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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
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
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.
ARTICLE IN PRESS
X. Wang et al. / Journal of Physics and Chemistry of Solids 71 (2010) 673676 675
Table 1
Experimental parameters and characteristics of products.
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
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