The electromagnetic property of chemically reduced graphene oxide and its

application as microwave absorbing material

Chao Wang, Xijiang Han, Ping Xu, Xiaolin Zhang, Yunchen Du et al.

Citation: Appl. Phys. Lett. 98, 072906 (2011); doi: 10.1063/1.3555436

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 APPLIED PHYSICS LETTERS 98, 072906 共2011兲

The electromagnetic property of chemically reduced graphene oxide and

its application as microwave absorbing material
Chao Wang,1 Xijiang Han,1,a兲 Ping Xu,1 Xiaolin Zhang,1 Yunchen Du,1 Surong Hu,1
Jingyu Wang,1 and Xiaohong Wang2
1
Department of Chemistry, Chemistry Laboratory Center, Harbin Institute of Technology, Harbin 150001,
People’s Republic of China
2
Beijing Institute of Aeronautical Materials, Beijing 100095, People’s Republic of China
共Received 4 December 2010; accepted 5 January 2011; published online 18 February 2011兲
The residual defects and groups in chemically reduced graphene oxide cannot only improve the
impedance match characteristic and prompt energy transition from contiguous states to Fermi level,
but also introduce defect polarization relaxation and groups’ electronic dipole relaxation, which are
all in favor of electromagnetic wave penetration and absorption. The chemically reduced graphene
oxide shows enhanced microwave absorption compared with graphite and carbon nanotubes, and
can be expected to display better absorption than high quality graphene, exhibiting a promising
prospect as microwave absorbing material. © 2011 American Institute of Physics.
关doi:10.1063/1.3555436兴

Graphene is a two-dimensional sheet of carbon atoms
that bonded together in a hexagonal lattice. The extended
honeycomb network of graphene is the basic building block
of other important allotropes including fullerenes, nanotubes,
and graphite.1,2 The development of graphene has attracted
much attention due to its remarkable physical and chemical
properties since it was discovered by mechanical exfoliation
in 2004.3 For example, graphene is a promising candidate in
the applications such as paperlike materials,4,5 liquid crystal
devices,6 super capacitor,7 and polymer composites.8,9
Graphene can usually be made by four different methods
including chemical vapor deposition,10 micromechanical ex-
foliation of graphite,11 epitaxial growth,12 and chemical re-
duction from graphene oxide.13,14 In this research, we pre-
pare chemically reduced graphene oxide 共r-GO兲 due to its
scalability, high yield, and the easiness of chemical function-
alization. These advantages mean the r-GO would be used
for a wide range of applications.
The microwave absorbing material has received much
attention because of their prospective applications in elec-
tronic instruments in industry, commerce, and military
affairs.15 Most of the microwave absorbing materials are
composed of magnetic loss powders such as ferrite,16
nickel,17 cobalt,18 and dielectric loss materials such as carbon
nanotubes 共CNTs兲 and conducting polymers.19–21 Though the
microwave absorbing ability of CNTs is extremely weak,
previous reports demonstrate that the composites of CNTs
and magnetic materials would exhibit excellent microwave
absorbing property.15,22,23 Therefore, first, as a kind of new
carbon material, r-GO may also be a potential microwave
absorbing material just as CNTs. Second, though the pub-
lished work shows that r-GO can be used as electromagnetic
interface shielding material,24 little research has concerned
the electromagnetic wave absorbing property of r-GO. The
above two reasons motivate us to investigate the electromag-
netic wave absorbing ability of r-GO. There is a traditional
view that the residual defects and groups in r-GO would
degrade the device performance,5 however, our research
a兲
Author to whom correspondence should be addressed. Electronic mail:
hanxj63@yahoo.com.cn.
demonstrates that the residual defects and groups may be
beneficial for the electromagnetic wave absorption, which is
an interesting and valuable exploration in the physical appli-
cation of r-GO.
Briefly, graphite oxide 共GO兲 was first synthesized from
graphite powder by a modified Hummers method, then it was
reduced with hydrazine to prepare r-GO according the re-
ported procedure.14 The permittivity real part 共␧⬘兲 and imagi-
nary part 共␧⬙兲 of graphite increase with the increase in fre-
quency from 2 GHz due to Maxwell–Wagner polarization
effect, till reaching the peaks at 2.5 GHz for ␧⬘ and 4 GHz
for ␧⬙ as shown in Fig. 1共a兲. Then, the permittivity starts to
decrease as the frequency increasing, exhibiting obvious
frequency-dependent dielectric response. This may arise
from the lag of the induced charges to follow the reversing
external field at high frequencies and finally causes a reduc-
tion in the electronic oscillations.25 The two permittivity
peaks of graphite indicate a resonance behavior, which usu-
ally emerges when the material is highly conductive.19
After strong oxidation, sp2-bonded carbon network of
graphite is intensively disrupted and a significant fraction of
the carbon network is bonded to hydroxyl, epoxide, carboxy-
lic, and carbonyl groups.26 Here, we do not list the permit-
tivity and permeability of GO due to its nonconductive and
nonmagnetic property. For r-GO, the excellent hexagonal
“graphene” framework cannot be completely recovered after
reduction due to the existence of residual groups and defects
such as the missing carbon atoms and sheet corrugation, so
the conductivity of r-GO would be decreased compared with
that of graphite.13,26 Therefore, the ␧⬘ and ␧⬙ resonance peaks
of r-GO disappear. According the free electron theory, low
conductivity would result in low permittivity,21,27 that’s why
the ␧⬘ and ␧⬙ of r-GO are low and exhibit a slightly decrease
as the frequency increasing compared with those of graphite.
Figure 1共b兲 exhibits the permeability real part 共␮⬘兲 and
imaginary part 共␮⬙兲 of graphite and r-GO, which demon-
strates that both ␮⬘ and ␮⬙ are very low due to the weak
magnetic characteristic. Especially, the ␮⬘ and ␮⬙ of graphite
vary little from 4 to 18 GHz, and ␮⬘ of r-GO increases while
␮⬙ of r-GO decreases compared with those of graphite.

0003-6951/2011/98共7兲/072906/3/$30.00 98, 072906-1 © 2011 American Institute of Physics

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072906-2 Wang et al.
FIG. 1. 共Color online兲 共a兲 Frequency dependence of relative complex per-
mittivity real part 共␧⬘兲 and imaginary part 共␧⬙兲. 共b兲 Frequency dependence of
relative complex permeability real part 共␮⬘兲 and imaginary part 共␮⬙兲.
The dependence of microwave absorption 共reflection
loss兲 property on permittivity and permeability can be evalu-
ated by the following equation:
RL = 20 log兩共Zin − Z0兲/共Zin + Z0兲兩,
where Z0 is the impedance of free space and Zin is the input
characteristic impedance, which can be expressed as
Zin = Z0冑共␮r/␧r兲tanh兵j共2␲ fd/c兲冑␮r␧r其,
where c is the velocity of light and d is the thickness of an
absorber. Figure 2 apparently demonstrates that r-GO exhib-
its much better microwave absorbing ability than graphite.
Generally, the real parts of relative complex permittivity and
permeability symbolize the storage ability of electromagnetic
energy, and the imaginary parts represent the electromagnetic
energy loss ability.28 Due to the magnetism is weak, dielec-
tric loss is the main microwave absorbing mechanism of
FIG. 2. Microwave absorption characteristics of graphite and r-GO at the
thickness of 2 mm.
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Appl. Phys. Lett. 98, 072906 共2011兲
FIG. 3. Typical Cole–Cole semicircles 共␧⬙ vs ␧⬘兲 for graphite 共a兲 and r-GO
共b兲 in the frequency range of 2–18 GHz.
r-GO, so the problem is why the r-GO with lower ␧⬙ owns
stronger microwave absorption than graphite?
First, based on previous reports,21,29 apart from dielectric
loss and magnetic loss, another important concept relating to
microwave absorption is impedance match characteristic, too
共1兲
high permittivity of absorber is harmful to the impedance
match and results in strong reflection and weak absorption.19
That is one of the reasons why r-GO with low permittivity
exhibits stronger microwave absorption than graphite. Sec-
共2兲 ond, energy transition of microwave band involves the elec-
tronic spin, which means greater spin states are required for
microwave absorption. It has been documented that localized
states near to the Fermi level could be created via introduc-
ing lattice defects30 and electromagnetic energy can be ab-
sorbed by the transition from contiguous states to Fermi level
when the irradiation is incident on the absorber surface.31
Therefore, the existence of defects in r-GO is in favor of the
electromagnetic energy absorption, which is another reason
why r-GO exhibits better absorbing ability.
Third, an important mechanism for dielectric loss mate-
rial to absorb electromagnetic wave arises from the relax-
ation process. According to the Debye relaxation expression,
the complex permittivity can be written as
共␧⬘ − ␧⬁兲2 + 共␧⬙兲2 = 共␧s − ␧⬁兲2 , 共3兲
where ␧s and ␧⬁ are the static dielectric constant and the
dielectric constant at infinite frequency, respectively. Thus,
the plot of ␧⬙ versus ␧⬘ would be a single semicircle, which
can be defined as the Cole–Cole semicircle.21,32 Figure 3
shows the curve characteristic of ␧⬙ versus ␧⬘, which pre-
sents a clear segment of three overlapped Cole–Cole semi-
circles for r-GO but only one semicircle for graphite. This
suggests that there is sole relaxation process for graphite and
ternary relaxation processes for r-GO, with each semicircle
072906-3 Wang et al.
corresponding to one Debye relaxation process. shows enhanced microwave absorption compared with
The sole relaxation process of graphite may arise as fol- graphite and CNTs, and can be expected to display better
lowing: under the alternating electromagnetic field, the lag of absorption than high quality graphene.
induced charges which counters the external applied field
1
results in the relaxation and transfers the electromagnetic en-
2
ergy to heat energy, so the microwave is attenuated.33,34 Be-
cause of numerous delocalized electrons in conductive 3
graphite, this dielectric relaxation process is obvious and a
big Cole–Cole semicircle emerges as shown in Fig. 3共a兲. 4
Hence, the dielectric relaxation is the main reason for graph-
5
ite to absorb microwave.
It is well-known that there are residual defects and
6
groups in r-GO.1,5,13,26 As to r-GO, carbon framework is
partly reconstructed, so the dielectric relaxation process that
7
caused by the lag of induced charges occurs just as it hap-
pens in graphite, but it is not as obvious as that in graphite
8
for the existence of disrupted graphene lattice. Therefore, the
corresponding Cole–Cole semicircle becomes smaller.
The additional two relaxation processes of r-GO are ob- 9
viously arising from defects and groups. First, defects can act
as polarization centers, which would generate polarization
relaxation under the altering electromagnetic field and at-
10
tenuate electromagnetic wave, resulting a profound effect on
the loss of microwave.19 Second, there are residual oxygen- 11
containing chemical bonds such as C u O, C v O in the
r-GO.26 The different ability to catch electrons between car- 12
bon atom and oxygen atom results in electric dipole polar-
ization, while this kind of dipole polarization is absent for
13
graphite. Therefore, the electron motion hysteresis in these
dipoles under alternating electromagnetic field induces addi-
tional polarization relaxation process which is favorable in 14
enhancing microwave absorbing ability.
15
Finally, we should compare the microwave absorbing
16
ability between r-GO and high quality graphene, CNTs. The
high quality graphene made by mechanical exfoliation 17
method would introduce little defect and chemical group,5
18
which is obviously more conductive than r-GO. As discussed
above, high conductivity can result in high permittivity,
19
which is harmful for microwave absorption according to the
impedance match characteristic. Hence, though we cannot 20
measure real microwave absorbing ability of high quality
21
graphene because of its low yield, it is reasonable to accept
that high quality graphene with little defect and group will
22
display poor microwave absorption compared with r-GO.
In addition, previous reports demonstrate that CNTs display 23
very poor microwave absorption no less than ⫺2 dB, but
the composites of CNTs and magnetic metals 共Fe, Co, and 24
Ni兲 would exhibit much enhanced microwave
25
absorption.15,19,20,22,23 In this research, the r-GO exhibits mi-
26
crowave absorbing intensity as much as ⫺6.9 dB at 7 GHz,
which is obviously stronger than the reported CNTs,19,20 so 27
we believe r-GO/magnetic metals composites will display
28
excellent microwave absorbing property. Further experiment
is undergoing.
29
In summary, there is only one dielectric relaxation pro- 30
cess for graphite and its impedance match characteristic is
poor, which result the weak microwave absorbing ability. 31
However, the residual defects and groups in r-GO not only
32
can improve the impedance match characteristic but also in-
troduce the transition from contiguous states to Fermi level,
33
defect polarization relaxation, and groups’ electronic dipole
polarization relaxation, which are all in favor of electromag-
34
netic wave penetration and absorption. As a result, r-GO
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