ARTICLE

pubs.acs.org/JPCC

Morphology-Controlled Synthesis and Novel Microwave

Absorption Properties of Hollow Urchinlike R-MnO2
Nanostructures
Min Zhou, Xin Zhang, Jumeng Wei, Shuli Zhao, Long Wang, and Boxue Feng*
School of Physical Science and Technology and Key Laboratory for Magnetism and Magnetic Materials of Ministry of Education,
Lanzhou University, Lanzhou 730000, People's Republic of China

bS Supporting Information
ABSTRACT: Three types of hollow urchinlike R-MnO2 nano-
structures, namely, columnar nanorod clusters, tetragonal nano-
tube clusters, and tetragonal nanorod clusters, have been
synthesized through a facile hydrothermal method. The micro-
structure and morphologies of the resulting materials were
investigated by X-ray diffraction, scanning electron microscopy,
transmission electron microscopy, and selected-area electron
diffraction, and the microwave absorption properties of these
nanostructures were investigated in terms of complex permittivity
and permeability. The results indicate an obvious magnetic loss
in the manganese oxide/paraffin wax composites. The tetragonal nanorod clusters exhibit enhanced microwave absorption properties
compared with columnar nanorod clusters and tetragonal nanotube clusters, which result from proper electromagnetic impedance
matching. These urchinlike manganese oxide nanostructures are considered to have great potential applications as microwave absorbents.

’ INTRODUCTION 25 nm display a strongest absorption peak of -27.1 dB at

Microwave absorption materials are of crucial importance in
solving the expanding electromagnetic interference problems caused
by the development of wireless communications and high-frequency
circuit devices in the gigahertz range. Conventional microwave
absorbents, such as magnetic ferrites, usually have high densities,
which limits their widespread applications. In addition, carbon
nanotubes1,2 and conducting polymers3,4 display good abilities
for microwave absorption, but the fabrication of these materials
involves complex processes. Therefore, it is desirable to exploit
new microwave absorption materials that are lightweight and
easy to synthesize and exhibit strong absorption in a wide range.
Recently, considerable research attention has been focused on
nanostuctured transition-metal oxides,5-8 which show highly
efficient microwave absorption properties because of their strong
dielectric loss. Microwave absorption properties of transition-
metal oxides often depend strongly on their morphologies. In
particular, enhanced microwave absorption properties can be
obtained from hierarchical nanomaterials with complicated geom-
etrical morphologies. For instance, Cao et al. found that cagelike
ZnO nanostructures exhibit relatively strong microwave absorption
in the X band, compared with ZnO nanoparticles.7 In another example,
the microwave absorption performance of ZnO dendritic nano-
structures was found to be better than that of ZnO nanowires.8
Manganese oxides have attracted great interest because of
their wide applications in energy storage,9 molecular sieves,10 and
catalysts.11 A few recent studies showed that manganese oxides
could also be used as microwave absorption materials. Yan et al.
reported that γ-Mn3O4 nanoparticles with diameters of about
3.1 GHz.12 Duan's group has studied the microwave absorption
properties of MnO2 nanomaterials prepared under different con-
ditions.13-16 Manganese oxides with hierarchical nanostructures
might be good candidates for microwave absorbents, yet their
microwave absorption properties have not been extensively studied.
Moreover, morphology-controlled synthesis of manganese oxide
nanostructures might offer an avenue to understanding the role
that morphology plays in affecting the corresponding microwave
absorption performance.
As one of the most attractive hierarchical architectures, on
the other hand, urchinlike manganese oxide nanostructures have
displayed enhanced physical and chemical properties.17-20 How-
ever, the synthesis of urchinlike nanostructures that consist of
morphology-controlled one-dimensional nanomaterials through
a simple route is still a challenge. Herein, we report a facile route
for preparing three types of hollow urchinlike R-MnO2 nano-
structures, namely, columnar nanorod clusters, tetragonal nano-
rod clusters, and tetragonal nanotube clusters. The microwave
absorption properties of these nanostructures with different
morphologies were investigated in terms of complex permittivity
and permeability. Manganese oxide urchins consisting of tetrag-
onal nanorods exhibit the best microwave absorption perfor-
mance among the three products. Furthermore, magnetic loss
was found to be important for the loss mechanisms.
Received: July 17, 2010
Revised: December 5, 2010

r XXXX American Chemical Society A dx.doi.org/10.1021/jp106652x | J. Phys. Chem. C XXXX, XXX, 000–000
The Journal of Physical Chemistry C ARTICLE

’ EXPERIMENTAL METHODS
Synthesis. All chemicals were of analytical grade and were
used without further purification. To prepare hollow urchinlike
R-MnO2 columnar nanorod clusters, a 30 mL aqueous solution
containing 2 mmol of KMnO4 and 10 mL of 1.0 M HCl aqueous
solution was transferred into a 46 mL Teflon-lined stainless steel
autoclave and kept at 150 °C for 6 h. The product was filtered,
washed with distilled water and ethanol, vacuum dried at 80 °C
for 6 h, and labeled as sample A. By decreasing the volume of HCl
aqueous solution to 3 mL, hollow urchinlike R-MnO2 tetragonal
nanotube clusters were formed and labeled as sample B. Hollow
urchinlike R-MnO2 tetragonal nanorod clusters were synthesized by
altering the volume of HCl aqueous solution to 3 mL and the
hydrothermal temperature to 120 °C and labeled as sample C.
Characterization. The as-synthesized products were charac-
terized by X-ray powder diffraction (XRD) on a Rigaku D/Max-2400 Figure 1. XRD patterns of samples (a) A, (b) B, and (c) C.
diffractometer using Ni-filtered Cu KR1 irradiation. Scanning
electron microscopy (SEM) measurements were obtained on a
Hitachi S-4800 field-emission scanning electron microscope.
Transmission electron microscopy (TEM) and selected-area
electron diffraction (SAED) measurements were carried out on
a JEM-2010 transmission electron microscope.
The composite samples used for measurements of relative
permittivity and permeability were prepared by mixing the
products and paraffin wax in a mass ratio of 1:1. The mixtures
were then pressed into toroidal-shaped samples (jout = 7.00 mm,
jin = 3.04 mm). The complex permittivity (εr = ε0 - jε00 ) and
permeability (μr = μ0 - jμ00 ) of the mixtures in the 0.1-18 GHz
frequency range were recorded on an Agilent E8363B vector
network analyzer. The reflection loss was calculated according to
the transmission line theory,21 expressed as follows
RL ¼ 20 logjðZin - Z0 Þ=ðZin þ Z0 Þj ð1Þ

Zin ¼ Z0 ðμr εr Þ1=2 tanh½jð2πfd=cÞðμr εr Þ1=2  ð2Þ

where f is the frequency of the electromagnetic wave, d is the thick-

ness of the absorber, c is the velocity of light, Z0 is the impedance
of free space, and Zin is the input impedance of the absorber.

’ RESULTS AND DISCUSSION

The phase and purity of the resulting materials were tested by
XRD. For sample A, all of the diffraction peaks from Figure 1a can
be indexed to the tetragonal phase of R-MnO2 (JCPDS 44-0141,
a = 9.784 and c = 2.863 Å). The products obtained with
decreased solution acidity (samples B and C) were also found to
be R-MnO2 but with less purity (Figure 1b,c, respectively).
Because poorly crystallized δ-MnO2 is formed in the initial step
of the reaction and a higher concentration of Hþ is favorable for
the phase transition from δ- to R-MnO2,17 therefore, the broad
peaks at 2θ angles between 20° and 30° in the patterns of samples
B and C indicate the presence of δ-MnO2, which is not dissolved.
The details of the formation process will be discussed later.
The morphologies of the products prepared under different
conditions were examined by SEM. Figure 2a shows that sample
A exhibits an urchinlike shape with the diameter of about 6 μm
and consists of straight and radially grown nanorods. Further
observation (Figure 2b) reveals that these nanorods have a
quasicolumnar shape. For sample B, well-defined urchins with
diameters of 4-5 μm are observed, as shown in Figure 2c.
Figure 2d reveals that these urchinlike nanostructures consist of
B dx.doi.org/10.1021/jp106652x |J. Phys. Chem. C XXXX, XXX, 000–000
Figure 2. SEM images of samples (a,b) A, (c,d) B, and (c,d) C.
tetragonal nanotubes with tetragonal open ends. Decreasing the
temperature of hydrothermal treatment to 120 °C (sample C)
leads to the formation of urchinlike nanorod clusters, as shown in
Figure 2e. The clear tetragonal cross section of a nanorod in
sample C is observed in Figure 2f.
The TEM images of samples A (Figure 3a), B (Figure 3c), and
C (Figure 3e) indicate that they have homogeneous hollow
structures. It can be noticed that sample B (Figure 3d) consists
of one-dimensional nanotubes, whereas samples A (Figure 3b)
and C (Figure 3f) consist of nanorods. These results agree well
with those of the SEM studies. The SAED pattern (Figure 3g)
of a single nanorod from sample C suggests it to be single-
crystalline. HRTEM analysis (Figure 3h) shows a lattice spacing
of about 0.5 nm, which corresponds to the interplanar distance
of (200) planes. The SAED and HRTEM patterns demonstrate
that the nanorods grow along the [001] axis. The SAED and
HRTEM patterns of samples A and B (not shown) are rather
The Journal of Physical Chemistry C
Figure 3. TEM images of samples (a,b) A, (c,d) B, and (e,f) C. (g) SAED
pattern and (h) HRTEM image of sample C.
similar to those of sample C, implying they have the same growth
direction.
On the basis of our observations of the time-dependent
evolutions of morphology (Figure S1, Supporting Information)
and crystallinity (Figure S2, Supporting Information), the mecha-
nisms by which the hollow urchinlike R-MnO2 nanostructures were
formed can be explained using the Ostwald ripening process.19,20
In the initial stage, a large number of flowerlike δ-MnO2 micro-
spheres were formed. Then, R-MnO2 nanorods grew along
[001] on the microspheres. Meanwhile, because δ-MnO2 is a
metastable phase and the inner core has a higher surface energy,
the δ-MnO2 microspheres were dissolved from inside to outside.
The rapid growth of nanorods and the dissolution of δ-MnO2
microspheres led to the formation of the hollow urchinlike nano-
rod clusters. For samples B and C, δ-MnO2 was not completely
dissolved because of the lower acidity of the solutions, as sug-
gested above. Moreover, the evolution process of the nanotubes
in sample B (Figure S3, Supporting Information) reveals that the
formation of the nanotubes can be proposed as “etching” of the
nanorods from the tips toward the interior along the [001] axis.22,23
Because the top areas of the nanorods are polar metastable (001)
C dx.doi.org/10.1021/jp106652x |J. Phys. Chem. C XXXX, XXX, 000–000
ARTICLE
Figure 4. Reflection loss curves of different composites at different thick-
nesses, consisting of mixed paraffin wax with samples (a) A, (b) B, and (c) C.
surfaces, it is more stable for the product to form hollow nano-
tubes with reduced metastable top areas.
The microwave absorption properties of these R-MnO2 nano-
structures were investigated by mixing the samples and paraffin
wax in a mass ratio of 1:1. Figure 4 shows the reflection loss (RL)
data for the sample/paraffin wax composites. The values of
minimum RL for samples A-C are -36 dB at 2.9 GHz with
a thickness of 3.8 mm, -21 dB at 4.9 GHz with a thickness of
3.0 mm, and -41 dB at 8.7 GHz with a thickness of 1.9 mm,
respectively. The minimum RL of -41 dB obtained from sample
C is much better than that of other manganese oxides reported
before.12,13 Moreover, by adjusting the thickness of the absorber,
the absorption bandwidths with RL lower than -10 dB (90%
absorption) of samples A-C are up to 4.6, 5.4, and 8.7 GHz. It is
worth noting that sample C displays enhanced microwave
absorption properties in terms of both the minimum RL value
and the absorption bandwidth compared with samples A and B.
To understand the possible microwave absorption mechanisms,
the real (ε0 ) and imaginary (ε00 ) parts of the relative permittivity
The Journal of Physical Chemistry C
Figure 5. (a) Real and (b) imaginary parts of relative permittivity and
(c) dielectric loss tangents of the sample/paraffin wax composites.
of different composites were investigated in the frequency range
of 0.1-18 GHz, as shown in Figure 5a,b. The ε0 curve of each
sample (Figure 5a) exhibits a decrease from 0.1 to 18 GHz, with
a small fluctuation in the range of 13-15 GHz. Meanwhile,
the values of ε00 (Figure 5b) exhibit abrupt decreases at low
frequency and then increase along with the frequency. In
addition, the ε00 curves of both samples A and C display obvious
fluctuations in the range of 14-18 GHz, suggesting the occurrence
of strong resonance. Figure 5c shows the dielectric loss tangents
(tan δε = ε00 /ε0 ) of samples A-C, in which the maximum values
of tan δε are 0.88, 0.82, and 0.26, respectively.
The relatively high values of ε00 and tan δε imply that the
hollow urchinlike R-MnO2 nanostructure/paraffin wax compos-
ites exhibit intense dielectric losses, which should be attributed
to such mechanisms as dominant dipolar polarization, interfacial
polarization and associated relaxation phenomena.24 Further-
more, we introduced a microcircuit model to explain the different
dielectric loss performances among different samples. The inner
walls of the urchinlike nanostructures can be considered as microloops,
D dx.doi.org/10.1021/jp106652x |J. Phys. Chem. C XXXX, XXX, 000–000
ARTICLE
Figure 6. (a) Real and (b) imaginary parts of relative permeability and
(c) magnetic loss tangents of the sample/paraffin wax composites.
whereas the actinomorphic one-dimensional manganese oxides
can be considered as numerous antennas that convert electro-
magnetic waves into vibrating microcurrent. Hence, micro-
current can be produced in the microloops, which leads to dielectric
resonant peaks in the ε00 curves. Compared with nanorods, nano-
tubes, which have a smaller cross-sectional area, exhibit a feebler
microcurrent intensity, thus resulting in weaker dielectric losses
in the nanotube clusters. The presence of poorly crystallized
δ-MnO2 might deteriorate the dielectric properties of the com-
posites. As a result, sample A exhibits the best dielectric loss values
whereas sample B exhibits the worst among the three of them.
Generally, MnO2 nanostructures are antiferromagnetic materials,
in which magnetic loss is negligibly small and dielectric loss
dominates the loss mechanisms.5 In this work, however, sample
C exhibits largely enhanced microwave absorption properties
compared with sample A despite the fact that the latter has higher
ε00 and tan δε values. According to eqs 1 and 2, the contribution
of magnetic loss to the loss mechanisms thus should be taken into
account. To confirm this assumption, the real (μ0 ) and imaginary
(μ00 ) parts of the relative permeability and the magnetic loss
The Journal of Physical Chemistry C
tangents (tan δμ = μ00 /μ0 ) of all samples are presented in Figure 6.
The μ0 values (Figure 6a) of all samples are about 1.0 and exhibit
a slow decline. The μ00 values (Figure 6b) fluctuate around zero at
low frequency, and strong peaks can be observed in the curves of
samples A and C in the range of 14-18 GHz. The maximum tan
δμ values of samples A and C (Figure 6c) are 0.22 and 0.27,
respectively, which are much higher than those of sample B and
other manganese oxides reported in the literature.12,13 Previous
reports showed that magnetic behavior can be disturbed by the
dielectric behavior at microwave frequency.25,26 Furthermore,
one can clearly see that the locations of the strong peaks in the μ00
curves for samples A and C are rather similar to those of ε00 . Thus,
the strong peaks in the μ00 curves are believed to be related to the
resonances in ε00 . The magnetic loss is supposed to indicate that
magnetic energy is transferred into electric energy and finally
dissipates in the composites. More experimental work is needed
to verify this proposal.
Therefore, we suggest that the loss mechanisms of the hollow
urchinlike R-MnO2 nanostructures consist of both dielectric and
magnetic losses. Because the electromagnetic impedance match-
ing requires that the magnetic loss and the dielectric loss be equal,
compared with sample A, impedance matching is more satisfied
in sample C, because of its relatively low tan δε values and high
tan δμ values. The enhanced microwave absorption perfor-
mance of sample C thus results from a proper electromagnetic
impedance matching.
’ CONCLUSIONS
In summary, a facile hydrothermal process was developed
to synthesize hollow urchinlike R-MnO2 nanostructures with con-
trollable morphologies. Columnar nanorod clusters, tetragonal
nanorod clusters, and tetragonal nanotube clusters could be obtained
by tuning the reaction conditions. Excellent microwave absorp-
tion performances were observed in the R-MnO2 nanostructure/
paraffin wax composites. The tetragonal nanorod clusters display
enhanced microwave absorption properties compared with
columnar nanorod clusters and tetragonal nanotube clusters.
Moreover, for the first time, we discovered that not only dielectric
loss, but also magnetic loss contributes to the loss mechanisms in
manganese oxides. A proper electromagnetic impedance match-
ing leads to the enhanced microwave absorption of the tetragonal
nanorod clusters. Considering the low-cost and facile synthesis
process of manganese oxide urchins, the present study offers
promising materials for microwave absorption.
’ ASSOCIATED CONTENT
bS Supporting Information. Time-dependent evolutions of
morphology and crystallinity of the hollow urchinlike R-MnO2
nanostructures and evolution process of the nanotubes. This
material is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Tel.: þ86-931-8912719. Fax: þ86-931-8913554. E-mail: fengbx@
lzu.edu.cn.
’ ACKNOWLEDGMENT
This work was supported by the National Science Foundation
of China (Grants 60536010 and 61006001). The authors appreciate
Xuhui Xu and De Yan for useful discussions.
E dx.doi.org/10.1021/jp106652x |J. Phys. Chem. C XXXX, XXX, 000–000
ARTICLE
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