Materials Letters 78 (2012) 6971

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Template-free synthesis of Co nanoporous structures and their electromagnetic wave

absorption properties
Jing Kong a, Fenglong Wang a, Xinzhen Wan a, Jiurong Liu a,, Masahiro Itoh b, Ken-ichi Machida b
a
b

Key Laboratory for LiquidSolid Structural Evolution and Processing of Materials, Ministry of Education, Shandong University, Jinan 250061, PR China
Center for Advanced Science and Innovation, Osaka University, Osaka 565-0871, Japan

a r t i c l e

i n f o

Article history:
Received 14 January 2012
Accepted 9 March 2012
Available online 17 March 2012
Keywords:
Cobalt porous particles
Magnetic materials
Microstructure
Electromagnetic wave absorption

a b s t r a c t
We report a template-free hydrogen reduction approach to prepare sponge-like cobalt nanoporous structures
employing Co3O4 as precursors, which were obtained by thermal-decomposing of CoCO3 intermediates prepared
by a facile solvent-thermal route. A three-step formation mechanism for the Co nanoporous structures was proposed. The epoxy resin composites with 65 wt.% rhomb-like and rod-like samples showed efcient electromagnetic wave absorption characteristics (RL b 20 dB) in the ranges of 12.818 GHz and 11.218 GHz over
absorber thicknesses of 1.051.5 mm and 1.01.6 mm, respectively. It is believed that the porous metallic magnets
would gain wide applications as more efcient electromagnetic wave absorbers.
Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction
In the family of nanomaterials with various morphologies, nanoporous materials with high specic surface area have been attracting
intensive attention since their unique physical properties different
from the solid counterparts, which make them critically important
in technological applications [14]. In recent years, nanostructured
magnets with different architectures were synthesized and have
shown applications in high-density magnetic recording, medical diagnosis, microwave absorption, etc. [57], while nanoporous magnets
are rarely reported. As important ferromagnetic materials, Co nano/
micro-structures have drawn extensive research interests for electromagnetic (EM) wave absorption applications. EM wave absorption
properties of Co nano/micro-structures such as ower-like Co
spheres, hollow Co nanochains, Co nanoplatelets etc. have been investigated, and the EM absorption characteristics, i.e., frequency,
thickness, and absorbing band-width are strongly related to Co microstructures [810]. However, to the best of our knowledge, no investigation in exploring Co porous nano/micro-structures as EM
absorption materials has been presented. Gu et al. synthesized mesoporous NiFe2O4 with enhanced EM absorption properties by using
mesoporous silica as a hard template, in which the porous structure
played a signicant role [11]. The above results suggest that Co porous nano/micro-structures might be good EM wave absorbers due
to their porous networks, low density, and large surface area.

Corresponding author. Tel.: + 86 531 88392036; fax: + 86 531 88392315.

E-mail address: jrliu@sdu.edu.cn (J. Liu).

Template-based approach is usually used to generate porous structures, but this approach is somewhat complicated. Other methods such
as microwave-assisted synthesis [12], reaction-limited aggregation of
nanoparticles [13], chemical/electrochemical de-alloying from a binary
or multi-component alloy [14,15], are also employed to generate selected porous structures. The above synthesis routes usually suffer from low
yield, and thus it is still desirable to nd new efcient routes to largescale synthesis of porous metallic materials. In this study, we report a
template-free hydrogen reduction approach to prepare Co nanoporous
structures and the electromagnetic wave absorption properties were investigated in detail.
2. Experimental
The CoCO3 intermediates were prepared by a facile solventthermal route, which was developed on the base of the previous report [16]. 1 g polyvinyl-pyrrolidone (PVP) was dissolved in 40 ml
diethylene glycol (DEG) or the mixed solution of 38 ml DEG and
2 ml deionized water, followed by the addition of 0.05 M Co(CH3COO)24H2O under magnetic stirring. After they were completely dissolved, 1.8 or 0.3 g urea was added. Then the clear transparent
solution was sealed in a teon-lined autoclave and maintained at
200 C for 24 h. The pink CoCO3 products were obtained. In air, the
CoCO3 intermediates were converted to Co3O4 precursors by thermal
decomposing at 400 C for 2 h. In order to get the nal Co products,
the Co3O4 precursors were treated at 300 C for 2 h under H2 ux
with a ramping rate of 2 C min 1 in a quartz tube furnace.
The microstructures of the products were examined using a
JSM-6700F eld emission scanning electron microscope (FESEM). X-ray diffraction (XRD) patterns were obtained by a Rigaku

0167-577X/$ see front matter. Crown Copyright 2012 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.03.026

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J. Kong et al. / Materials Letters 78 (2012) 6971

Fig. 1. (a) Schematic for the formation of Co nanoporous structures, and the XRD patterns of CoCO3 intermediates (b), Co3O4 precursors (c), and Co products (d).

Fig. 2. SEM images of as-prepared Co nanoporous structures with rhomb-like (a, c), and rod-like (g, h) morphologies.

Dmax-rc X-ray diffractometer. For evaluation of microwave absorption properties, epoxy resin composites were prepared by homogeneously mixing epoxy resin with 65 wt.% Co powders and
compressed into toroidal-shaped samples (out: 7 mm, in:
3 mm). The relative permeability (r) and permittivity (r) were
measured by a vector network analyzer (Agilent Technologies
E8363A) in the range of 0.0518.05 GHz.
3. Results and discussion
Fig. 1a illustrates the three-step formation process for the Co
nanoporous particles. When the as-prepared CoCO3 intermediates
were gradually heated, CO2 started to release from the surface of particles. With temperature increasing, the inner CoCO3 was decomposed quickly and thus the gathered gas pressure made a mass of
CO2 release from inside. The CO2 gas ran through channels originating
from structure defects or vacancies of oxygen and carbon atoms, and
the channels (See Fig. S1 in Supplementary Material) were reserved
from the assembly of inner particles for decreasing the surface energy. In the next stage, the reduction gas molecules could homogeneously go through the existing channels and reduced the Co3O4
ligaments to Co. By kinetically controlling the thermal reduction, the
crystallization of Co nanoparticles can be induced to constitute a 3D
sponge-like structure. The XRD patterns of products in every step of
transformation process were revealed in Fig. 1b. All diffraction

Fig. 3. The relative permittivity r (a) and permeability r (b) curves plotted against frequency for the resin composites with 65 wt.% nanoporous Co powders of sample H1
and H2 in the 0.518.0 GHz.

J. Kong et al. / Materials Letters 78 (2012) 6971

71

to evaluate the EM wave absorption properties [19]. The RL values of

the resin composites less than 20 dB, implying 99% of EM wave absorption, were obtained in the 12.818 GHz range with absorber
thicknesses of 1.051.5 mm for sample H1 as shown in Fig. 4a. A minimum RL value of 42 dB was observed at 17.3 GHz with a matching
thickness of 1.05 mm. For sample H2, the RL values less than 20 dB
were recorded in the 11.218.0 GHz range with absorber thicknesses
of 1.01.6 mm, and a minimum RL of 38.7 dB was obtained at
14.8 GHz with a thickness of 1.2 mm. Comparing with some other
Co hierarchical structures [810], the Co nanoporous structures
exhibited more efcient EM wave absorption in GHz range, which
can be attributed to that the special porous network is vital for the
EM wave absorption since porous materials have better impedance
matching with free space than the corresponding solid materials
due to their low effective permittivity [20], meanwhile porous particles are available for suppressing the eddy current loss of metallic
magnets and maintaining high permeability at high frequency,
which will induce more EM energy attenuation.

4. Conclusions

Fig. 4. Frequency dependences of the reection loss (RL) for the resin composites with
65 wt.% nanoporous Co powders of sample H1 (a) and H2 (b) at different absorber
thicknesses in the 418.0 GHz.

peaks of the nal products could be indexed to hcp Co phase (JCPDS

5-727), indicating the high purity of the Co nanoporous structures.
SEM images of the as-prepared Co nanoporous products are demonstrated in Fig. 2. Monodispersed rhomb-like nanoporous particles
with a diameter of ca. 1 m were obtained when CoCO3 were synthesized in solution of 40 ml DEG and 1.8 g urea (Fig. 2a). When 0.3 g
urea was added into the mixed solution of DEG and deionized water
and the other experimental parameters were kept, rod-like nanoporous particles were prepared (Fig. 2b). Close inspection reveals that
the sponge-like porous network is actually built from particle-like ligaments and there are a lot of holes on the surface. If CoCO3 are directly reduced by hydrogen without the rst decomposing process,
obvious cracks can be observed (See Fig. S2 in Supplementary
Material).
Fig. 3 shows the frequency dependences of the relative permittivity and relative permeability for the two resin composites containing
65 wt.% Co nanoporous structures with rhomb-like and rod-like morphologies, which were denoted as H1 and H2. As it is shown in Fig. 3a,
the real part () and imaginary part () of relative permittivity for
H1 and H2 were low between 0.5 and 18.0 GHz, in which the relative
permittivity (r = r jr) showed less variation. For the metalinsulator composites, the shape of permittivity could be ascribed to
polarization ability, which mainly arises from space charge polarization and dipolar polarization [17]. The enhanced dipolar polarization
dominated in the metal-insulator composites with increasing frequency [18], resulting in a little uctuation at 9.3 GHz (H1) and
10.4 GHz (H2) of complex permittivity. Fig. 3b shows the real part
of relative permeability (r) declined gradually with frequency in
the range of 0.518.0 GHz, whereas the imaginary part of relative permeability (r) exhibited a broad peak in the 6.018.0 GHz with a
maximum point at 10.0 GHz (for H1) and 10.8 GHz (for H2).
The reection loss (RL) curves calculated from the measured r
and r at the given frequency and absorber thickness were employed

In conclusion, monodispersed cobalt nanoporous structures have

been synthesized by a novel hydrogen reduction approach employing
Co3O4 as precursors. The epoxy resin composites with 65 wt.% of
rhomb-like and rod-like Co nanoporous samples showed efcient
EM wave absorption (RL b 20 dB) in ranges of 12.818 GHz and
11.218 GHz, respectively. It is proposed that the nanoporous cobalt
exhibited more efcient EM wave absorption, mainly due to the 3D
porous structure.
Supplementary materials related to this article can be found online at doi:10.1016/j.matlet.2012.03.026.

Acknowledgements
This work was supported by the grants from the Qi-Lu Young
Scholar program, the Doctoral Program of Higher Education of China
(20090131120032) and the New Century Excellent Talent Program
(NCET-10-0545), State Education Ministry.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]

Wittstock A, Biener J, Baume M. Chem Phys Chem 2010;12:1291930.

Lana-Villarreal T, Mao Y, Wong SS, Gomez R. Nanoscale 2010;2:16908.
Wei SY, Wang Q, Zhu JH, Sun LY, Line HF, Guo ZH. Nanoscale 2011;3:4474502.
Hakamada M, Matsumura S, Mabuchi M. Mater Lett 2012;70:1324.
Porthun S, Abelmann L, Lodder C. J Magn Magn Mater 1998;182:23873.
Zhang SJ, Liu XH, Zhou LP, Peng WJ. Mater Lett 2012;68:2436.
Ohlan A, Singh K, Chandra A, Dhawan SK. ACS Appl Mater Int 2010;2:92733.
Wang C, Han XJ, Zhang XL, Hu SR, Zhang T, Wang JY, et al. J Phys Chem C
2010;114:1482630.
Shi XL, Cao MS, Yuan J, Fang XY. Appl Phys Lett 2009;95:163108.
Li JG, Huang JJ, Qin Y, Ma F. Mater Sci Eng B 2007;138:199204.
Gu X, Zhu WM, Jia CJ, Zhao R, Schmidt W, Wang YQ. Chem Commun 2011;47:
53379.
Chen SQ, Wang Y. J Mater Chem 2010;20:97359.
Vishwanath B, Patra S, Munichandraiah N, Ravishankar N. Langmuir 2009;25:
311521.
Ding Y, Erlebacher J. J Am Chem Soc 2003;125:77723.
Zhang Q, Zhang ZH. Phys Chem Chem Phys 2010;12:145372.
Li CC, Yin XM, Wang TH, Zeng HC. Chem Mater 2009;21:498492.
Zhao LJ, Duan LF, Wang YQ, Jiang Q. J Phys Chem C 2010;114:106916.
Ma F, Qin Y, Li YZ. Appl Phys Lett 2010;96:202507.
Liu JR, Itoh M, Machida KI. Appl Phys Lett 2003;83:4017.
Fang ZG, Li CS, Sun JY, Zhang HT, Zhang JS. Carbon 2007;45:28739.