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

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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.

Alternatively, in situ synthesis approaches provide a more
Since their discovery in 1991 [1], carbon nanotubes (CNTs) promising way. Jiang and Gao [21] have prepared CNTmagnetite
have attracted considerable attention due to their unique composites by solvothermal method from a mixture of Feurea
structural, electrical and mechanical properties [2]. In recent coordination complex and CNTs in an ethylenediamine medium.
years, much attention has been paid to the decoration of CNTs, i.e. Wan et al. [22] reported the decoration of CNTs with Fe3O4
lled inside [36] or supported on the outside of CNTs [79] by nanoparticles by high-temperature treatment of iron (III) acet-
foreign materials, in order to further improve their properties and ylacetonate and CNTs in liquid polyols. Here, we describe a one-
functions with the aim of extending their applications in various step solvothermal approach to the production of magnetiteCNT
technology elds. Under this driving force, numerous ways have nanocomposites, in which ferrocene was used as iron source, and
been developed to fabricate CNT-based nanocomposites, includ- benzene was used as solvent. It is shown that when the reaction
ing the conventional impregnation method [10], solgel techni- was conducted at 500 1C, the as-formed magnetite nanoparticles
que [11], hydrothermal and solvothermal process [12,13], were efciently assembled on the sidewalls of carbon nanotubes.
chemical vapor deposition [14,15] and electron-beam evaporation The resulting composites exhibit ferromagnetic property at room
[16]. With these methods, many types of active inorganic temperature (RT).
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
2. Experimental
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]. 2.1. Synthesis
Magnetic iron oxides (magnetite Fe3O4 or maghemite g-Fe2O3)
have long been the focus of basic research and practical Multi-wall CNTs, with a purity of about 95% and an outer
applications. Various techniques such as wet-chemistry methods diameters of 4060 nm (from Shenzhen Nanotech Port Co. Ltd),
have been used for loading iron oxide nanoparticles on the outer were puried with 1 M HNO3 solution for 6 h at room tempera-
surface of CNTs [2427]. However, these methods are normally ture (RT), and then washed several times with distilled water and
tedious and complicated, and it is difcult to control the 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
Corresponding author. Tel.: + 86 411 39893994; fax: + 86 411 39893991.
(Fig. 1B). The pretreated CNTs are sinuous and highly entangled.
E-mail address: (J. Qiu). Their lengths are several tens of micrometer (see Fig. 2a). For a
Current address: Zhongshan Road 158, Dalian 116012, PR China. typical procedure to fabricate the magnetic CNT nanocomposites,

0022-3697/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
674 X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676

* graphite a CNTs
1000 b Fe3O4-CNTs

Transmittance %
800 1630
Intensity /a.u.

* 3430
600 b
111 400 440
511 1630
400 422

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. cooled back to RT. The black precipitates formed in the reactor
Then, 15 mg of CNTs was dispersed into the above solution under were collected using a magnet, and washed with absolute ethanol
sonication, and the mixture was transferred into a 10 mL 3 times. Finally, the products were dried at RT in a vacuum oven.
stainless-steel autoclave. The autoclave was sealed without By changing the solvent and the reaction temperature, different
removing air, and maintained at 500 1C for 12 h before being products can be obtained.
X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676 675

2.2. Characterization Fe3O4CNT nanocomposites are more efciently formed at 2:1

ratio of ferrocene to CNTs; the outer surfaces of carbon nanotubes
The crystal phases of the as-prepared products were examined are more densely decorated with magnetite nanoparticles (Fig. 2c).
using Rigaku D/MAX-2400 diffractometer (XRD) equipped with a A further detailed examination of a single Fe3O4CNT in Fig. 2d
rotating anode and a CuKa radiation source (l =0.15418 nm). The reveals that quasi-spherical Fe3O4 nanoparticles, of diameter ca.
morphology and the size of the products were characterized by 1025 nm and a narrow size distribution, are densely and uniformly
scanning electron microscopy (SEM, JSM-5600LV) and transmis- distributed on the external surface of carbon nanotubes. This is
sion electron microscopy (TEM, JEM-2000EX). FTIR spectra of the similar to the results in polyol process [22], but different from those
CNTs and the composites were recorded on a Nicolet 560 synthesized by the pyrolysis of pure ferrocene (CNTs decorated by Fe
spectroscopy. Magnetic measurements were performed at RT nanoparticles on the outer surface and with the central cavity lled
using a vibrating-sample magnetometer (VSM, JDM-13). 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
3. Results and discussion during the purication process. The electron diffraction (ED)
patterns show a set of spotty rings derived from the random
The formation of magnetic CNT composites is sensitive to orientation of the nanoparticles, in which four rings corresponding
the reaction temperature and the solvent used. Table 1 lists to the (1 1 1), (2 2 0), (3 1 1) and (4 0 0) planes of the cubic Fe3O4
the experimental parameters and the characteristics of the phase of inverse spinel structure can be seen [30], which is
corresponding products. The details will be discussed in the consistent with the XRD results. The HRTEM examination (Fig. 2e)
following sections. shows that the parallel lattice fringe of 0.21 nm of an individual
Fig. 1A shows the XRD pattern of the typical Fe3O4CNT nanoparticle and the lattice fringe of 0.34 nm of the CNT outer shell
composites. The diffraction peak at 2y =26.21 is ascribed to the are clearly visible, which is in good agreement with the separation
(0 0 2) reection of graphite, while other diffraction peaks in the between the (4 0 0) lattice planes of magnetite and the (0 0 2) lattice
range of 101o2y o801 match well with the (1 1 1), (2 2 0), (3 1 1), planes of graphite. Furthermore, energy dispersive X-ray (EDX)
(4 0 0), (4 2 2), (5 1 1) and (4 4 0) reections of the standard fcc analysis (Fig. 2f) conrms that only Fe, O and C elements are present
phase of magnetite (space group: Fd3m(2 2 7), JCPDS No. 89- in the composites, and the calculated atomic ratio of Fe to O is close
0691). No peaks corresponding to impurities are detected. The to 3:4, which is in good agreement with the stoichiometric
peak broadening of the pattern indicates that the as-prepared composition of magnetite.
magnetite crystallites are signicantly small. The average crystal- It is also found that the formation of the magnetic composites
lite size of the magnetite crystals, calculated by Scherrers is sensitive to the reaction media. When other conditions remain
formula, is about 14 nm. unchanged, and acetone or ethanol is used as solvent instead of
It is known that maghemite is similar to magnetite in structure benzene, microsized Fe3O4carbon dendritic composites with an
and lattice parameter (0.8350 nm for g-Fe2O3 and 0.8396 nm for average length of several tens of micrometers and a width of 2 mm
Fe3O4). Both have spinel-type structure. Therefore, it is not easy to are obtained (see Figs. 3a and b). This implies that oxygen-
identify maghemite and magnetite simply based on the ordinary containing solvent does not favor the formation of magnetite
XRD pattern [28]. To clarify the phase of the as-prepared nanoparticles and their assembly on CNTs.
magnetite crystallites, more direct evidence is required. Fig. 1B The effect of reaction temperature on the composites was also
shows FTIR spectra of the puried CNTs and the typical Fe3O4 investigated, and the typical SEM images are shown in Figs. 3c and d.
CNT composites. Compared to the pristine CNTs, a peak at When the experiment was conducted in benzene at 600 1C, with the
570 cm 1 for the composites can be seen, which is due to the initial ferrocene to CNTs of 2:1 and the reaction time 12 h, a large
FeO stretching mode of the tetrahedral and octahedral sites. This amount of elliptic carbon spheres of size 510 mm and irregular
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)


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 Fig. 3. SEM images of (a) Fe3O4carbon dendritic composites prepared in acetone
particles and CNTs 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
Reaction time was 12 h. Fe3O4 particles prepared in benzene at 400 1C.
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, 4. Conclusion
no CNT composites are formed. At 400 1C, only a mixture of CNTs
and irregular Fe3O4 particles of ca. several hundred nanometers are A simple solvothermal route for in situ synthesis of Fe3O4
obtained separately (Fig. 3d). Obviously, this is different from the nanoparticles decorated multi-wall CNTs is developed, by using
product prepared at 500 1C, in which small iron oxide nanoparticles ferrocene as the precursor and benzene as solvent. The Fe3O4CNT
adhered to the surface of CNTs (Fig. 2c). nanocomposites exhibit good ferromagnetic property at room
On the basis of the information and observations discussed temperature. The synthesis method can be extended for deposit-
above, the formation process of Fe3O4CNT nanocomposites is ing other metals, alloys or oxides nanoparticles onto CNTs using
proposed as below. It is known that ferrocene is a highly volatile appropriate precursors and solvents.
organometallic compound, and its decomposition temperature in
the gas phase is reported to be as high as 400 1C [20,23]. As such, Acknowledgements
the synthesis of magnetic CNT composites should be carried out at
temperatures higher than 400 1C. At 600 1C, the solvent (benzene)
This work is partly supported by the National Natural Science
decomposes rapidly, resulting in microsized carbon spheres,
Foundation of China (Nos. 50672013, 50772017, 20725619,
while at an appropriate temperature of 500 1C, ferrocene decom-
20836002). We thank Profs. L.J. Zou and L. Qi at Dalian University
poses, yielding clusters made of iron atoms that are subsequently
of Technology for SEM, TEM and VSM measurements.
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
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