Chemical Engineering Journal 339 (2018) 487–498

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

A facile fabrication and highly tunable microwave absorption of 3D flower- T

like Co3O4-rGO hybrid-architectures
⁎
Junru Maa, Xixi Wanga, Wenqiang Caoa, Chen Hana, Huijing Yangb, Jie Yuanc, Maosheng Caoa,
a
School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
b
Department of Physics, Tangshan Normal University, Tangshan 063000, China
c
School of Information Engineering, Minzu University of China, Beijing 100081, China

H I G H L I G H T S G RA P H I C A L AB S T R A C T

• Ahybrid
facile, green and highly tunable
method is proposed for the first
time.
• interfaces
The flower-like Co O -rGO with multi-
3 4
shows integrated function.
• The unique 3D hierarchical structure
endows efficient microwave absorp-
tion.
• Microwave absorption is investigated
at elevated temperature.
• The microwave response mechanism
is researched.

A R T I C L E I N F O A B S T R A C T

Keywords: Electromagnetic absorption materials have drawn increasing attention owing to their wide applications in
Flower-like Co3O4 military, aerospace, communication and the electronic industry. Efficient microwave absorption with tunable
rGO bandwidth and thermal stability is a great challenge. Herein, we fabricate a novel 3D hierarchical Co3O4-rGO
3D hybrid-architectures hybrid-architecture by a facile, green and highly tunable strategy. The porous Co3O4 flower is assembled uni-
Electromagnetic characterization
formly, introducing great amount of interfaces. Tailoring Co3O4 flowers could improve interfacial polarization
Microwave absorption
and dipole polarization as well as conductive network, highly tuning the hybrid-architectures and electro-
magnetic properties. The reflection loss (RL) reaches −61 dB at Co3O4/rGO ratio of 2:1, as well as frequency-
selective absorption. Furthermore, the RL are relatively stable and the bandwidth is broadened almost covering
the whole investigated frequency at elevated temperature of 353–473 K. The result is ascribed to utilizing multi-
interface magnetic micro-flowers to tune impedance matching, which is accompanied with strong relaxation loss
and electrical loss, as well as magnetic loss. Our work confirms that 3D hierarchical Co3O4-rGO hybrids as a
potential candidate for high-efficiency microwave absorbers in harsh environment, and provide a novel pathway
for designing microwave absorber in the future.

1. Introduction various fields of military and daily life, such as the satellite commu-
nication, broadband radar, information counterwork, and wireless
The electronic information technology has been widely used in electronic devices. The hazards of electromagnetic radiation on the

⁎
Corresponding author.
E-mail address: caomaosheng@bit.edu.cn (M. Cao).

https://doi.org/10.1016/j.cej.2018.01.152
Received 8 December 2017; Received in revised form 24 January 2018; Accepted 30 January 2018
Available online 01 February 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
J. Ma et al.
environment and human health have been increasingly severe, as well
as caused trouble on the security of electronic information on in-
dividuals and countries. Hence, the high-efficiency microwave absor-
bers with thermal stabilities are greatly demanded to attenuate and
even eliminate adverse electromagnetic waves in wide frequency and
temperature ranges [1–6].
Excellent microwave absorption properties can be determined by
complex permittivity and permeability and electromagnetic matching
[7,8]. The microwave absorption materials, including dielectric loss
materials and magnetic loss materials, have been extensively in-
vestigated [9–14]. However, these unilateral loss materials are difficult
to achieve electromagnetic matching. For further enhancement of mi-
crowave absorption, decorating the dielectric loss materials with var-
ious magnetic particles is an efficient method [15–19]. For example,
Fe3O4@TiO2 microspheres exhibit the minimal RL of −23.3 dB at
7 GHz [20]. Nevertheless, the dielectric/magnetic materials with high
density are greatly restricted in practical applications [21]. It is urgent
to develop the more high-efficiency and light-weight microwave ab-
sorption materials with thin matching thicknesses.
As reported in the previous literatures, the microstructure, mor-
phology and physical properties of absorbing materials have an im-
portant effect on light weight for the practical applications. For ex-
ample, Li et al. fabricated Fe3O4 nanofibers and reported that the RL of
23 wt% concentration in paraffin could reach −52 dB at 3 mm [22].
Recently, more attentions are focusing on innovative dielectric mate-
rials, due to their unique electrical properties. Enhancing permittivity
and permeability are both necessary for thinner matching thickness
[23]. Yang et al. reported the rGO/porous Bi2Fe4O9 composites possess
an optimal RL of −72 dB with a sample thickness of 2.0 mm [24].
Carbon nanomaterials, as light weight, low cost and high conductive
materials, are performing tremendous potential in the field of electro-
magnetic attenuation [25,26]. The various carbon materials have been
used as the components in the composites for high-efficiency and light-
weight microwave absorbers [27–33]. The two-dimensional (2D) gra-
phene, with low density, strong mechanical stiffness, large specific
surface area and high charge carrier mobility, has been extensively
investigated as a promising candidate to construct magnetic metals/
graphene composites. Its large specific surface area facilitates the high
and controllable loadings of various magnetic particles, and superior
electrical and thermal conductivity can promote the incident wave
convert into thermal energy for strong attenuation. Furthermore, re-
duced graphene oxide (rGO) with residual defects and functional
groups, which synthesized by chemical reduction from graphene oxide,
can achieve the synergistic effect of polarization loss and conduction
loss. Hence, the rGO can be used as a component of composites, de-
corated with magnetic component to possess excellent microwave ab-
sorption [34–38].
Cobalt oxide (Co3O4) performs unique properties in optical, elec-
trochemistry and so on, leading to great potentials in gas sensors, het-
erogeneous catalysts and Li-ion battery electrodes [39–41]. The Co3O4
nanostructures have been studied, such as nanosphere, nanosheet and
nanoflower, which may have geometrical effects on microwave ab-
sorption [42–45]. Based on the ideas, decorating rGO with three di-
mensional (3D) hierarchical Co3O4 could be an effective approach to
adjust the electromagnetic parameters for proper impedance and strong
microwave absorption.
In this paper, we fabricated porous flower-like Co3O4-rGO hybrid-
architectures by a novel and facile approach. We investigated the
growth from flower-like Co3O4 to Co3O4-rGO hybrid-architectures. The
electromagnetic properties and microwave absorption were discussed
in detail. Moreover, the microwave absorption of the hybrid-archi-
tecture at elevated temperature is studied intensively for a candidate as
promising high-temperature absorber.
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Chemical Engineering Journal 339 (2018) 487–498
2. Experimental
2.1. Materials and reagents
The graphite powder (flake graphite, grade 325) was purchased
from Haida Corporation (Qingdao, China). Cobalt chloride hexahydrate
(CoCl2·6H2O), sodium chloride (NaCl), Hexamethylenetetramine
(C6H12N4), absolute ethyl alcohol (C2H6O), hydriodic acid (HI, 55 wt
%), acetic acid (AcOH) and anhydrous ether (C4H10O) were purchased
from Beijing Chemical Factory (Beijing, China). All the chemical re-
agents were analytically pure.
2.2. Synthesis of flower-like hierarchical Co3O4
The uniform flower-like hierarchical Co3O4 were prepared via a
facile surfactant-free low temperature hydrothermal process. In a ty-
pical experiment, 0.4758 g (2 mmol) of CoCl2·6H2O, 0.5844 g of NaCl
(10 mmol) and 1.6823 g of C6H12N4 (12 mmol) were added into 200 mL
of solvent composed of deionized water and anhydrous ethanol with a
volume ratio of 9:1. Then the solution was stirred for 10 min to obtain a
transparent light pink solution, and subsequently heated at 110 °C for
1 h under the condition of oil bath. After cooling suspension to room
temperature, the obtained green precipitates were collected by cen-
trifugation and washed with deionized water and ethanol for several
times, then air-dried at room temperature. The as-synthesized Co(OH)2
powders were heated at 400 °C for 2 h followed by gradually cooling to
room temperature in air to obtain 3D flower-like Co3O4 powders.
2.3. Synthesis of 3D Co3O4-rGO hybrid-architectures
The GO was obtained by harsh oxidation of the natural graphite
powders according to the modified Hummers method [46,47]. And the
rGO powders were obtained by reducing GO with HI and AcOH, then
dried at room temperature [48]. To obtain Co3O4-rGO hybrids, the
Co3O4 powders were added into rGO suspension with vigorous stirring,
followed by sonication for 1 h to form a homogeneous dispersion. The
obtained black precipitates were collected by centrifugation and wa-
shed with absolute ethanol for several times, finally dried at 60 °C for
12 h.
2.4. Samples preparation for electromagnetic parameters
Typically, the various mass ratios of Co3O4/rGO hybrids changed
from 1:1 to 5:1 for comparative experiments. Then the hybrids (20, 30,
40 and 50 wt%) and paraffin wax (80, 70, 60 and 50 wt%) were dis-
persed into C4H10O with vigorous stirring to evaporate the solution
completely. Finally, the mixtures were pressed into a toroidal shape
with an inner diameter of 3.00 mm, an outer diameter of 7.03 mm and a
thickness of ∼2.00 mm.
The hybrids of 2:1 (50 wt%) and SiO2 xerogel powers (50 wt%) were
added into alcohol solvent with vigorous stirring to evaporate the sol-
vent completely. The SiO2 xerogel was used as the matrix, which in-
creased the thermal stability of sample [49]. According to our previous
works, it had almost no effect on the microwave absorption perfor-
mances [50,51]. Then the prepared mixtures were pressed into a rec-
tangular shape (22.86 mm × 10.16 mm × ∼1.5 mm). The electro-
magnetic parameters of samples were measured at elevated
temperature in air atmosphere.
2.5. Characterization and measurement
The SEM images were characterized on a scanning electron micro-
scope (SEM, Hitachi S-4800), and EDS spectra and mappings were ob-
tained on energy dispersive spectrometer (EDS, Thermo scientific
NORAN system 7). The TEM and HRTEM images were characterized on
a transmission electron microscope (TEM, JEM-2100f) coupled with
J. Ma et al.
copper grids. X-ray powder diffraction (XRD) patterns were identified
on an XPert PRO system (Cu-Kα). The electromagnetic parameters
consisted of complex permittivity/permeability were measured on a
vector network analyser (VNA, Anritsu 37269D) in the frequency range
of 2–18 GHz at the room temperature. Besides, the complex permit-
tivity/permeability was measured at elevated temperature of
353–473 K by the waveguide method in the X band (8.2–12.4 GHz).
3. Results and discussion
3.1. Growth of Co3O4 flowers and Co3O4-rGO hybrid-architectures
The flower-like hierarchical cobalt precursor was synthesized via a
facile and mild process with the co-assistant of solvents (H2O:C2H5OH)
and NaCl. According to the previous reports, the properties of solvents
have an important effect on the solubility, diffusion behavior and re-
activity of reagents and intermediate. It leads to the various morphol-
ogies and microstructures of the samples owing to the trends of redu-
cing the whole system energy [52]. In this case, the final morphology of
cobalt precursor is sensitive to the solvents, which determined by the
volume ratio of water to alcohol (Vw/Va). With the increases of initial
Vw/Va, the cobalt precursors exhibit a strong growth tendency to con-
vert from sheet-like to flower-like nanocrystals. The results indicate
hierarchical flower-like architectures with multiple interior interfaces
at the highest Vw/Va of 9:1. That is, a higher Vw/Va facilitates the
growth of more 3D flower-like hierarchical microstructures with an
appropriate thickness for the minimization of surface energy.
To further investigate the formation multiple interfaces, a probable
mechanism of 3D hierarchical Co3O4 and Co3O4-rGO hybrid-archi-
tectures is illustrated in Fig. 1. First, cobalt precursor gradually form as
nucleation centers in a weak alkaline environment, and nanocrystals
grow faster along with layer structure with the coordination of alcohol
and cobalt ions. Second, a new growing point will appear and new
nanoplates vertically grow on initial nanoplates, resulting in the for-
mation of interfaces as shown in Fig. 1a and b. Fig. 1c and g show that
the small nanoplates are assembled into flower-like nanocrystals with
an average diameter of ∼1 μm at the reaction time of 15 min. It pos-
sesses abundant interior interfaces and vertical growing points. New
petals will gradually grow and a 3D hierarchical flower is self-as-
sembled successfully with more interfaces and thinner nanoplates, as
shown in Fig. 1d and h. Third, Fig. 1e shows that the porous Co3O4 are
obtained from the thermal decomposition by releasing of gas from the
cobalt precursors. The hierarchical Co3O4 and rGO could suspend
Fig. 1. The formation process of the Co3O4-rGO hybrid-architectures.
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Chemical Engineering Journal 339 (2018) 487–498
homogeneously in the solution during the ultrasound process. They
collide with each other, which are beneficial to connection of Co3O4
flowers and rGO layers due to strong interaction between 3d orbits of
Co and graphene [53]. Finally, 3D hierarchical Co3O4-rGO hybrid-ar-
chitectures are well achieved with the assistance of acoustic cavitation
and molecular force in Fig. 1f and i [54].
3.2. Structure and morphology
The microstructures of Co3O4 are analysed in Fig. 2. The Co3O4 with
uniform sizes and morphologies are only 2–3 μm in diameters, and it is
assembled by many 2D cambered nanoplates, generating multiple in-
terfaces in 3D hierarchical microstructures. Fig. 3a and b are the TEM
images of petals of the as-obtained Co3O4 flower. The nanoplates are
ultrathin and porous, due to H2O gases could be released to yield a
number of pores through oxidation process, leading to the formation of
3D hierarchical porous nanostructures. It can effectively reduce density
of Co3O4. Moreover, the lattice spacing in Fig. 3c are 0.2021 nm and
0.2436 nm, corresponding to the (4 0 0) and (3 1 1) crystal planes of
cubic Co3O4, respectively. The SAED pattern in Fig. 3d exhibits a hex-
agonal distribution, indicating the nanoplates have single-crystal
characteristics. Furthermore, the diffraction peaks of XRD pattern in
Fig. 3e are also indexed to cubic structure of Co3O4, which is consistent
with 1D profile pattern in Fig. 3f. All these results demonstrate that
hierarchical Co3O4 are well achieved, which are assembled by porous
single-crystal-like nanoplates [55].
As shown in Fig. 4, the flower-like Co3O4-rGO hybrid-architectures
are fabricated by facile and generic method, which can tailor the
multiple interfaces and conductive networks by various hybrid ratios.
The hierarchical Co3O4 flowers are precisely implanted on the rGO with
large specific surface area, inducing a number of new interfaces and
various conductive networks. Fig. 4a shows the few interfaces between
rGO and Co3O4 flowers. As the addition of Co3O4 flowers, the multiple
interfaces increase gradually. The samples with high hybrid ratios lead
to stack among Co3O4 flowers, which may hinder the conducting
channel on rGO network, as shown in Fig. 4c and d. The rGO na-
nosheets are thin and flexible with wrinkle and crumpled structures, as
shown in Fig. S1.
Figs. 5 and S2 show the element distribution of Co3O4-rGO hybrid-
architectures. The Co, O and C elements uniformly distribute and
overlap each other in the circled area, implying the interconnection of
porous Co3O4 flowers and rGO. The Co3O4 flowers may be implanted
randomly due to the confined sites. Further, the microstructures of
Co3O4-rGO hybrid-architectures are investigated by Raman spectro-
scopy, as shown in Fig. S3. The weak peaks of Co3O4 are consistent with
crystalline structure in the range of 100–800 cm−1, which agrees well
with previous reports [41,45]. D peak and G peak are characteristic
peaks of rGO. The D peak is associated with lattice defects in carbon
atoms or random arrangement of graphite. The D peak is significantly
high, confirming that a number of defects are generated, strengthening
dipole polarization.
As shown in Fig. S4, the static magnetic properties of Co3O4-rGO
hybrids with different ratios are characterized with hysteresis loop. The
saturation magnetization (Ms) is raised by increasing the ratios, which
could be mainly attributed to the increase of Co3O4 [56]. Furthermore,
according to the previous reports, the values of Ms are gradually de-
creased at the elevated temperature [57].
3.3. Electromagnetic properties
According to the Debye theory, real permittivity (ε') represents the
storage ability of electromagnetic energy, and imaginary permittivity
(ε″) represents the electromagnetic energy loss ability. The dielectric
loss could be determined by polarization loss and conductive loss,
clarified by the following equations [23,58],
J. Ma et al. Chemical Engineering Journal 339 (2018) 487–498

Fig. 2. The SEM images of (a–d) 3D flower-like Co3O4 with different magnifications.

Fig. 3. (a, b) TEM images, (c) HRTEM image, (d) SAED pattern, (e) XRD pattern, and (f) diffraction profile generated by the SAED pattern of 3D flower-like Co3O4.

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Fig. 4. The SEM images and schematic diagrams of Co3O4-rGO samples with different Co3O4/rGO ratios of (a) 1:1, (b) 2:1, (c) 3:1 and (d) 4:1.

εs−ε∞ where εs is the static dielectric constant, ε∞ is the relative dielectric

ε′ = ε∞ +
1 + ω2τ 2 (1) constant at the high-frequency limit, ω is the angular frequency, σ is the
εs−ε∞ σ electrical conductively, and τ is the polarization relaxation time which
ε″ = ωτ + are the function of frequency and temperature.
1 + ω2τ 2 ωε0 (2)

Fig. 5. (a) The SEM image and (b) corresponding weight percentage histogram of the Co3O4-rGO samples; The elemental mapping images of (c) Co, (d) O, (e) C and (f) Si.

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Fig. 6. (a) The real permittivity, (b) imaginary permittivity and (c-f) Cole-Cole plots of the Co3O4-rGO samples with different Co3O4/rGO ratios. The insets are the single relaxation
process.
The ε′ and ε″ of Co3O4-rGO hybrid-architectures with different hy-
brid ratios of Co3O4/rGO were investigated in the frequency range of
2–18 GHz, as shown in Figs. 6a and b and S5. Both of them decrease
gradually as the ratio of Co3O4 is raised, which change from 20.88 to
4.39 and 24.35 to 0.57, respectively. They present a declined trend with
increasing frequency. For ε″, two relaxation peaks locate at ∼12 GHz
and ∼15 GHz, ascribed to the dipole polarization and interfacial po-
larization. The dipole polarization results from the bound charges of
Co3O4 flowers and function groups/defects of rGO. The interfacial po-
larization exists in abundant interfaces in Co3O4 flowers, as well as
interfaces between Co3O4 flowers and rGO [23]. They are further
confirmed by the Cole-Cole plots showing analogical semicircles in the
enlarged insets of Fig. 6c–f [59]. In addition, the slopes of Cole-Cole
plots become smooth with the increase of Co3O4/rGO ratios, indicating
the decreased conductivity.
The real permeability (μ') and imaginary permeability (μ″) are
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Chemical Engineering Journal 339 (2018) 487–498
shown in Fig. 7. They both trend to decline with the increase of fre-
quency, changing from 1.15 to 0.93 and 0.24 to 0.01, respectively. As
the ratio of Co3O4 rises, the values of μ′ change a little, while μ″ has a
rising tendency. It indicates the hybrid ratios may have stable influence
on magnetic loss. Meanwhile, the multiple magnetic resonance peaks
for μ″ are observed obviously. As reported in the previous literature
[11], resonance frequencies could be determined by effective aniso-
tropy field, which depend on the magneto-crystalline anisotropy, the
size and geometry of Co3O4 flowers and the dipole interaction between
the nanoplates of Co3O4 crystals. The peaks at ∼4 GHz may be owing to
natural resonance, and the peaks in high frequency may arise from
exchange resonance. Therefore, the magnetic loss of flower-like Co3O4-
rGO consists of natural resonance, exchange resonance and eddy cur-
rent loss (Fig. S6).
The magnetic loss tangent (tan δm) and dielectric loss tangent (tan
δe) are shown in Fig. S7. The value of tan δe decreases rapidly with the
J. Ma et al. Chemical Engineering Journal 339 (2018) 487–498

Fig. 7. The complex permeability versus frequency of Co3O4-rGO samples with different Co3O4/rGO ratios.

Fig. 8. 3D RL plots of Co3O4-rGO samples versus frequency and thickness with different Co3O4/rGO ratios of (a) 1:1, (b) 2:1, (c) 3:1 and (d) 4:1 under the 50% loadings.

ratios change from 1:1 to 3:1, while it tends to steady from 3:1 to 5:1. In
addition, the tan δe reduces relatively slowly with the increase of fre-
quency. This provides possibilities for the design of impedance
matching, further promoting the penetration of electromagnetic waves
and leading to optimal microwave attenuation.
3.4. Microwave absorption properties
The microwave absorption properties of Co3O4-rGO hybrid-archi-
tectures are illustrated in Fig. 8. It is calculated based on transmission
line theory, which determined by complex permittivity and complex
permeability. The corresponding RL equations as below [60],

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Fig. 9. 3D RL plots of Co3O4-rGO samples versus frequency and thickness with (a) 20%, (b) 30%, (c) 40% and (d) 50% loadings at the ratio of 2:1.

Fig. 10. 3D RL plots of Co3O4-rGO samples versus frequency and thickness at T = (a) 353 K, (b) 393 K, (c) 433 K and (d) 473 K at the ratio of 2:1.

RL = 20log10
|Zin−Z0 | impedance of free space, εr and μr are the complex permittivity and
|Zin + Z0 | (3) permeability of the absorber, respectively. f is the microwave fre-
quency, c is the velocity of light, and d is the thickness of absorber.
μr 2π The as-constructed flower-like Co3O4-rGO hybrid is an effective
Zin = tanh ⎡j μr εr fd⎤
εr ⎣ c ⎦ (4) microwave absorber with highly tunable bandwidth and great stability
at elevated temperature. As shown in Fig. 8, it features multi-band
where Zin is the normalized input impedance of the absorber, Z0 is the

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J. Ma et al.
Fig. 11. (a) Reflection loss of 3D flower-like Co3O4; (b–e) Reflection loss of Co3O4-rGO samples versus frequency with different Co3O4/rGO ratios; (f) The bandwidth and minimal
reflection loss of Co3O4-rGO samples with different Co3O4/rGO ratios.
absorption and frequency-selective absorption. Adding the implanta-
tion of Co3O4 flowers, the absorption peaks shift toward higher fre-
quency, obviously improving the absorption capacity. The RL reaches
up to −61 dB at the ratio of 2:1. The microwave absorption of the
hybrid-architecture is further investigated in Figs. 9 and S8, exhibiting
advantages of multiple tuning strategies, including hybrid ratio and
filling concentration of Co3O4-rGO hybrids as well as thickness of
sample. The absorption peaks of Co3O4-rGO composites shift to lower
frequency as well as lower thickness with the increasing of Co3O4-rGO,
leading to significantly thin matching thickness of 2.4 mm. The optimal
RL value is improved by raising filling concentration, because the
content of absorbing materials in matrix is increased, with better for-
mation of 3D conductive networks. Meanwhile, more interfaces and
dipoles are induced leading to strengthen electromagnetic attenuation.
Moreover, changing thickness could promote the effective absorption
band covering ∼75% of the whole investigated frequency, as shown in
Fig. 9d.
Fig. 10 shows microwave absorption of Co3O4-rGO hybrid-archi-
tectures with the ratio of 2:1 at elevated temperature. The Co3O4-rGO
architectures possess high efficiency and thermal stability. As the
temperature rises, the values of RL are enhanced to −38 dB, followed
by gradual attenuation. The bandwidth can reach 4.1 GHz with a
thickness of 1.9 mm at the elevated temperature. It covers almost the
whole investigated X-band frequency, which is attributed to the
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Chemical Engineering Journal 339 (2018) 487–498
enhanced conduction loss. The electrons are active at elevated tem-
perature, leading to enhanced conduction loss and strengthened at-
tenuation of incident wave. The optimal RL reaches the −38.3 dB at the
393 K with thickness of 1.8 mm. These results demonstrate that the
porous flower-like Co3O4-rGO hybrid is a fascinating practical micro-
wave absorber, especially at elevated temperature.
Figs. 11 and 12 describe absorption mechanism of the porous
flower-like Co3O4-rGO hybrid-architectures. As shown in Fig. 11a, the
3D flower-like Co3O4 possess RL of -5 dB, almost all arising from the
dipole and interfacial polarizations. To implant Co3O4 flowers onto
rGO, absorption capacitors could be well tuned, due to the great tai-
loring-ability of multiple interfaces and conductive network. Actually,
reported literatures have proposed a model of Aggregation-Induced
Charge Transport (AICT) which is well applicable to our flower-like
Co3O4-rGO hybrid [61,62]. As shown in Fig. 11b–f, the Co3O4 flowers
and rGO will connect with others to form a conductive network, in-
creasing the conduction loss. Tailoring implantation of Co3O4 flower,
the hybrid-architectures present the optimal RL of −61 dB with broad
bandwidth of ∼4 GHz. This is significantly higher than pure Co3O4
flower or rGO samples [26,60].
Electromagnetic attenuation consists of relaxation loss, conduction
loss, natural resonance, exchange resonance and eddy current loss.
Higher conductivity may leads to a poor absorption capacity due to
strong reflection towards incident wave on the first surface, as shown in
J. Ma et al.
Fig. 12. Schematic illustrations of the (a) High Concentration with Good Conductivity Network, (b) Failure in Constructing Conductive Network, (c) Net Model, (d) Charge Transport, (e)
Multiple Interface Polarization and (f) Dipole Polarization in the Co3O4-rGO hybrid-architectures.
Fig. 12a. However, to decrease conductivity will result in weak at-
tenuation, owing to the dramatically decreased conduction loss, as
shown in Fig. 12b. As for an excellent microwave absorber, relaxation
loss plays an important role. The 3D hierarchical flower-like Co3O4
features great amount of interfaces. These multiple interfaces can
generate capacitor-like structures, as reported by previous models,
bringing strong relaxation loss arising from multiple interfacial polar-
ization [26,63]. It is easy for rGO to construct conductive networks in
matrix due to the high conductivity and large specific surface. There-
fore, to implant Co3O4 flowers on rGO layers could achieve outstanding
electromagnetic attenuation as realizing good impedance matching, as
shown in Fig. 12c–f.
The Co3O4 flowers act as multiple polarization centers, especially
interfacial polarization. Additionally, Co3O4 flowers also induce great
dipole polarization, since defects and functional groups appear on the
edges of plentiful holes of their petals [60]. To implant Co3O4 flowers
may affect the electron hopping on rGO conductive networks. That is,
tailoring implantation of Co3O4 flowers could tune the impedance
matching as bringing strong relaxation loss not only in Co3O4 flowers
but between Co3O4 flowers and rGO layers. Implantation of Co3O4 also
introduces magnetic loss, as well as strengthens multi-scattering and
multi-reflection in flower-like Co3O4-rGO networks. Therefore, com-
pare to the other Co-based composites (Table S1) and graphene-based
composites (Table S2), implanting Co3O4 flowers and tailoring the hy-
brid ratio are effective for inducing multiple polarization centers,
tuning conductive network and impedance matching, leading to multi-
advantage integration of outstanding absorption with broadened
bandwidth and smaller thickness at elevated temperature. This is an
effect, especially generic and green approach to obtain excellent mi-
crowave absorption.
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Chemical Engineering Journal 339 (2018) 487–498
4. Conclusions
In summary, a facile, generic and highly tunable strategy is pro-
posed to achieve outstanding microwave absorption. The 3D hier-
archical Co3O4 flower features multiple interfaces and holes, providing
strong interfacial and dipole polarization. Utilizing this multi-interface
and porous magnetic flower to tune the impedance matching is sig-
nificantly effective for companying with strong relaxation loss and
magnetic loss, as well as reducing the density. The RL reaches up to
−61 dB. Moreover, its microwave absorption is stable at the elevated
temperature ranging from 353 to 473 K, along with broadened band-
width almost covering the whole investigated frequency. The porous
flower-like Co3O4-rGO hybrid-architecture is a promising absorption
material with high efficiency, tunable bandwidth and thermal stability.
Our findings open up a horizon for designing absorbers, especially at
elevated temperature.
Acknowledgements
This work was supported by National Natural Science Foundation of
China (No. 11774027, 11574261, 11604237, 51372282 and
51132002).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cej.2018.01.152.
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