Carbon 127 (2018) 209e217

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Chemical reduction dependent dielectric properties and dielectric loss

mechanism of reduced graphene oxide
Boya Kuang, Weili Song, Mingqiang Ning, Jingbo Li*, Zhengjing Zhao, Deyu Guo,
Maosheng Cao, Haibo Jin**
School of Material Science and Engineering, Beijing Institute of Technology, Beijing, 100081, PR China

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

Article history: Reduced Graphene Oxide (rGO) is expected to be the most promising candidate for high-efficiency
Received 14 June 2017 electromagnetic wave absorption materials. However, its defect-related dielectric loss mechanism has
Received in revised form not been clarified up to date, especially when it comes to the pure rGO system. Here, the rGO with
10 October 2017
controllable reduction degree is prepared. The oxygen-containing functional groups are regularly
Accepted 30 October 2017
Available online 30 October 2017
removed from rGO during reduction. Accompanying with the decrease of oxygen-containing functional
groups, the content of lattice-defects in rGO is increased with increasing reduction degree of rGO. The
dielectric and microwave absorption properties of rGO with different reduction degrees are investigated
over 2e18 GHz. Compared to the GO, rGO exhibits obvious dielectric relaxation behaviors with a
relaxation peak at ~10 GHz. The dielectric relaxation of rGO is enhanced by increasing reduction degree
of rGO. The experimental results evidence that the enhanced dielectric relaxation behavior originates
from the increased vacancy defect dipoles in rGO generated through chemical reduction, and rule out the
contribution of oxygen-containing functional groups to the dielectric relaxation. This work reveals the
mechanism of defect-related dielectric relaxation of rGO, which may contribute to the correct under-
standing of dielectric loss of carbon-based materials for designing and/or modifying carbon-based mi-
crowave attenuation materials.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction contributing strong scattering loss of EM waves [14]. The hopping

Nowadays, the rapid development of electronic industry leads to
serious electromagnetic (EM) interference which becomes a po-
tential hazard to the performance of delicate electronic equipments
and human health. Novel EM absorption materials that are light-
weight and high efficient in wide frequency range are in high de-
mand in microelectronic devices, military equipment and
aerospace applications [1e4]. Carbon materials, such as carbon
nanotube (CNT) [5e7], carbon nanocoil (CNC) [8,9], graphite
nanosheet (GN) [10,11] and carbon nanofiber (CNF) [12,13] have
received wide interest in the field of microwave attenuation due to
their lightweight, low-dimensional structure and unique electric
and dielectric properties in the microwave frequency range. The
low-dimensional structure provides high specific surface area,
* Corresponding author.
** Corresponding author.
E-mail addresses: lijb@bit.edu.cn (J. Li), hbjin@bit.edu.cn (H. Jin).
carriers associated with defect states enhance the dielectric loss of
the carbon materials [15]. The carbon nanomaterials decorated by
magnetic metal and oxide nanocrystals or semiconductor nano-
crystals present improved microwave absorption performance
[16e18]. The improvement of EM attenuation is attributed to the
interfacial polarization resulting from the introduced nanoscale
interfaces and the synergistic effect of magnetic and dielectric
resonances [19e21].
Recently, reduced graphene oxide (rGO), the thinnest and most
lightweight 2D carbon material, is proved a promising candidate for
microwave absorbers [22e24]. The enhanced attenuation ability of
rGO is believed resulting from its high specific surface area, acti-
vated carrier mobility, abundant surface defects (such as vacancies
and various oxygen-containing functional groups) [25,26].
Although a series of research has been focused on the dielectric loss
mechanism of rGO [27e31], little knowledge has been reported on
which defect dominated the dielectric relaxation of rGO among the
various surface defects of rGO. However, this is of quite significance
for exploiting novel rGO-based EM attenuators and their

https://doi.org/10.1016/j.carbon.2017.10.092
0008-6223/© 2017 Elsevier Ltd. All rights reserved.
210 B. Kuang et al. / Carbon 127 (2018) 209e217
applications. Han et al. reported that the residual defects and
functional oxygen-containing groups of rGO introduced two addi-
tional relaxation processes by comparing rGO with the graphite,
but which one determined the dielectric loss and microwave ab-
sorption was not investigated [29]. Wu et al. analyzed the dielectric
behavior of MoS2/rGO composite, and figured out the dielectric loss
arising from both the polarization of oxygen-containing groups and
the imperfect carbon structures in rGO [30]. Huang et al. reduced
GO by an annealing process, and pointed out that the dielectric loss
and microwave absorption performance were strongly related with
chemical reduction degree of rGO [31]. In their work, accompa-
nying with the removal of oxygen-containing functional groups,
unfortunately, the crystallinity of rGO was also changed in the
annealing process, which hindered the deep understanding of the
dielectric behaviors of rGO.
For clearly understanding the contributions of various surface
defects to the dielectric loss and microwave absorption properties,
here, rGO with different chemical reduction degrees was prepared
by a mild and green chemical reduction method. The concentra-
tions of oxygen-containing functional groups in rGO were
controlled by adding different amounts of reductant (ascorbic acid:
VC). The dielectric properties and microwave absorption perfor-
mance of rGO/wax composites were investigated in the frequency
range of 2e18 GHz. A broad dielectric relaxation was observed,
which was dramatically enhanced by increasing reduction degree
of rGO. The dielectric relaxation and microwave absorption
mechanisms were discussed below.
2. Experimental
2.1. Materials
Graphite powder (~325 mesh), sodium nitrate (NaNO3),
concentrated sulfuric acid (H2SO4, 98%), potassium permanganate
(KMnO4), hydrogen peroxide (H2O2), and hydrochloric acid (HCl,
38%), ascorbic acid were all purchased from Beijing Chemical Cor-
poration. All the chemicals were used as received without further
purification.
2.2. Synthesis of GO
GO was prepared by a modified Hummers method [32]. Briefly,
1.5 g NaNO3 was dissolved in concentrated sulfuric acid (70 ml)
under stirring in an ice bath for 30 min. Then 3.0 g of graphite
powder was added, keep stirring for 1 h. Under vigorous agitation,
KMnO4 (9.0 g) was added slowly to the above solution and the
temperature was kept lower than 10
C, followed by stirring at
35
C for 2 h. Then, 140 ml of deionized water was added drop by
drop, causing violent effervescence and increase of temperature.
After 15 min stirring at 98
C, an additional 500 ml of deionized
water and 30% H2O2 was added, making the color of the suspension
change from brown to yellow. The mixture was kept to settle down
for overnight and was centrifuged with dilute hydrochloric acid
(1:10) and water by several times to remove all the impurities. The
graphene oxide was obtained by drying in a vacuum oven at 60
C
for 48 h.
2.3. Synthesis of rGO
The rGO was prepared using chemical reduction method. In
detail, different concentrations (from 30 mg to 160 mg) of VC were
added into 30 ml GO aqueous dispersion (2 mg/ml), respectively,
followed by sonicating for 30 min. The as-prepared dispersion was
kept at 95
C for 2 h without stirring to form rGO hydrogels. Then
the rGO hydrogels were immersed in deionized water for 12 h to
remove the residual impurities. The final rGO was obtained after
freeze-dried for 48 h to remove absorbed water.
2.4. Synthesis of rGO/wax composites
For measurement of complex permittivities, wax-matrix rGO
composites were prepared. In a typical preparation procedure, the
as-prepared rGO and paraffin wax (with rGO loading of 10, 20 and
30 wt%) were dispersed in ether solution under ultrasonic treat-
ment. After the solvent of the mixed solution was completely
evaporated, a portion of the mixtures was pressed into a toroidal
shape (outer radius: 7.00 mm; inner radius: 3.00 mm) with thick-
ness ~2 mm. The prepared composites are expressed as rGO-n-x%,
where n represents the concentration of VC (mg), and x% stands for
the rGO loading.
2.5. Characterizations
The morphology and microstructure of prepared samples were
observed by Hitachi S-4800 Scanning electron microscopy (SEM)
and JEM-2100F Transmission electron microscope (TEM). X-ray
photoelectron spectroscopy (XPS) measurements were carried out
on a PHI Quantera system with a C60 ion gun. Powder X-ray power
diffraction (XRD) was performed on a Bruker-AXS diffractometer
(Model D8 ANVANCE) with a Cu-Ka radiation source. Raman
spectroscopy measurements were performed on a Lab RAM Aramis
with a 532 nm laser. Electrical conductivity (s) was measured using
Solartron 1287 electrochemical workstation (Advanced Measure-
ment Technology Inc. USA) with the DC measurement model. The
complex permittivity was measured at 2e18 GHz on an Anritsu
37269D vector network analyzer using the coaxial method.
3. Results and discussion
3.1. Characterizations
The synthetic process of rGO via chemical reduction method
with VC as reducing agent is schematically depicted in Fig. 1.
Different amounts of VC were added respectively to achieve
different reduction degrees. The microstructure, structure and
reduction degree of rGO are characterized by various techniques.
Fig. 2 shows the morphology of GO and rGOs reduced with 30,
60 and 90 mg VC. GO exhibits thin and crumpled sheets with
random aggregations to form disordered powders. After being
reduced, all the rGOs show similar interconnected porous network
microstructures with graphene sheets partially overlapping in 3D
space. When the VC concentration is lower (30 mg), the graphene
oxides are not adequately reduced, in which the rGO sheets are
loosely interconnected and poorly restacked to form open network
structure. Upon increased concentration of VC (60 mg), the
continuous microscopic walls form and the internal pore size is in
the range of 1e4 mm. As the concentration of VC rises to 90 mg, the
graphene sheets assemble more tightly and the pore size keeps
shrinking to 1e2 mm. The specific surface area was measured by
Brunauer-Emmett-Teller (BET) method. The values of the specific
area for GO and rGO-30, rGO-60 and rGO-90 are 548.74, 536.95,
319.74 and 282.38 m2/g respectively. The results show a decreasing
trend of the specific area in the chemical reduction process, which
is consistent with the microstructure observation. This novel 3D
interconnected porous microstructure of rGO is not destoryed by
ultrasonic treatment in the mixture of rGO and paraffin wax, as
shown in Fig. S1 (S denotes the supporting information). The TEM
images of rGO-60 are shown in Fig. S2. The rGO sheets are flexible
and quite thin, presenting a 3e4 layered structure.
The structure evolution of the reduction process from GO to
 B. Kuang et al. / Carbon 127 (2018) 209e217 211

Fig. 1. The schematic illustration for synthetic process of rGO with different amounts of VC. (A colour version of this figure can be viewed online.)

Fig. 2. The SEM images of GO (a) (e), rGO-30 (b) (f), rGO-60 (e) (g) and rGO-90 (d) (h).

rGOs is characterized by XRD and Raman as shown in Fig. 3. For
comparison, the XRD pattern of graphite is also presented in
Fig. 3(a). The graphite shows a strong XRD peak at 2q~26.4
, which
corresponds to the (002) plane of graphite. The GO displays a strong
characteristic peak at 2q~10.2
, indicating remarkable expansion of
interlayers due to the formation of hydroxyl, epoxy and carboxyl
groups in the basal surface after oxidization [33]. Upon reducing by
VC, the sharp peak at 2q~10.2
disappears, and a broaden peak
around 2q~23
is alternatively observed, which is the typical rGO
XRD patterns [34]. With increasing the addition of VC, the broaden
peak becomes stronger and shifts to higher angle, indicating the
gradually decreased interlayer distance because of the partial
removal of such oxygen-containing functional groups. When VC is
over 90 mg, the interlayer distance tends to stay at a constant
(Fig. S3(a)), suggesting that there would be a saturation addition of
VC for the effective reduction.
Fig. 3(b) shows Raman spectra of the GO and rGOs samples. In
particular, two typical Raman peaks of G and D are observed. The G
peak at 1580-1600 cm1 corresponds to one-phonon Raman scat-
tering process at the 1st Brillouin zone center and consists of the
collective in-plane bond stretching of the polyaromatic carbon
atoms (E2g symmetry). The D peak at about 1330e1340 cm1
originates from the breathing modes of six-membered rings and its
activation resonance process involves peculiar electron-phonon
interaction mediated by defects [35e37]. Thus, the intensity ratio
ID/IG is generally used as an indicator of the lattice-defect density in
carbon materials. The more lattice-defects exist, the higher in-
tensity ratio of ID/IG is obtained. As depicted in Fig. 3(b), the ID/IG
increases from 0.97 (for GO) to 1.21 (for rGO-90) with the addition
of VC, implying the increase of lattice-defects in reduction process,
which is in good agreement with previous studies [38e40]. On the
basis of previous research about the defects in rGO [41e44], the
increased lattice-defects are probably formed in the following way.
The carbon atoms bonding with the oxygen-containing functional
groups are removed along with the oxygen-containing functional
groups in the chemical reduction process, leaving some vacancy
defects at the original position [41e44]. When the VC is above
90 mg, no obvious change is observed in ID/IG ratio, which indicates
the reduction degree reaches to the up limit (Fig. S3(b)).
XPS spectroscopy is used to investigate the reduction behavior
of rGOs. Fig. 4(a) clearly shows that the relative intensity of C1s
increases while that of O1s decreases with the addition of VC,
indicating the gradual reduction of GO. Fig. 4(b)e(e) present the
C1s XPS spectra of rGOs. The C1s peak could be split into four
components at ~284.6 eV, ~286.1 eV, ~287.0 eV and ~288.7 eV,
corresponding to C]C/CeC in aromatic, CeO (epoxy and hydroxyl),
C]O (carbonyl) and OeC]O (carboxyl) groups, respectively
[39,45,46]. Apparently, the CeO is the major oxygen-containing
group in GO. After being reduced with 30 mg VC, the intensity of
CeO group decreases evidently while the C]C/CeC bonding in
aromatic increases accordingly compared with those of GO. After
reducing with 60 mg and 90 mg VC, the CeO, C]O and OeC]O
212
Fig. 3. The XRD (a) and Raman (b) patterns of GO and rGOs. (A colour version of this
figure can be viewed online.)
groups are further removed, suggesting that the reduction degree
gradually increases as expected. The percentages of individual
oxygen-containing functional groups are estimated by fitting the
B. Kuang et al. / Carbon 127 (2018) 209e217
peak area of each type, and the values are presented by histograms
in Fig. 4(f)e(i). The relative proportion of the C]C/CeC bonds in
aromatic increases from 39.25% (for GO) to 67.19% (for rGO-90), and
the relative proportion of the CeO group has a marked drop from
40.65% (for GO) to 11.15% of (for rGO-90), indicating that the GO is
effectively reduced by VC. With more addition of VC (Fig. S4), the
XPS results of rGOs show that the relative proportions of oxygen-
containing functional groups have no significantly decrease when
the VC amount is greater than 90 mg. According to the atomic ratio
of carbon to oxygen (C/O) deduced from XPS data in Fig. 4(a), the
variation of reduction degree of rGOs via the VC amount is dis-
played in Fig. 5 (in black line). The reduction degree of rGOs first
increases with the increasing VC amount and then tends to be
stable when the VC amount is beyond 90 mg. The electrical con-
ductivity (s) of rGOs exhibits a positive correlation versus the
reduction degree, and it increases from 4.13  107 S/m to 0.28 S/m
as shown in Fig. 5(a) and (b).
Based on the above analysis, the possible reduction mechanism
of rGO with presence of VC has been illustrated in Fig. 6. The gra-
phene oxide contains hydroxyl, carbonyl, epoxy and carboxyl
functional groups in the basal plane or at the edge of the sheets
[47]. In the chemical reduction process by VC, the VC can release
two protons to form dehydroascorbic acid, and the released protons
which have commonly high binding affinity to the oxygen-
containing groups react with those groups to form water mole-
cules [48,49]. Meanwhile, some of neighboring carbon atoms could
be taken away along with the removal of oxygen-containing
groups, which leaves some vacancy defects in the graphene struc-
ture. With the increase of VC addition, the number of oxygen-
containing groups decreases, and consequently increasing va-
cancy defects have been observed.
3.2. Dielectric and microwave absorption properties
Fig. 7 shows the complex permittivities of GO/wax and rGO/wax
composites with different loadings of 10 wt%, 20 wt% and 30 wt%.
The increase of loading results in considerable increment in ε0 and
ε00 , which could be interpreted rationally according to the effective
medium theory [50]. The GO/wax composites present typical fre-
quency dependent permittivities, and both ε0 and ε00 decrease with
increasing frequency. Compared to GO/wax composites, rGO/wax
composites exhibit obvious dielectric relaxation behavior, ε00 ap-
pears a broad peak at ~10 GHz and ε0 abruptly decreases in the
corresponding frequency. The dielectric anormaly is well under-
stood by the Debye relaxation theory as expressed in Eqs. (1) and
(2). The ε00 is regarded as the joint contributions from polarization
relaxation and electrical conductivity [51].
εs  ε∞
ε0 ¼ ε∞ þ (1)
1 þ u2 t2
00 εs  ε∞ s
ε ¼ ut þ (2)
1 þ u2 t2 uε 0
where u is the angular frequency, t the polarization relaxation
time, εs the static permittivity, ε∞ the relative dielectric permit-
tivity at the high frequency limit, s the alternative conductivity, and
ε0 the dielectric constant in vacuum ðε0 ¼ 8:854  1012 F=mÞ. The
observed dielectric relaxation in rGO/wax composites originates
probably from the increased defect dipoles caused by chemical
reduction. When the GO is reduced, a large number of oxygen-
containing functional groups are removed, leaving some va-
cancies at the same position of graphene. And the defect dipoles are
generated by the unbalanced charge around the vacancies [52], as
exhibited in Fig. 8(a).
 B. Kuang et al. / Carbon 127 (2018) 209e217 213

Fig. 4. XPS spectra of GO and r-GOs (a); C1s XPS spectra of GO (b), rGO-30 (c), rGO-60 (d) and rGO-90 (e). The peaks 1, 2, 3 and 4 correspond to C]C/C-C in aromatic, C-O (epoxy and
hydroxyl), C]O (carbonyl) and OeC]O (carboxyl) groups, respectively; Percentage of individual oxygen-containing functional group of GO (f) and rGO-30 (g), rGO-60 (h) and rGO-
90 (i). (A colour version of this figure can be viewed online.)

Fig. 5. (a) Electrical conductivity and C/O atomic ratio of GO and rGOs with VC contents; (b) Electrical conductivity with C/O atomic ratio. (A colour version of this figure can be
viewed online.)

Increasing reduction degree of rGO results in the increase of ε0
and ε00 of rGO/wax at each loading (from 10 wt% to 30 wt%), as
shown in Fig. 7. This attributes to the improvement of electrical
conductivity and reconstruction of electrically conductive paths for
hopping electrons by largely removing the oxygen-containing
functional groups from GO sheets through chemical reduction
process. The hopping electrons enable to jump across defects or
between the graphene nanosheets, which makes a significant
contribution to the dielectric loss, as illustrated in Fig. 8(b) [53].
Moreover, increasing reduction degree of rGO also enhances the
dielectric relaxation, which is reflected by the increased relative
intensity of relaxation peak at ~10 GHz, particularly for the rGO/
wax composites with 10 wt% and 20 wt% loadings as shown in
Fig. 7(d) and (e). This phenomenon is understood as a result of
increased vacancy defects in rGO. Larger amount of vacancy defects
would lead to increased intensive relaxation. For the 30 wt%
loading, however, the relative contribution of the dielectric relax-
ation to ε00 becomes weaker compared with the composites with
10 wt% and 20 wt% loadings. It could be interpreted by the syner-
gistic effects of polarization relaxation and conductivity loss on the
dielectric loss. When the rGO loading reaches 30 wt%, the con-
duction network would be established. As a result, the leakage loss
massively contributes to ε00 according to Eq. (2). For the loadings of
10 wt% and 20 wt% in Fig. 7(d) and (e), the conduction network has
not be completely formed, and the ε00 mainly depends on the po-
larization relaxation from vacancy defect dipoles in the rGO.
Consequently, the results prove that the dielectric relaxation
behavior of rGO/wax composites is mainly ascribed to the increased
vacancy defects formed in the chemical reduction process, rather
than the oxygen-containing functional groups or the interfacial
polarization. The chemical reduction increases both vacancy de-
fects and electrical conductivity of rGOs, resulting in the
enhancement of the dielectric loss.
The microwave absorption performance of the rGOs/wax com-
posites is further investigated, and the reflection loss (RL) values at
various thicknesses from 2 to 18 GHz are obtained according to the
relation [54].




Z  1

RLðdBÞ ¼ 20log

in
(3)
Zin þ 1

pffiffiffiffiffiffiffiffiffiffiffi  pffiffiffiffiffiffiffiffiffi 
Zin ¼ mr =εr tan h jð2pfd=cÞ εr mr (4)
214 B. Kuang et al. / Carbon 127 (2018) 209e217

Fig. 6. Proposed reaction mechanism for rGO reduced by VC. The oxygen-containing functional groups removed in the second, third and fourth drawing are marked in blue, green
and purple color, respectively; Vacancy defects are marked in red color. (A colour version of this figure can be viewed online.)

Fig. 7. The real part (a)e(c) and imaginary part (d)e(f) of permittivities of rGO/wax composites over 2e18 GHz. (A colour version of this figure can be viewed online.)

where Zin is the input impedance of the sample, mr the complex
permeability (mr ¼ m0  jm00 ), εr the complex permittivity
(εr ¼ ε0  jε00 ), f the frequency, d the thickness of material and c the
speed of light. Considering the ignorable magnetic properties of
GO/wax and rGO/wax composites, mr is taken as 1.
Fig. 9 shows the RL values of the GO/wax and rGO/wax com-
posites coupled with different loadings at various thicknesses over
2e18 GHz. In overall, the RL values of the composites tend to in-
crease with both increasing reduction degree and increasing
loadings. Among them, the rGO-90-30% composite delivers the
 B. Kuang et al. / Carbon 127 (2018) 209e217 215

Fig. 8. Proposed mechanism of defect-related polarization relaxation (a) and hopping conductivity of electrons (b). (A colour version of this figure can be viewed online.)

largest absorption intensity of 37.2 dB for the absorber with
3.5 mm thickness at 5.92 GHz.
The composites with increased loadings exhibit enhanced EM
absorption capability. The increased rGO loadings constitute more
capacitor-like structure network in the wax matrix and this
network favors the motion of hopping electrons, forming oscilla-
tory current and generating increased conduction loss [55].
Therefore, the microwave absorption properties are obviously
improved from the loading of 10 wt% to 30 wt%, as shown in Fig. 9.
Moreover, the increased reduction degree of rGO is another

Fig. 9. Microwave absorption performances of GO/wax and rGOs/wax composites over 2e18 GHz at different thickness of 1e5 mm. (A colour version of this figure can be viewed
online.)
216 B. Kuang et al. / Carbon 127 (2018) 209e217
factor favor of EM attenuation. At the same loading, the composites
with increased reduction degree of rGO present enhanced RL
values. It is ascribed to the enhanced dielectric loss resulting from
increased vacancy defects (dielectric relaxation) and conductivity
of rGO (conduction loss) during reduction as mentioned above.
Hence, the improvement in microwave attenuation depends on the
loading and reduction degree is caused by the synergistic effect of
conduction loss and dielectric relaxation.
4. Conclusion
In summery, rGO with controllable reduction degrees was ob-
tained by using different contents of VC. Compared to the GO, rGO
exhibits obvious dielectric relaxation behaviors. The dielectric
relaxation of rGO is enhanced by increasing reduction degree of
rGO. The comprehensive investigations demonstrate that the con-
tents of oxygen-containing groups in rGO are greatly decreased
while the vacancy defects are generated during the reduction
process. The results evidence that it is vacancy defects rather than
oxygen-containing groups that contributes to the dielectric relax-
ation behaviors of rGO in the experimental frequency range. This
work provides a deep understanding to the dielectric relaxation
behavior of rGO over 2e18 GHz, which would be of significance in
theory and practice to develop advanced carbon-based EM
attenuators.
Acknowledgements
This study is supported by the National Natural Science Foun-
dation of China under Grant No. 51772029 and 51572027.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.carbon.2017.10.092.
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