J Sol-Gel Sci Technol (2009) 51:169–174
DOI 10.1007/s10971-009-1978-2
ORIGINAL PAPER
A comparative study of hydrothermal and sol–gel methods
in the synthesis of MnO2 nanostructures
Fatemeh Hashemzadeh Æ M. Mehdi Kashani Motlagh Æ
Amir Maghsoudipour
Received: 27 October 2008 / Accepted: 7 April 2009 / Published online: 25 April 2009
Ó Springer Science+Business Media, LLC 2009
Abstract In this work, MnO2 nanostructure powders with
different crystalline phases have been successfully prepared
by hydrothermal and sol–gel methods. The obtained prod-
ucts were characterized by XRD and SEM techniques and
their crystallographic phases and morphological properties
compared. Results showed that a-MnO2, b-MnO2, and
d-MnO2 nanorods were synthesized by hydrothermal
method and c-MnO2 polymorph was obtained by sol–gel
method.
Keywords MnO2 nanostructure
Hydrothermal method

Sol–gel 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], WS2 [2], MX2 (M = Mo or W,
X = S or Se) [3–5] 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
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
been carried out concerning the preparation of MnO2 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 [13–24], owning to its interesting fundamental
physical properties and technological importance. Different
structural forms of MnO2 exist in the nature, such as a, b, c,
and d-type. The different forms of MnO2 are exactly based
on the same structural units [MnO6] octahedral. a-, b-,
c-MnO2 have [MnO6] 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 [MnO6] octahedral.1 Figure 1
shows the schematic diagrams of a-MnO2 (Hollandite),
b-MnO2 (Pyrolusite), d-MnO2 (Birnessite) and c-MnO2
(Nsutite).
Templates or catalysts have been widely used to grow
1-D nanostructures [7, 9], in which templates are used to
confine 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 difficulty for scale-up production of 1-D
nanostructures. Therefore, it would be of value to find
techniques without involving templates or catalysts.1 On
the basis of the redox reactions of MnO4- and/or Mn2?,
several methods have been developed to prepare MnO2
with different crystallographic forms, such as thermal [25],
1
Xun Wang, Yadong Li. Department of Chemistry, Tsinghua
University, Beijing 100084, Peoples’ Republic of China.
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170 J Sol-Gel Sci Technol (2009) 51:169–174

In this work, synthesis of nanostructure MnO2 by

hydrothermal and sol–gel 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

Fig. 1 Schematic diagrams of a a-MnO2 (Hollandite), b b-MnO2
(Pyrolusite), c d-MnO2 (Birnessite), d c-MnO2 (Nsutite)
Analytical grade manganese sulfate hydrate (MnSO4
H2O,
99.99% Merck) and potassium permanganate(VII)
reflux [26–28], hydrothermal [27–30], and sol–gel [31, 32],
(KMnO4, 99% Merck) were used as starting materials.
etc.2
Three different molar ratios of KMnO4/MnSO4 (2.5/1,
Hydrothermal synthesis has been an interesting tech-
2/3, and 6/1) were used to synthesis MnO2 by hydrothermal
nique to prepare materials with different nanoarchitectures
method. So the appropriate amount of manganese sulfate
such as nanowires, nanorods, nanobelts, nanourchins, and
and potassium permanganate were mixed in distilled water
so forth. The main advantage of the hydrothermal tech-
at room temperature to produce a solution. Then the pre-
nique over other soft chemical routes is the ability to
pared solution transferred into a Teflon-lined stainless steel
control the nanostructures ranging from nanoparticles to
autoclave, sealed and maintained at temperatures of 140
nanorods or nanourchins to nanotubes by properly choos-
and 160 °C for different dwell times. After the reaction was
ing the temperature or time of the reaction or the active fill
completed, the resulting brownish-black solid product was
level in the pressure vessel or solvent used for the reaction
filtered off and washed with distilled water to remove ions
without any major structure-directing agents or templates.3
that possibly remaining in the final products. Washing
Xueliang Li and his co-workers reported the hydrothermal
repeated until the pH of the washed water reached to 7. The
synthesis of a-MnO2 nanostructures by a simple hydro-
filtered products finally dried at 100 °C in air.
thermal method.4 Xie and his co-workers also reported the
hydrothermal preparation of MnO2 by using ions and
2.2 Sol–gel synthesis
polymers [33, 34].
Beside hydrothermal synthesis, sol–gel method is a
Manganese acetate (MnAc2
4H2O, 99% Merck) and Citric
simply and low temperature and pressure method for the
acid (C6H708
H2O, 99% Merck) with a molar ratio of 1/2
synthesis of nanostructured metal oxides. Xingyan Wang
were dissolved in distilled water. pH of the solution was
and his co-workers reported sol–gel template synthesis of
adjusted to 6 by addition of ammonia. The solution was
highly ordered MnO2 nanowire arrays.5
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 °C in an electric oven.
2
Synthesis and Formation Mechanism of Manganese Dioxide Then the dried gel was calcined at 380 °C for 12 h in a muffle
Nanowires/Nanorods Xun Wang and Yadong Li. furnace. In order to increase the degree of oxidation, the
3
V. Subramanian, Hongwei Zhu, Robert Vajtai, P. M. Ajayan, and calcined product was acid treated in 2 M H2SO4 solution
Bingqing Wei, Department of Electrical and Computer Engineering with a magnetic stirrer for 2 h at 80 °C. After acid-treatment,
and Center for Computation and Technology, Louisiana State
the product was rinsed with distilled water and filtered.
University, Baton Rouge, Louisiana 70803, and Rensselaer Nano-
technology Center and Department of Materials Science and Engi- Finally the brownish-black manganese dioxide material was
neering, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New obtained after drying the filtered product at 105 °C.
York 12180. The crystalline structures were identified at room tem-
4
Xueliang Li, Wenjie Li, Xiangying Chen, Chengwu Shi, School of perature by powder X-ray diffractometer (philips pw 3710,
Chemical Engineering, Hefei University of Technology, Hefei, Anhui
operated at 40 kV, 30 mA) employing Cu Ka radiation
230009, P R China, Journal of Crystal Growth, 2006, 297, 387–389.
5 (k = 1.5418 Å). Particle morphology of the prepared
Xingyan Wanga, Xianyou Wanga, Weiguo Huanga, P. J. Sebas-
tianb, Sergio Gamboac, Chemistry College, Xiangtan University, MnO2 powders were elucidated by scanning electron
Hunan 411105, China, Journal of Power Sources, 2005, 140,211–215. microscopy (SEM) (S360 Cambridge).

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J Sol-Gel Sci Technol (2009) 51:169–174 171

Table 1 MnO2 nanostructure powders synthesized at different conditions by hydrothermal method (pH = 6)
Sample Molar ratio Temperature [°C] Time [h] Crystalline phase Morphology
KMnO4/MnSO4

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

3 Results and discussion

30

3.1 Discussion about hydrothermal synthesis of MnO2 25

nanostructure powders
20

Intensity
Table 1 illustrates results of X-ray diffraction and SEM
analysis for samples which synthesized by hydrothermal 15

methods. It shows different polymorph of MnO2 (a, b, and

10
c) can be synthesized by hydrothermal method.
For this method the whole reaction of KMnO4 with 5
MnSO4 as starting materials is given in equation (1):
0
2KMnO4 þ 3MnSO4 þ 2H2 O 0 10 20 30 40 50 60 70 80
! 5MnO2 þ K2 SO4 þ 2H2 SO4 ð1Þ 2θ

On the other hand, KMnO4 can decompose in the Fig. 2 XRD pattern of the d-MnO2 nanorods obtained from the
solution and so we get equation(2): KMnO4/MnSO4 reaction system (6/1, 160 °C)

KMnO4 þ ½ð1  x þ 2yÞ=2H2 O

! Kx MnO2
yH2 O þ ð1  xÞKOH þ ½ð3 þ xÞ=4O2
ð2Þ
Suib et al. have prepared a-MnO2 by a similar
hydrothermal method with the same reaction, in which pH
plays an important role in influencing the crystallographic
form of the final products; the b-type was obtained when the
temperature was kept above 120 °C [35]. In the present
work, the MnO2 nanorods with different crystallographic
forms were obtained in a wide temperature range by
different molar ratio of KMnO4 and MnSO4. Fig. 3 SEM image of d-MnO2 nanorods with larger aspect ratios
obtained from the KMnO4/MnSO4 (6/1, 160 °C) reaction system
3.1.1 Consideration the effect of reactant’s molar ratio on
crystallinity and crystal structure of synthesized
powder When the molar ratio of KMnO4/MnSO4 was reduced to
2.5/1, the a-MnO2 phase was formed. Figure 4 illustrates
Figure 2 illustrates XRD pattern of the sample that syn- XRD pattern of the sample that synthesized with KMnO4/
thesized with KMnO4/MnSO4 molar ratio of 6/1 and MnSO4 molar ratio of 2.5/1. It shows the a-MnO2 phase
hydrothermally treated at 160 °C for 4 h. Presence of peaks with 37.46, 28.68 and 12.78 2h peaks was the only crys-
at 12.18, 29.19 and 56.14 two thetas (refer to JCPDS 80- talline phase that can be detected by XRD in the samples
1098) confirms that the d-MnO2 phase is the sole crystal- which synthesized by hydrothermal method.
line phase which can be detected by XRD. SEM micro- a-MnO2 nanorods have mean diameter (D) of 65 nm
graph of this sample in Fig. 3 shows the nonorods (Fig. 5) which was calculated by Sherrer equation
morphology with a high aspect ratio. (D = Kk57.3/b1/2cost). In this equation K is a constant

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172 J Sol-Gel Sci Technol (2009) 51:169–174

80

70

60

50

Intensity
40

30

20

10

0
0 10 20 30 40 50 60 70 80
Fig. 4 XRD patterns of a-MnO2 nanostructures obtained from the
2θ
KMnO4/MnSO4 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. 6 XRD pattern of b-MnO2 nanorods obtained from the KMnO4/
MnSO4 (2/3, 160 °C) reaction system

(&1), whereas k is wave length of the used radiation and

b1/2 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 coefficient of b1/2 to angle
degrees. When the molar ratio of reactants is adjusted to
about 2/3, the reaction results in b-MnO2 phase with dif-
fraction peaks of 28.88, 37.32 and 56.65 2h (Fig. 6).
b-MnO2 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 Fig. 7 SEM micrograph of b-MnO2 nanorods obtained from the
synthesis, since no additional OH- or H? are added to the KMnO4/MnSO4 (2/3, 160 °C) reaction system

Fig. 5 SEM micrograph of

a-MnO2 prepared at different
hydrothermal dwell times: a
room temperature, b 3 h, c 6 h,
d 18 h

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J Sol-Gel Sci Technol (2009) 51:169–174
system and pH does not change much when the molar ratio
is changed. The a-, b- and d-MnO2 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 H2O molecules to be stable. So
d-MnO2 was produced at a higher concentration of K?
ions, and a- and b- MnO2 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-MnO2 (KMnO4/MnSO4:2.5/1)
V. Subramanian et al. synthesized various nanostructures
of MnO2 by a hydrothermal route under mild conditions.3
The XRD patterns of the MnO2 powders which were
prepared at different times have been shown in Fig. 4. The
obtained powder at room temperature showed an amor-
phous MnO2 having peaks evolving to a a-MnO2 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-MnO2 JCPDS 44-0141).
The evolution of the MnO2 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 MnO2 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
35
30
25
Intensity
20
15
10
5
0 depends on the dwell times of hydrothermal process. The
0 10 20 30 40 50 60 70
2θ
Fig. 8 XRD pattern of c-MnO2 synthesized by Sol–Gel method
173
Fig. 9 SEM micrograph of c-MnO2 synthesized by Sol–Gel method
morphological manipulations are the biggest advantage of
hydrothermal technique.
3.2 Discussion about sol–gel synthesis of MnO2
nanostructure powders
The c-MnO2 phase is one of the most important manganese
dioxide polymorphs due to its widespread use in alkaline
Zn-MnO2 cells. The most recent quantitative structural
model for describing the XRD pattern of c-MnO2 has been
proposed by Chabre and Pannetier [36]. Figure 8 shows
X-ray diffraction pattern of powder that synthesized by
sol–gel method. The pattern is similar to that of a typical
commercial electrolytic manganese dioxide (EMD) and the
c-MnO2 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-MnO2 (refer to PDF no.14-0644). Except for
these characteristic peaks, no additional peaks could be
observed, indicating the pure phase of c-MnO2. 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 MnO2 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 MnO2 powders were synthesized with different crys-
tallographic structure of a-, b- and d-MnO2 by hydrother-
mal method which their morphologies depend on the molar
ratio of KMnO4/MnSO4, on the other hand the c-MnO2
phase was synthesized by sol–gel method. It was found that
morphology of the hydrothermally synthesized powder
80
diameters of nanorods synthesized by hydrothermal
method were between 50–100 nm, which was smaller than
those for samples synthesized by sol–gel method.
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174
References
1. Li YD, Wang JW, Deng ZX, Wu YY, Sun XM, Yu DP, Yang PD
(2001) J Am Chem Soc 123:9905
2. Li YD, Li XL, He RR, Zhu J, Deng ZX (2002) J Am Chem Soc
124:1411
3. Tenne R, Margulis L, Genut M, Hodes G (1992) Nature 360:444
4. Feldman Y, Masserman E, Srolovita DJ, Tenne R (1995) Science
267:222
5. Tenne R, Homyonfer M, Feldman Y (1998) Chem Mater 10:3225
6. Pan ZW, Dai ZR, Wang ZL (2001) Science 291:1947
7. Han WQ, Fan SS, Li QQ, Hu YD (1997) Science 277:1287
8. Duan XF, Huang Y, Cui Y, Wang JF, Lieber CM (2001) Nature
409:66
9. Morales AM, Lieber CM (1998) Science 279:208
10. Li YD, Li XL, Deng ZX, Zhou BC, Fan SS, Wang JW, Sun XM
(2002) Angew Chem Int Ed 41:333
11. Dakhel AA (2006) Thin Solid Film 496:353
12. Sanchez L, Farcy J, Pereira-Ramos JP (1996) J Mater Chem 6:37
13. Hsieh Y-C, Lee K-T, Lin Y-P, Wu N-L, Donne SW (2008) J
Power Sources 177:660–664
14. Brousse T, Toupin M, Dugas R, Athouël L, Crosnier O, Bélanger
D (2006) J Electrochem Soc 153:A2171–A2180
15. Brousse T, Taberna P-L, Crosnier O, Dugas R, Guillemet P,
Scudeller Y, Zhou Y, Favier F, Bélanger D, Simon P (2007) J
Power Sources 173:633–641
16. Rios EC, Rosario AV, Mello RMQ, Micaroni L (2007) J Power
Sources 163:1137–1142
17. Li J, Zhitomirsky I (2008) Mater Chem Phys 112:525–530
18. Naoi K, Simon P (2008) Interface 17(1):34
19. Djurfors B, Broughton JN, Brett MJ, Ivey DG (2008) J Mater Sci
38:4817–4830
123
J Sol-Gel Sci Technol (2009) 51:169–174
20. Feng Z-P, Li G-R, Zhong J-H, Wang Z-L, Ou Y-N, Tong Y-X
(2009) Electrochem Commun 11:706–710
21. Wang G-X, Zhang B-L, Yu Z-L, Qu M-Z (2005) Solid State
Ionics 176:1169–1174
22. Reddy RN, Reddy RG (2004) J Power Sources 132:315
23. Sugantha M, Ramakrishman PA, Hermann AM (2003) Int J
Hydrogen Energy 28:597
24. Laurie I, Verbaere A, Guyomard D (2003) J Power Sources 119–
121:226
25. Muraoka Y, Chiba H, Atou T, Kikuchi M, Hiraga K, Syono Y
(1999) J Solid State Chem 144:136–142
26. Kijima N, Yasuda H, Sato T, Yoshimura Y (2001) J Solid State
Chem 159:94–102
27. Xiao TD, Strutt PR, Benaissa M, Chen H, Kear BH (1998)
Nanostruct Mater 10:1051–1061
28. DeGuzman RN, Shen YF, Neth EJ, Suib SL, O’Young CL,
Levine S, Newsam JM (1994) Chem Mater 6:815–821
29. Golden DC, Chen CC, Dixon JB (1986) Science 231:717–719
30. Shen YF, Zerger RP, DeGuzman RN, Suib SL, McCurdy L,
Potter DI, O’Young CL (1993) Science 260:511–515
31. Ching S, Petrovay DJ, Jorgensen ML (1997) Inorg Chem 36:883–
890
32. Ching S, Roark JL, Duan NG, Suib SL (1997) Chem Mater
9:750–754
33. Wu CZ, Xie Y, Wang D (2003) J Phys Chem B 107:13583
34. Li ZQ, Ding Y, Xiong YJ (2005) Cryst Growth Des 5:1953
35. Walanda DK, Lawrance GA, Donne SW (2005) J Power Sources
139:325
36. Chabre Y, Pannetier J (1995) Prog Solid State Chem 23:1