR spectra of the
CNTs and the composites were recorded on a Nicolet 560
spectroscopy. Magnetic measurements were performed at RT
using a vibrating-sample magnetometer (VSM, JDM-13).
3. Results and discussion
The formation of magnetic CNT composites is sensitive to
the reaction temperature and the solvent used. Table 1 lists
the experimental parameters and the characteristics of the
corresponding products. The details will be discussed in the
following sections.
Fig. 1A shows the XRD pattern of the typical Fe3O4CNT
composites. The diffraction peak at 2y =26.21 is ascribed to the
(0 0 2) reection of graphite, while other diffraction peaks in the
range of 101o2y o801 match well with the (1 1 1), (2 2 0), (3 1 1),
(4 0 0), (4 2 2), (5 1 1) and (4 4 0) reections of the standard fcc
phase of magnetite (space group: Fd3m(2 2 7), JCPDS No. 89-
0691). No peaks corresponding to impurities are detected. The
peak broadening of the pattern indicates that the as-prepared
magnetite crystallites are signicantly small. The average crystal-
lite size of the magnetite crystals, calculated by Scherrers
formula, is about 14 nm.
It is known that maghemite is similar to magnetite in structure
and lattice parameter (0.8350 nm for g-Fe2O3 and 0.8396 nm for
Fe3O4). Both have spinel-type structure. Therefore, it is not easy to
identify maghemite and magnetite simply based on the ordinary
XRD pattern [28]. To clarify the phase of the as-prepared
magnetite crystallites, more direct evidence is required. Fig. 1B
shows FTIR spectra of the puried CNTs and the typical Fe3O4
CNT composites. Compared to the pristine CNTs, a peak at
570 cm 1 for the composites can be seen, which is due to the
FeO stretching mode of the tetrahedral and octahedral sites. This
is different from that of maghemite (the absorbing peaks at
630 cm 1) [29]. Undoubtedly, the Fe3O4 phase of the composites
is magnetite. In addition, the weak peaks at 3430 and 1630 cm 1
indicate that the pretreatment in diluted acid does not generate
functional groups such as hydroxyl groups (3424 cm 1) and
carbonyl groups (1626 cm 1) [7] on the CNT surface.
The size and the morphology of the composites prepared at
500 1C in benzene were examined by TEM, of which the typical
results are shown in Fig. 2, conrming that Fe3O4CNT
nanocomposites have been successfully fabricated. Compared with
the case of initial mass ratio of 1:1 (ferrocene to CNTs, Fig. 2b),
Table 1
Experimental parameters and characteristics of products.
Temp. Solvent Productsn (from XRD characterization)
(1C)
500 Benzene Fe3O4CNT nanocomposites
500 Acetone or Microsized Fe3O4carbon dendritic
ethanol composites and CNTs
600 Benzene Mixture of microsized carbon spheres,
irregular Fe3O4 particles and CNTs
400 Benzene Mixture of microsized, irregular Fe3O4
particles and CNTs
n
Reaction time was 12 h.
675
Fe3O4CNT nanocomposites are more efciently formed at 2:1
ratio of ferrocene to CNTs; the outer surfaces of carbon nanotubes
are more densely decorated with magnetite nanoparticles (Fig. 2c).
A further detailed examination of a single Fe3O4CNT in Fig. 2d
reveals that quasi-spherical Fe3O4 nanoparticles, of diameter ca.
1025 nm and a narrow size distribution, are densely and uniformly
distributed on the external surface of carbon nanotubes. This is
similar to the results in polyol process [22], but different from those
synthesized by the pyrolysis of pure ferrocene (CNTs decorated by Fe
nanoparticles on the outer surface and with the central cavity lled
by Fe nanowires) [23]. The interaction between magnetite nano-
particles and CNTs is strong enough, and few free nanoparticles are
observed on the copper grids after repeated washing and sonication
during the purication process. The electron diffraction (ED)
patterns show a set of spotty rings derived from the random
orientation of the nanoparticles, in which four rings corresponding
to the (1 1 1), (2 2 0), (3 1 1) and (4 0 0) planes of the cubic Fe3O4
phase of inverse spinel structure can be seen [30], which is
consistent with the XRD results. The HRTEM examination (Fig. 2e)
shows that the parallel lattice fringe of 0.21 nm of an individual
nanoparticle and the lattice fringe of 0.34 nm of the CNT outer shell
are clearly visible, which is in good agreement with the separation
between the (4 0 0) lattice planes of magnetite and the (0 0 2) lattice
planes of graphite. Furthermore, energy dispersive X-ray (EDX)
analysis (Fig. 2f) conrms that only Fe, O and C elements are present
in the composites, and the calculated atomic ratio of Fe to O is close
to 3:4, which is in good agreement with the stoichiometric
composition of magnetite.
It is also found that the formation of the magnetic composites
is sensitive to the reaction media. When other conditions remain
unchanged, and acetone or ethanol is used as solvent instead of
benzene, microsized Fe3O4carbon dendritic composites with an
average length of several tens of micrometers and a width of 2 mm
are obtained (see Figs. 3a and b). This implies that oxygen-
containing solvent does not favor the formation of magnetite
nanoparticles and their assembly on CNTs.
The effect of reaction temperature on the composites was also
investigated, and the typical SEM images are shown in Figs. 3c and d.
When the experiment was conducted in benzene at 600 1C, with the
initial ferrocene to CNTs of 2:1 and the reaction time 12 h, a large
amount of elliptic carbon spheres of size 510 mm and irregular
Fig. 3. SEM images of (a) Fe3O4carbon dendritic composites prepared in acetone
at 500 1C; (b) magnied image of (a); (c) mixture of microsized carbon spheres and
irregular Fe3O4 particles prepared in benzene at 600 1C and (d) mixture of irregular
Fe3O4 particles prepared in benzene at 400 1C.
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676 X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676
Fe3O4 particles of 12 mm size are formed (Fig. 3c); at the same time,
no CNT composites are formed. At 400 1C, only a mixture of CNTs
and irregular Fe3O4 particles of ca. several hundred nanometers are
obtained separately (Fig. 3d). Obviously, this is different from the
product prepared at 500 1C, in which small iron oxide nanoparticles
adhered to the surface of CNTs (Fig. 2c).
On the basis of the information and observations discussed
above, the formation process of Fe3O4CNT nanocomposites is
proposed as below. It is known that ferrocene is a highly volatile
organometallic compound, and its decomposition temperature in
the gas phase is reported to be as high as 400 1C [20,23]. As such,
the synthesis of magnetic CNT composites should be carried out at
temperatures higher than 400 1C. At 600 1C, the solvent (benzene)
decomposes rapidly, resulting in microsized carbon spheres,
while at an appropriate temperature of 500 1C, ferrocene decom-
poses, yielding clusters made of iron atoms that are subsequently
oxidized by oxygen in the reactor to form Fe3O4 nanoparticles.
Then the Fe3O4 nanoparticles subsequently grow and deposit on
the external surface of CNTs, resulting in magnetiteCNT
composites [20]. Considering poor functional groups on the
surface of CNTs (identied by FTIR), electrostatic interaction
may be responsible for the attachment of magnetite nanoparticles
on the outside of CNTs, implying the unique sp2 structure of the
CNTs is not destroyed by acid pretreatment and their electronic
properties remain unchanged [7,31].
Fig. 4 is the magnetic hysteresis curve of the typical Fe3O4CNT
composites at RT, indicating that the composites exhibit
ferromagnetic behavior, which differs from the iron oxides lled
CNTs displaying superparamagnetic property [4,27,32]. The curve
shows clear saturation up to 5000 Oe, and the saturation
magnetization (Ms) is about 32.5 emu g 1, which is much lower
than that of the bulk phase (85100 emu g 1) [33]. For the Fe3O4
CNT composites, the coercivity eld (Hc) is about 110 Oe, and the
remnant magnetization (Mr) is 6.4 emu g 1. The reason for the high
Hc value might be due to the quasi-one-dimensional arrangement of
magnetite nanoparticles decorated on the outside of CNTs [33]. The
Ms value is close to 29.35 emu g 1 reported by Wan et al. [22], but
much higher than the value of CNT/Fe3O4 composites fabricated
previously [27,34]. This is attributed to the fact that more Fe3O4
nanoparticles are attached to the sidewalls of CNTs in the as-prepared
composites. The magnetic property of the composites is important for
their applications such as in catalysis, electronic devices, sensors and
magnetic purpose, which needs to be further explored.
40
30
20
10
M (emu/g)
0 20
15
-10 10
M (mu/g)
5 [28] M.F. Casula, Y.W. Jun, D.J. Zaziski, E.M. Chan, A. Corrias, A.P. Alivisatos, J. Am.
0 Chem. Soc. 128 (2006) 16751678.
-20 -5
-10
-15
-30 -20
-200 -100 0 100
H (Oe)
-40
-4000 -2000 0 2000 4000
H (Oe)
Fig. 4. Magnetic hysteresis curves measured at RT for Fe3O4CNT composites
prepared in benzene at 500 1C and an initial mass ratio of ferrocene to CNTs of 2:1.
The author has requested enhancement of the downloaded file. All in-text references underlined in blue are linked to publications on ResearchGate.
4. Conclusion
A simple solvothermal route for in situ synthesis of Fe3O4
nanoparticles decorated multi-wall CNTs is developed, by using
ferrocene as the precursor and benzene as solvent. The Fe3O4CNT
nanocomposites exhibit good ferromagnetic property at room
temperature. The synthesis method can be extended for deposit-
ing other metals, alloys or oxides nanoparticles onto CNTs using
appropriate precursors and solvents.
Acknowledgements
This work is partly supported by the National Natural Science
Foundation of China (Nos. 50672013, 50772017, 20725619,
20836002). We thank Profs. L.J. Zou and L. Qi at Dalian University
of Technology for SEM, TEM and VSM measurements.
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