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 Materials Letters 64 (2010) 817–819

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

One-step pyrolysis route to C/Fe3O4 hybrids from EDTA ferric sodium salt
Jingchun Zhang a, Wenqing Shen b, Zongwen Zhang b, Dengyu Pan b,⁎, Minghong Wu a,⁎
a
Shanghai Applied Radiation Institute, Shanghai University, Shanghai 200444, PR China
b
Institute of Nanochemistry and Nanobiology, Shanghai University, Shanghai 200444, PR China

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

Article history: C/Fe3O4 hybrid materials have potential applications in sensors and anode materials for lithium-ion batteries.
Received 10 December 2009 In this text, a one-step pyrolysis method was used to prepare C/Fe3O4 hybrid materials from EDTA ferric
Accepted 8 January 2010 sodium salt. The magnetic Fe3O4 nanoparticles can be homogeneously incorporated into carbon materials to
Available online 15 January 2010
form C/Fe3O4 hybrids during the reaction. The morphology and magnetism of the C/Fe3O4 hybrids are strongly
affected by pyrolysis temperature. This method supplies an ideal template to facilely synthesize C/metal-oxide
Keywords:
hybrid materials from EDTA metallic salts.
One-step pyrolysis
EDTA ferric sodium salt
© 2010 Elsevier B.V. All rights reserved.
C/Fe3O4 hybrids
Magnetism

1. Introduction of nitrogen. The magnetic Fe3O4 nanoparticles were encapsulated in

Fe3O4 nanoparticles have been an intriguing material due to the
unique electric and magnetic properties and various applications in
environment [1,2], biology[3], lithium-ion batteries [4–7], sensor [8],
magnetic record [9] and solid phase extract [10], etc. At present, various
methods have been developed to synthesize Fe3O4 nanoparticles for
different applications such as hydrothermal synthesis [4,11–13],
combustion synthesis [14], sol–gel method [15]. Among these methods,
the thermal decomposition of suitable metal organic molecular
precursor such as ferric acetylacetonate is the most facile and practical
techniques [16,17]. Furthermore, surface modification could avoid the
aggregation of Fe3O4 nanoparticles caused by the strong magnetic
interaction as well as increase their biocompatibility and functions. For
example, surfactant and polymer coated Fe3O4 nanoparticles hybrids
were synthesized with well dispersal properties and biocompatibility,
respectively [18,19]. Otherwise, carbon can improve the electronic
conductivity and surface area of Fe3O4 nanoparticles, therefore carbon
coated Fe3O4 nanoparticles show potential value from the viewpoints of
fundamental studies and technological applications in lithium-ion
batteries [6,7] and sensors [8].
During the synthesis of C/Fe3O4 hybrids, polymer [6] and
carbohydrate [7] were usually used as carbon precursors. However,
no one-step method has been reported to synthesize C/Fe3O4 hybrid
materials so far. Herein, we report a facile and large-scale way to
prepare such materials by pyrolysis of EDTA ferric sodium salt as a
single molecular precursor at 300 °C and 400 °C under the protection
⁎ Corresponding authors. Pan is to be contacted at Institute of Nanochemistry and
Nanobiology, Shanghai University, Shanghai 200444, PR China. Wu, Shanghai Applied
Radiation Institute, Shanghai University, Shanghai 200444, PR China
E-mail addresses: dypan617@shu.edu.cn (D. Pan), mhwu@staff.shu.edu.cn (M. Wu).
carbon materials during the reaction. The as-prepared C/Fe3O4
hybrids with saturation magnetization ∼ 12.5 emu/g (300 °C) and
∼29.5 emu/g (400 °C) are expected to have potential applications in
sensors and anode materials for lithium-ion batteries.
2. Experimental
EDTA ferric sodium salt was purchased from Sinopharm Chemical
Reagent Co. Ltd and was used after grinded into powder.
A facile route to C/Fe3O4 hybrid materials was developed as shown in
Scheme 1. A quartz boat filled with EDTA-FeNa (1.0 g) was thrust into a
tube furnace and calcined under nitrogen atmosphere at 300 °C and
400 °C for 2 h at a heating rate of 10 °C/min. The products were dissolved
in distilled water (30 mL) under ultrasonication (500 W, 40 kHz) for
10 min. After high-speed centrifugation (15,000 rpm) for ten minutes,
the C/Fe3O4 hybrid materials (precipitation) were obtained.
The crystallographic states of the obtained products were deter-
mined by XRD (Japan Regaku D/max-2500 using Cu Kα radiation). TEM
(JEOL JEM-2010F) observations were performed to study the morphol-
ogy of the hybrids on the carbon coated copper grids. Fourier transform
infrared (FT-IR) spectra were recorded with a FT-IR spectrometer
FTS165. The magnetic properties were measured using vibration sample
magnetization (VSM) at room temperature.
3. Results and discussion
Fig. 1 illustrates the XRD patterns of the C/Fe3O4 hybrids obtained
at 300 °C and 400 °C. It can be seen from the diffraction peaks that the
temperature played important roles in the crystallization and grain
size of the Fe3O4 nanoparticles. Higher temperature during synthesis
yielded higher crystallization and larger size. According to the Debye-

0167-577X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2010.01.023
818 J. Zhang et al. / Materials Letters 64 (2010) 817–819

Scheme 1. Scheme of the preparation process of C/Fe3O4 hybrids. Left: the C/Fe3O4 hybrids dissolved in distilled water. Right: the C/Fe3O4 hybrids dissolved in distilled water under a
magnetic field.

Fig. 1. XRD patterns of C/Fe3O4 hybrids prepared at 300 °C (a) and 400 °C (b).

Scherrer formula [20], the average diameters of Fe3O4 nanocrystals Carbon plays a key role in the formation of C/Fe3O4 hybrids: 1) reduce
increased from 9.1 nm (300 °C) to 14.9 nm (400 °C). Furthermore, the part of Fe3+ to Fe2+ under N2 atmosphere. 2) encapsulate Fe3O4
diffraction peak at 26° indicated the existence of carbon and the nanoparticles in carbon materials simultaneously.
content of carbon decreased as the temperature increased.
The FT-IR spectra of C/Fe3O4 hybrids prepared at 300 °C and 400 °C
are presented in Fig. 2. The strong peaks at about 565 cm−1 are 4. Conclusion
assigned to the vibration of the Fe–O bond of Fe3O4 [13]. The broad
bonds at about 3400 cm−1 are related to the absorbed H2O molecules In summary, we develop a facile and large-scale way to synthesize
on the surface of C/Fe3O4 hybrids. Furthermore, the absorbing peaks at C/Fe3O4 hybrid materials by pyrolysis of EDTA ferric sodium salt. The
about 1633 cm−1 (1616 cm−1) and 1453 cm−1 (1439 cm−1) are formation mechanism of carbon coated Fe3O4 hybrids is also discussed.
assigned to the asymmetric and symmetric stretching vibration of C O The size and ratio of Fe3O4 nanoparticles in C/Fe3O4 hybrids are
(COO−) on the surface of the sample prepared at 300 °C (400 °C). strongly affected by pyrolysis temperature. The saturation magneti-
TEM images of C/Fe3O4 hybrids are shown in Fig. 3 to illuminate zation (Ms) and coercive field (Hc) of the C/Fe3O4 hybrids are also
the morphology of the as-prepared products. As shown in Fig. 3 (a), tuned. This work provides a new insight for the synthesis of C/Fe3O4
most of the Fe3O4 nanoparticles were unattached and encapsulated in hybrids. More importantly, such C/Fe3O4 hybrids show potential
carbon. The statistical average particle size of the product prepared at applications in sensors and anode materials for lithium-ion batteries.
300 °C is about 9.6 nm, which is consistent with that obtained by Additionally, such method supplies an ideal template to facilely
Debye-Scherrer formula. The morphology of the C/Fe3O4 hybrid is synthesize C/metal-oxide hybrid materials such as C/SnO2 for different
strongly affected by the reaction temperature as shown in Fig. 3 (b). applications.
The particle size of Fe3O4 prepared at 400 °C seems inconsistent with
that obtained by Debye-Scherrer formula. Indeed, due to the lower
content of carbon and stronger magnetism (Fig. 4) than that of the
product prepared at 300 °C, the Fe3O4 nanoparticles easily aggregate
into larger ones.
Fig. 4 shows the magnetization hysteresis loops of the C/Fe3O4
hybrids. It can be seen that both of the products prepared at 300 °C and
400 °C are ferromagnetic at room temperature. The saturation
magnetization (Ms) values of the C/Fe3O4 hybrids increased from
12.5 emu/g (300 °C) to 29.5 emu/g (400 °C), which is mainly affected
by particle size, crystallinity and ratio of Fe3O4 nanoparticles in C/Fe3O4
hybrids. Moreover, the coercive field (Hc) ascends from 40 Oe to
360 Oe with the increased size of Fe3O4 nanoparticles.
The formation mechanism of carbon coated Fe3O4 hybrids is
discussed. During the pyrolysis, the part of Fe3+ in the molecular
precursor was broken up. The carbonaceous part of EDTA ferric sodium
salt was carbonized under high temperature and N2 atmosphere. Fig. 2. FT-IR spectra of C/Fe3O4 hybrids prepared at 300 °C and 400 °C.
 J. Zhang et al. / Materials Letters 64 (2010) 817–819 819

Fig. 3. TEM images of C/Fe3O4 hybrids prepared at 300 °C (a) and 400 °C (b).

Fig. 4. M–H curves of the C/Fe3O4 hybrids prepared at 300 °C (a) and 400 °C (b).

Acknowledgments [5] Cui ZM, Jiang LY, Song WG, Guo YG. Chem. Mater 2009;21:1162–6.
[6] Wang L, Yu Y, Chen PC, Zhang DW, Chen CH. J Power Sources 2008;183:717–23.
[7] Zhang WM, Wu XL, Hu JS, Guo YG, Wan LJ. Adv Funct Mater 2008;18:3941–6.
The authors thank analysis and test center of shanghai university, [8] Wu Y, Xing SX, Jing SY, Zhou TL, Zhao C. Polymer Bulletin 2007;59:227–34.
Prof. Bo Lu and Prof. Weijun Yu for experimental assistance. This work [9] Kim DK, Zhang Y, Kehr J, Klason T, Bjelke B, Muhammed MJ. Magn Magn Mater
2001;225:256.
is supported by Natural Science Foundation of China (10774118), [10] Zargar B, Parham H, Hatamie A. Talanta 2009;77:1328–31.
Innovation Program of Shanghai Municipal Education Commission [11] Yan J, Mo S, Nie J, Chen W, Shen X, Hu J, Hao G, Tong H. Colloids Surf A Physicochem
(10YZ03), Science and Technology Commission of Shanghai Munic- Eng Asp 2009;340:109–14.
[12] Song Ge Shi XY, Sun K, Li CP, Uher C, Baker Jr JR, Holl MMB, et al. J Phys Chem C
ipality (No. 08520512200) and Shanghai Leading Academic Discipline 2009;113:13593–9.
Project (No. S30109). [13] Wu X, Tang J, Zhang Y, Wang H. Mater Sci Eng B 2009;157:15781–6.
[14] Amara D, Felner I, Nowik I, Margel S. Colloids surf a physicochem. Eng Aspects
2009;339:106–10.
References
[15] Tang NJ, Zhong W, Jiang HY. J Magn Magn Mater 2004;92:282.
[16] Thapa D, Palkar VR, Kurup MB, Malik SK. Mater Lett 2004;58:2692–4.
[1] Martos C, Dufour J, Ruiz A. Int J Hydrogen Energy 2009;34:4475–81.
[17] Sun S, Zeng H, Robinson DB. J Am Chem Soc 2004;126:273–9.
[2] Zhang SX, Zhao XL, Niu HY, Shi YL, Cai YQ, Jiang GB. J Hazard Mater 2009;167:
[18] Yan H, Zhang JC, You CX, Song ZW, Yu BW, Shen Y. Int J Miner. Metall Mater
560–6.
2009;16:226.
[3] Yang XY, Zhang XY, Ma YF, Huang Y, Wang YS, Chen YS. J Mater Chem 2009;19:
[19] Du BY, Mei AX, Tao PJ, Zhao B, Cao Z, Nie JJ, et al. J Phys Chem C 2009;113:10090–6.
2710–4.
[20] Ge JP, Hu YX, Biasini M, Dong CL, Guo JH, Beyermann WP, Yin YD. Chem Eur J 2007;13:
[4] Ni SB, Wang XH, Zhou G, Yang F, Wang JM, Wang Q, He DY. Mater Lett 2009;63:
7153–61.
2701–3.

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