ORI GI NAL PAPER

A comparative study of hydrothermal and solgel methods

in the synthesis of MnO
2
nanostructures
Fatemeh Hashemzadeh M. Mehdi Kashani Motlagh
Amir Maghsoudipour
Received: 27 October 2008 / Accepted: 7 April 2009 / Published online: 25 April 2009
Springer Science+Business Media, LLC 2009
Abstract In this work, MnO
2
nanostructure powders with
different crystalline phases have been successfully prepared
by hydrothermal and solgel methods. The obtained prod-
ucts were characterized by XRD and SEM techniques and
their crystallographic phases and morphological properties
compared. Results showed that a-MnO
2
, b-MnO
2
, and
d-MnO
2
nanorods were synthesized by hydrothermal
method and c-MnO
2
polymorph was obtained by solgel
method.
Keywords MnO
2
nanostructure Hydrothermal method
Solgel method Morphology
1 Introduction
In recent years, there has been considerable interest on
fabrication of one-dimensional (1-D) nanostructured
materials such as Bi [1], WS
2
[2], MX
2
(M = Mo or W,
X = S or Se) [35] nanotubes, semiconducting oxides
nanobelts [6], and GaN [7], InP [8], Ge [9], W [10]
nanowires, for their potential uses in mesoscopic research
and in the development of nanodevices. However, com-
paratively few studies, to the best of our knowledge, have
been carried out concerning the preparation of MnO
2
1-D
nanostructures.
1
Manganese dioxide has attracted special attention in
technological applications, such as selective heterogeneous
catalysts, battery materials [11, 12] and electrochemical
capacitors [1324], owning to its interesting fundamental
physical properties and technological importance. Different
structural forms of MnO
2
exist in the nature, such as a, b, c,
and d-type. The different forms of MnO
2
are exactly based
on the same structural units [MnO
6
] octahedral. a-, b-,
c-MnO
2
have [MnO
6
] chains in their structures, and are
typical of 1 9 1, 2 9 2, 1 9 2 1D channels, respectively,
while d-type is well known for its layer structure, which is
composed of edge-sharing [MnO
6
] octahedral.
1
Figure 1
shows the schematic diagrams of a-MnO
2
(Hollandite),
b-MnO
2
(Pyrolusite), d-MnO
2
(Birnessite) and c-MnO
2
(Nsutite).
Templates or catalysts have been widely used to grow
1-D nanostructures [7, 9], in which templates are used to
conne the growth of wires, while catalysts may act as the
energetically favorable sites for the adsorption of reactant
molecules. However, the introduction of templates or cat-
alysts to the reaction system will greatly complicate the
process, and increases the production cost, and thus
increases the difculty for scale-up production of 1-D
nanostructures. Therefore, it would be of value to nd
techniques without involving templates or catalysts.
1
On
the basis of the redox reactions of MnO
4
-
and/or Mn
2?
,
several methods have been developed to prepare MnO
2
with different crystallographic forms, such as thermal [25],
F. Hashemzadeh M. Mehdi Kashani Motlagh (&)
Department of chemistry, Iran University of science and
technology, Tehran, Iran
e-mail: M.Kashani@iust.ac.ir
F. Hashemzadeh
e-mail: Fa_Hashemzadeh@chem.iust.ac.ir
A. Maghsoudipour
Material and energy research center, Tehran, Iran
e-mail: a-maghsoudi@merc.ac.ir
1
Xun Wang, Yadong Li. Department of Chemistry, Tsinghua
University, Beijing 100084, Peoples Republic of China.
1 3
J Sol-Gel Sci Technol (2009) 51:169174
DOI 10.1007/s10971-009-1978-2
reux [2628], hydrothermal [2730], and solgel [31, 32],
etc.
2
Hydrothermal synthesis has been an interesting tech-
nique to prepare materials with different nanoarchitectures
such as nanowires, nanorods, nanobelts, nanourchins, and
so forth. The main advantage of the hydrothermal tech-
nique over other soft chemical routes is the ability to
control the nanostructures ranging from nanoparticles to
nanorods or nanourchins to nanotubes by properly choos-
ing the temperature or time of the reaction or the active ll
level in the pressure vessel or solvent used for the reaction
without any major structure-directing agents or templates.
3
Xueliang Li and his co-workers reported the hydrothermal
synthesis of a-MnO
2
nanostructures by a simple hydro-
thermal method.
4
Xie and his co-workers also reported the
hydrothermal preparation of MnO
2
by using ions and
polymers [33, 34].
Beside hydrothermal synthesis, solgel method is a
simply and low temperature and pressure method for the
synthesis of nanostructured metal oxides. Xingyan Wang
and his co-workers reported solgel template synthesis of
highly ordered MnO
2
nanowire arrays.
5
In this work, synthesis of nanostructure MnO
2
by
hydrothermal and solgel methods has been reported and
also crystallographic and morphological properties of the
products have been compared. In addition effect of molar
ratio of the reactants and dwell time of hydrothermal
reaction on crystallinity nature and morphological proper-
ties of the resulting nanostructured materials in hydro-
thermal method have been considered.
2 Experimental procedure
2.1 Hydrothermal synthesis
Analytical grade manganese sulfate hydrate (MnSO
4
H
2
O,
99.99% Merck) and potassium permanganate(VII)
(KMnO
4
, 99% Merck) were used as starting materials.
Three different molar ratios of KMnO
4
/MnSO
4
(2.5/1,
2/3, and 6/1) were used to synthesis MnO
2
by hydrothermal
method. So the appropriate amount of manganese sulfate
and potassium permanganate were mixed in distilled water
at room temperature to produce a solution. Then the pre-
pared solution transferred into a Teon-lined stainless steel
autoclave, sealed and maintained at temperatures of 140
and 160 C for different dwell times. After the reaction was
completed, the resulting brownish-black solid product was
ltered off and washed with distilled water to remove ions
that possibly remaining in the nal products. Washing
repeated until the pH of the washed water reached to 7. The
ltered products nally dried at 100 C in air.
2.2 Solgel synthesis
Manganese acetate (MnAc
2
4H
2
O, 99% Merck) and Citric
acid (C
6
H
7
0
8
H
2
O, 99% Merck) with a molar ratio of 1/2
were dissolved in distilled water. pH of the solution was
adjusted to 6 by addition of ammonia. The solution was
heated up to 80 C and stirred with a magnetic stirrer and
kept this temperature for several hours until a wet gel was
obtained. The wet gel was dried at 110 Cin an electric oven.
Then the dried gel was calcined at 380 Cfor 12 h in a mufe
furnace. In order to increase the degree of oxidation, the
calcined product was acid treated in 2 M H
2
SO
4
solution
with a magnetic stirrer for 2 h at 80 C. After acid-treatment,
the product was rinsed with distilled water and ltered.
Finally the brownish-black manganese dioxide material was
obtained after drying the ltered product at 105 C.
The crystalline structures were identied at room tem-
perature by powder X-ray diffractometer (philips pw 3710,
operated at 40 kV, 30 mA) employing Cu Ka radiation
(k = 1.5418 A

). Particle morphology of the prepared

MnO
2
powders were elucidated by scanning electron
microscopy (SEM) (S360 Cambridge).
Fig. 1 Schematic diagrams of a a-MnO
2
(Hollandite), b b-MnO
2
(Pyrolusite), c d-MnO
2
(Birnessite), d c-MnO
2
(Nsutite)
2
Synthesis and Formation Mechanism of Manganese Dioxide
Nanowires/Nanorods Xun Wang and Yadong Li.
3
V. Subramanian, Hongwei Zhu, Robert Vajtai, P. M. Ajayan, and
Bingqing Wei, Department of Electrical and Computer Engineering
and Center for Computation and Technology, Louisiana State
University, Baton Rouge, Louisiana 70803, and Rensselaer Nano-
technology Center and Department of Materials Science and Engi-
neering, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New
York 12180.
4
Xueliang Li, Wenjie Li, Xiangying Chen, Chengwu Shi, School of
Chemical Engineering, Hefei University of Technology, Hefei, Anhui
230009, P R China, Journal of Crystal Growth, 2006, 297, 387389.
5
Xingyan Wanga, Xianyou Wanga, Weiguo Huanga, P. J. Sebas-
tianb, Sergio Gamboac, Chemistry College, Xiangtan University,
Hunan 411105, China, Journal of Power Sources, 2005, 140,211215.
170 J Sol-Gel Sci Technol (2009) 51:169174
1 3
3 Results and discussion
3.1 Discussion about hydrothermal synthesis of MnO
2
nanostructure powders
Table 1 illustrates results of X-ray diffraction and SEM
analysis for samples which synthesized by hydrothermal
methods. It shows different polymorph of MnO
2
(a, b, and
c) can be synthesized by hydrothermal method.
For this method the whole reaction of KMnO
4
with
MnSO
4
as starting materials is given in equation (1):
2KMnO
4
3MnSO
4
2H
2
O
! 5MnO
2
K
2
SO
4
2H
2
SO
4
1
On the other hand, KMnO
4
can decompose in the
solution and so we get equation(2):
KMnO
4
1 x 2y=2H
2
O
! K
x
MnO
2
yH
2
O 1 xKOH 3 x=4O
2
2
Suib et al. have prepared a-MnO
2
by a similar
hydrothermal method with the same reaction, in which pH
plays an important role in inuencing the crystallographic
form of the nal products; the b-type was obtained when the
temperature was kept above 120 C [35]. In the present
work, the MnO
2
nanorods with different crystallographic
forms were obtained in a wide temperature range by
different molar ratio of KMnO
4
and MnSO
4
.
3.1.1 Consideration the effect of reactants molar ratio on
crystallinity and crystal structure of synthesized
powder
Figure 2 illustrates XRD pattern of the sample that syn-
thesized with KMnO
4
/MnSO
4
molar ratio of 6/1 and
hydrothermally treated at 160 C for 4 h. Presence of peaks
at 12.18, 29.19 and 56.14 two thetas (refer to JCPDS 80-
1098) conrms that the d-MnO
2
phase is the sole crystal-
line phase which can be detected by XRD. SEM micro-
graph of this sample in Fig. 3 shows the nonorods
morphology with a high aspect ratio.
When the molar ratio of KMnO
4
/MnSO
4
was reduced to
2.5/1, the a-MnO
2
phase was formed. Figure 4 illustrates
XRD pattern of the sample that synthesized with KMnO
4
/
MnSO
4
molar ratio of 2.5/1. It shows the a-MnO
2
phase
with 37.46, 28.68 and 12.78 2h peaks was the only crys-
talline phase that can be detected by XRD in the samples
which synthesized by hydrothermal method.
a-MnO
2
nanorods have mean diameter (D) of 65 nm
(Fig. 5) which was calculated by Sherrer equation
(D = Kk57.3/b
1/2
cost). In this equation K is a constant
Table 1 MnO
2
nanostructure powders synthesized at different conditions by hydrothermal method (pH = 6)
Sample Molar ratio
KMnO
4
/MnSO
4
Temperature [C] Time [h] Crystalline phase Morphology
1 2.5/1 Room temperature 24 a Flower-like nanowiskers
2 2.5/1 140 3 a Plate like morphology
3 2.5/1 140 6 a Plate like morphology and nanorods
4 2.5/1 140 18 a Nanorods
5 2/3 160 4 b Nanorods
6 6/1 160 4 d Nanorods
0
5
10
15
20
25
30
0 10 20 30 40 50 60 70 80
I
n
t
e
n
s
i
t
y
2
Fig. 2 XRD pattern of the d-MnO
2
nanorods obtained from the
KMnO
4
/MnSO
4
reaction system (6/1, 160 C)
Fig. 3 SEM image of d-MnO
2
nanorods with larger aspect ratios
obtained from the KMnO
4
/MnSO
4
(6/1, 160 C) reaction system
J Sol-Gel Sci Technol (2009) 51:169174 171
1 3
(&1), whereas k is wave length of the used radiation and
b
1/2
is broadness of peak with maximum intensity in half
height. Also, t is the wave number of peak with maximum
intensity and 57.3 is inversion coefcient of b
1/2
to angle
degrees. When the molar ratio of reactants is adjusted to
about 2/3, the reaction results in b-MnO
2
phase with dif-
fraction peaks of 28.88, 37.32 and 56.65 2h (Fig. 6).
b-MnO
2
phase has nanorod morphology with diameters of
45 nm (Fig. 7) (from Sherrer equation). It might be
believed that the reaction (1) only occurs at the molar ratio
of 2/3, while a combination of reactions (1) and (2) occurs
simultaneously at molar ratios of 2.5/1 and 6/1. The con-
centration of K
?
ions may be the key to phase controlled
synthesis, since no additional OH
-
or H
?
are added to the
Fig. 4 XRD patterns of a-MnO
2
nanostructures obtained from the
KMnO
4
/MnSO
4
reaction system (2.5/1) at (a) room temperature, and
hydrothermally at 140 C for different times: (b) 3 h, (c) 6 h, (d) 18 h
Fig. 5 SEM micrograph of
a-MnO
2
prepared at different
hydrothermal dwell times: a
room temperature, b 3 h, c 6 h,
d 18 h
0
10
20
30
40
50
60
70
80
0 10 20 30 40 50 60 70 80
I
n
t
e
n
s
i
t
y
2
Fig. 6 XRD pattern of b-MnO
2
nanorods obtained from the KMnO
4
/
MnSO
4
(2/3, 160 C) reaction system
Fig. 7 SEM micrograph of b-MnO
2
nanorods obtained from the
KMnO
4
/MnSO
4
(2/3, 160 C) reaction system
172 J Sol-Gel Sci Technol (2009) 51:169174
1 3
system and pH does not change much when the molar ratio
is changed. The a-, b- and d-MnO
2
phases have [2 9 2],
[1 9 1] tunnels and layer structures, respectively. The K
?
ion can serve as a template in the formation of these tunnel
or layer structures, therefore the different structures can be
formed by different amounts of K
?
. Layer structures may
need more cations or H
2
O molecules to be stable. So
d-MnO
2
was produced at a higher concentration of K
?
ions, and a- and b- MnO
2
were obtained at comparatively
lower K
?
concentrations when the molar ratio was adjusted
to 2.5/1 and 2/3, respectively.
2
3.1.2 Effect of different dwell times on hydrothermal
synthesis of a-MnO
2
(KMnO
4
/MnSO
4
:2.5/1)
V. Subramanian et al. synthesized various nanostructures
of MnO
2
by a hydrothermal route under mild conditions.
3
The XRD patterns of the MnO
2
powders which were
prepared at different times have been shown in Fig. 4. The
obtained powder at room temperature showed an amor-
phous MnO
2
having peaks evolving to a a-MnO
2
structure
(Fig. 4a). There is an increase in crystallinity with respect
to the increase of hydrothermal dwell time from 3 to 18 h,
as evidenced by the appearance of sharper peaks. As can be
seen from the Fig. 4c, all the peaks of the sample prepared
at a dwell time of 6 h can be indexed to a pure tetragonal
phase (space group I4/m of a-MnO
2
JCPDS 44-0141).
The evolution of the MnO
2
nanostructures prepared at
different hydrothermal dwell times is clearly shown in
SEM micrographs of Fig. 5. It can be seen from the Fig. 5,
there is a strong correlation between time and morphology
of the resulting nanostructure powder. For the powder
prepared at room temperature, there are largely agglom-
erated nanowhiskers of MnO
2
which change to nano-
structured plate like morphology with few rods evolving on
hydrothermal treatment after 3 and 6 h. Further increasing
of the hydrothermal reaction time to 18 h leads to forma-
tion of large amount of individual nanorods. All these
morphological manipulations are the biggest advantage of
hydrothermal technique.
3.2 Discussion about solgel synthesis of MnO
2
nanostructure powders
The c-MnO
2
phase is one of the most important manganese
dioxide polymorphs due to its widespread use in alkaline
Zn-MnO
2
cells. The most recent quantitative structural
model for describing the XRD pattern of c-MnO
2
has been
proposed by Chabre and Pannetier [36]. Figure 8 shows
X-ray diffraction pattern of powder that synthesized by
solgel method. The pattern is similar to that of a typical
commercial electrolytic manganese dioxide (EMD) and the
c-MnO
2
reported in the literature [35]. The diffraction
peaks occurred at 37.55, 22.88, 42.50, 55.96 and 67.30 two
thetas, respectively, should be assigned to the characteristic
peaks for c-MnO
2
(refer to PDF no.14-0644). Except for
these characteristic peaks, no additional peaks could be
observed, indicating the pure phase of c-MnO
2
. The visible
broad peaks and unsmooth basal of diffraction pattern
suggest that the material may possess a nanostructure with
some amorphous nature.
Figure 9 shows SEM micrograph of the MnO
2
sample.
It can be seen from Fig. 9 that the material is composed of
particles that their surface is covered with needle-like
nanorods.
4 Conclusion
The MnO
2
powders were synthesized with different crys-
tallographic structure of a-, b- and d-MnO
2
by hydrother-
mal method which their morphologies depend on the molar
ratio of KMnO
4
/MnSO
4
, on the other hand the c-MnO
2
phase was synthesized by solgel method. It was found that
morphology of the hydrothermally synthesized powder
depends on the dwell times of hydrothermal process. The
diameters of nanorods synthesized by hydrothermal
method were between 50100 nm, which was smaller than
those for samples synthesized by solgel method.
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70 80
I
n
t
e
n
s
i
t
y
2
Fig. 8 XRD pattern of c-MnO
2
synthesized by SolGel method
Fig. 9 SEM micrograph of c-MnO
2
synthesized by SolGel method
J Sol-Gel Sci Technol (2009) 51:169174 173
1 3
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