Materials Letters 79 (2012) 288–291

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

MnO2 Nanosheet-Assisted Hydrothermal Synthesis of β-MnO2 Branchy Structures

Junli Zhou, Lin Yu ⁎, Ming Sun, Bang Lan, Fei Ye, Jun He, Qian Yu
Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, PR China

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

Article history: Branchy structures of β-MnO2 were prepared through a two-step process including MnO2 nanosheet-assisted
Received 21 February 2012 hydrothermal synthesis of branchy γ-MnOOH precursor and followed by calcination of the obtained precursor.
Accepted 11 April 2012 After the calcination, the branchy feature was retained for β-MnO2 with two types of the end structures, i.e.,
Available online 19 April 2012
pyramidate ends and opened ends. The assembly and shedding mechanism was proposed to explain the
formation of the branchy structure. This nanosheet-assisted hydrothermal method studied here offers a new
Keywords:
MnO2 nanosheet
approach for synthesis of other layered materials. Furthermore, the decolorization experiments of methyl blue
Branchy β-MnO2 (MB) showed that the obtained β-MnO2 exhibited excellent ability to remove the MB dye with the assistance
Hydrothermal process of hydrogen peroxide.
Particles © 2012 Elsevier B.V. All rights reserved.
Crystal growth

1. Introduction
MnO2 exists in many polymorphic forms (such as α, β, γ, δ), because
the basic unit [MnO6] octahedral can be linked together in different
ways. Nowadays, α-, β- and γ-MnO2 with different morphologies,
such as nanowires, nanorods, spheres, etc., have already been synthe-
sized by a variety of methods [1–3]. Among the various morphologies
of manganese oxides, the branchy MnO2 has been a focus of research
[4,5]. The conventional synthetic method involves the reaction of
MnII (MnSO4) and oxidizing agent (KMnO4, NaClO3) via the hydrother-
mal method. Permanganate or other manganese salts (e.g., MnSO4) is
generally used, and thus introducing the metal cation (e.g., K +, Na +),
which would affect the crystal and the morphologies of the final
product.
Herein, we report a novel synthetic route of branchy β-MnO2 di-
rected by a MnO2 nanosheet-assisted hydrothermal process followed
by a calcination treatment. MnO2 nanosheets here were used directly
as a reactant rather than permanganate or manganese salt to prepare
the MnOOH precursor. Therefore, no metal ions were introduced into
the lattice structure during the reaction process. More importantly,
the β-MnO2 maintained the branchy morphology of the γ-MnOOH
precursor, which is different from those in the previous report [5].
Specifically, some branches were found to have sunk structures, with
some pyramidate ends closed and others opened. The formation
mechanism leading to the branchy γ-MnOOH precursor and its
conversion to β-MnO2 with the same branchy structure are also
discussed. Moreover, simply by altering the calcination conditions,
the as-synthesized MnOOH precursor was transformed into MnO2,
⁎ Corresponding author. Tel.: + 86 20 39322202; fax: + 86 20 39322231.
E-mail address: gych@gdut.edu.cn (L. Yu).
Mn2O3 or Mn3O4, three of the most common manganese oxides [2,6].
And these manganese oxides are usually a strong oxidizing agent. To
investigate the catalytic oxidation ability of the obtained branchy
β-MnO2, the decolorization of MB was chosen as a probe reaction.
2. Experimental
MnO2 nanosheets were prepared using the same method as previous-
ly reported [7]. The MnO2 nanosheets thus obtained were mixed with
SDBS (sodium dodecyl benzene sulphonate) solution (0.15 mol L− 1)
under stirring. The resulting solution was adjusted to pH=4.05 and
then heated at 160 °C for 24 h. The solid precipitate was centrifuged,
washed and then dried at 60 °C for 12 h, which can be indexed to mono-
clinic MnOOH (manganite, JCPDS No. 41–1379) as characterized by XRD
(Fig. 1h). The MnOOH was calcined at 400 °C for 2 h to form the branchy
β-MnO2. (The instrument characterization information is attached in
the supplementary data.)
Decolorization experiment of the MB: The original solution was pre-
pared by adding 2.0 mL H2O2 (30%) to 100 mL MB solution (20 mg/L),
then 10 mg branchy β-MnO2 was added into the solution. The mixture
reacts at room temperature under stirring. A small quantity of reaction
mixture (e.g., 5 mL) was taken out from the reaction vessel at definite
intervals until the end of the reaction and then centrifuged to remove
the catalyst before UV analysis.
3. Results and discussion
SEM images show that the γ-MnOOH displays the branchy structure
(Fig. 1a). Monorods, tripods, tetrapods, pentapods and hexapods can be
found in the sample (Fig. 1c–g). The hexapods have six branches with
a length of 3.0–7.8 μm and a plane angle of 59.7° between adjacent
branches (Fig. 1g). Most of the branches of these multipods possessing

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 J. Zhou et al. / Materials Letters 79 (2012) 288–291 289

Fig. 1. SEM images of branchy γ-MnOOH: (a) low magnification image; (b) high-magnification image. The subsequent images were the variously shaped particles: (c) monopod;
(d) tripod; (e) tetrapod; (f) pentapod; (g) hexapod. (h) XRD patterns of the branchy γ-MnOOH. High-magnification image of the closed ends (i) and the open ends (ii). Schematic
diagram illustrates how the pyramidate ends are formed (iii).

Fig. 2. (a and b) SEM images of branchy β-MnO2. (c) The XRD pattern of branchy β-MnO2. (d) High-magnification image of the hexapods sample.
290 J. Zhou et al. / Materials Letters 79 (2012) 288–291

clear edges as tetragonal prism are usually several micrometers in

length. Interestingly, as shown in the SEM images (Fig. 1b–h), some
branches were found to have sunk structures, with some pyramidate
ends closed and other ends opened (indicated with arrows). The for-
mation of the γ-MnOOH branchy structures is of considerable interest
and will be discussed later.
SEM images of the branchy β-MnO2 are presented in Fig. 2. The
products keep the branchy morphology as the γ-MnOOH precursor
(Fig. 2a and b), which could be indexed to a pure tetragonal phase
(space group P42/mnm) of β-MnO2 with lattice constants a = 4.399 Å
and c = 2.874 Å (JCPDS 24–0735) as characterized by XRD (Fig. 2c).
Also in Fig. 2d, the angles between adjacent branches of the hexapods
and the length of two branches are indicated. The angles between any
adjacent branches are almost 60°.
The vibrational spectroscopic methods, Raman spectroscopy, afford
useful supplements to XRD for the transformation from γ-MnOOH to
β-MnO2 (Fig. 3). The RS spectrum of γ-MnOOH shows well main
peaks at 563 and 626 cm− 1. However, the RS spectrum of β-MnO2
shows one main peak at 661 cm− 1 attributing to the stretching mode
of the Mn–O lattice and three small peaks at 273, 538 and 631 cm− 1
attributing to the deformation modes of the metal–oxygen chain of
Mn–O–Mn in the MnO2 octahedral lattice [8]. The sharp differences
on RS properties between γ-MnOOH and β-MnO2 indicate that the
transformation from γ-MnOOH to β-MnO2 has occurred.
The growth process of the branchy γ-MnOOH was similar to the
previous report [9]. However, in our study, some branches were
found to have sunk structures, with some pyramidate ends closed
and other ends opened (shown by arrows in Figs. 1 and 2 above).
Specially, the pyramidate ends and the opened ends coming from
γ-MnOOH were observed in the magnification image (Fig. 1i and ii).
It can be seen that the size and shape of the pyramidate ends are
matched well with that of the opened ends. Therefore, it can be inferred
that the nanorods spontaneously crystallizes and grows together with
a co-axis in an inlaid manner in the initial stage, while some inlaid
pyramids become separated during the growth of the crystals. The inte-
rior pyramid separates from the complex structures and leaves a
hole in the exterior shell, which is depicted in the scheme of Fig. 1iii. Fig. 4. (a) UV‐vis absorption spectra of the (MB + H2O2 + as-prepared β-MnO2)
Therefore, this may account for the co-existence of the pyramidate solution as a function of time. (b) Time profiles of MB decolorization.
ends and the opened ends in the sample. The whole process for the
growth of the branchy γ-MnOOH may be concluded as nucleation- strength of [MnO6] octahedral with two long and four short Mn–O
growth-assembling-recrystallization-shedding [10]. bonds in γ-MnOOH is stronger than that in β-MnO2. In the calcination
On the other hand, after calcination, the β-MnO2 maintains the bran- process, γ-MnOOH can be oxidized to β-MnO2, while the orientation
chy structure of the precursor γ-MnOOH. This may be because the β- of the octahedral framework still remains.
MnO2 and γ-MnOOH have the same arrangement of the chains of To investigate the catalytic oxidation ability of the obtained branchy
[MnO6] octahedral [11]. However, the difference is that the elongation β-MnO2, the decolorization of MB with the assistance of H2O2 was
chosen as a probe reaction. The UV‐vis spectra of the MB solution as
well as the decolorization rate at different reaction time are shown
in Fig. 4a and b. The characteristic absorption peak of MB decreased
gradually with the time prolonged. Moreover, the original absorp-
tion maximum at 663 nm shifted to 656, 654 and 648 nm after
reaction for 5, 15 and 60 min, respectively. The blue shifts of the
absorption band indicated the catalytic degradation of MB [12].
Within 150 min, the characteristic absorption peak became very
broad and weak, suggesting the high efficiency for decolorization
of MB. As shown in Fig. 4b, it could be seen that in the absence
of β-MnO2 (only MB + H2O2), no obvious dye decolorization was
observed after 150 min. When the as-prepared β-MnO2 was added to
the solution, obvious decolorization occurred. Remarkably, the use of
β-MnO2 as an efficient catalyst allowed the decolorization rate to
reach 58% in only 2 min and as high as 80% in 120 min.

4. Conclusions

The branchy β-MnO2 from the branchy γ-MnOOH precursor has

been prepared through a MnO2 nanosheet-assisted hydrothermal
Fig. 3. Raman spectrum of the branchy γ-MnOOH and β-MnO2. process followed by a calcination treatment. The advantages of the
 J. Zhou et al. / Materials Letters 79 (2012) 288–291 291

method for synthesizing branchy β-MnO2 lie in its reactant using
nanosheets, which may be extended to other kinds of layered materials.
The branchy structures with pyramidate ends and opened ends were
formed through the assembling and shedding route. The as-prepared
β-MnO2 shows excellent ability to remove organic pollutants and is
expected to show potential applications.
Acknowledgements
This work was supported by Natural Science Foundation of
Guangdong Province (10251009001000003) and the 211 Project of
Guangdong Province.
Appendix A. Supplementary material
[10] Ding YS, Shen XF, Gomez S, Luo H, Aindow M, Suib SL. Hydrothermal growth of
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.matlet.2012.04.055.
[11] Zhang Y, Liu Y, Guo F, Hu Y, Liu X, Qian Y. Single-crystal growth of MnOOH and
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