Materials Letters 86 (2012) 18–20

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

Manganese oxides with different crystalline structures: Facile hydrothermal

synthesis and catalytic activities
Ming Sun, Bang Lan, Lin Yu n, Fei Ye, Wei Song, Jun He, Guiqiang Diao, Yuying Zheng
School 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: Manganese oxides with different crystalline structures, namely a-, b-, and g-, were synthesized by a
Received 24 April 2012 facile hydrothermal method and characterized by X-ray powder diffraction (XRD), surface area
Accepted 3 July 2012 analyzer, scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy
Available online 11 July 2012
(XPS) and hydrogen temperature-programmed reduction (H2-TPR) techniques. The dimethyl ether
Keywords: combustion was used as a probe reaction to explore the crystalline phase effect of the manganese
Manganese oxide oxides. The results revealed that a-MnO2 with nanorod shape possesses higher catalytic activity
Nanocrystalline materials compared to the other two manganese oxides. Their different catalytic activities for dimethyl ether
Oxdation combustion have also been discussed in terms of surface areas, crystalline structures and oxygen
Raman
mobilities.
& 2012 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

Crystalline phase and morphology greatly influence the phy-
sical and chemical activities of nanomaterials [1]. Recently, Mou
et al. [2] reported that nano Fe2O3 showed apparent crystal-phase
effect in the reaction of NO reduction, and g-Fe2O3 nanorod was
more active than a-Fe2O3. Bau et al. [3] also reported that uniform
octahedral Cu2O showed higher activity in CO oxidation than
cubic Cu2O. These studies showed that the structure–activity
relationship is important for nanomaterials.
Manganese oxides with many types of crystalline structures
such as a-, b-, g- and d-, have been extensively studied due to
their structural varieties and excellent chemical characteris-
tics [4]. The electrochemical performance of manganese oxides,
such as specific capacitance or electro-catalytic activity for oxy-
gen reduction, is highly dependent on the crystalline phase and
morphology [5–7]. However, the relationship between manga-
nese oxide crystalline phase and its catalytic activity is seldom
reported [8]. To further explore the structure/catalytic perfor-
mance relationship, we synthesized a-, b-, and g-MnO2 with 1D
tunnel structure via a facile hydrothermal method, and the
crystalline phase effect on catalytic combustion of dimethyl ether
(DME) was discussed.
n
Corresponding author. Tel.: þ86 20 39322202; fax: þ 86 20 39322231.
E-mail addresses: gych@gdut.edu.cn, hukis@126.com (L. Yu).
The protocol of Mn2 þ oxidation was used to prepare different
types of manganese oxide by adjusting oxidant (KMnO4 and
KClO3), Mn2 þ salts (MnSO4 and MnCl2), mole ratio of oxidant to
Mn2 þ , reaction temperature and time. To synthesize a-MnO2,
MnSO4 (7.4 mmol) and KMnO4 (5.6 mmol) were put into 18 ml
distilled water adjusted by concentrated nitric acid (pH¼1–2),
then transferred into a 25 ml Teflon-lined stainless steel auto-
clave, sealed and maintained at 160 1C for 24 h. To synthesize
g-MnO2, MnCl2  4H2O (1 mmol), KClO3 (1.5 mmol) and 15 ml
distilled water were put into the autoclave and maintained at
140 1C for 12 h. For synthesis of b-MnO2, MnCl2  4H2O (1 mmol),
KClO3 (0.75 mmol) and 15 ml distilled water were put into the
autoclave and maintained at 180 1C for 12 h. After the reaction
was complete, the solid precipitate was washed with distilled
water, and then dried at 60 1C for 12 h to get the product.
The details of characterization are supplied in the Supplementary
data. The catalytic test is as reported elsewhere [9].
3. Results and discussion
The XRD patterns of MnO2 are shown in Fig. 1. From the XRD
patterns, the products are indexed to be pure a-MnO2 (JCPDS 29-
1020), g-MnO2 (JCPDS 14-0644), and b-MnO2 (JCPDS 24-0735).
b-MnO2 shows a perfect crystalline structure for its clear diffrac-
tion peaks. However, a- and g-MnO2 display relatively poor
crystalline phase. Based on the different configurations of the
basic [MnO6] octahedral unit, MnO2 can show polymorphs [10].

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.07.011
 M. Sun et al. / Materials Letters 86 (2012) 18–20 19

Fig. 1. XRD patterns of the manganese oxides.

a-MnO2 has (2  2) tunnels constructed from the double chains of

[MnO6] octahedral sharing their corners with each other parallel to
the a-b plane [11]. g-MnO2 has the intergrowth of (1  1) tunnels
and (1  2) tunnels constructed from [MnO6] octahedral with edge
or corner sharing [12]. b-MnO2 has (1  1) tunnels composed of
single chains of the [MnO6] octahedral [13]. The difference in
crystal structure of MnO2 could possibly affect their catalytic
properties.
The Raman bands of MnO2 are determined by the [MnO6]
octahedral environments; thus we can use Raman spectra to
identify the structure of the different crystalline phases. Raman
bands in the range between 200–500 cm  1 and 500–700 cm  1 are
assigned to the Mn–O–Mn bending vibrations in the MnO2 lattice
and the Mn–O stretching of [MnO6] octahedral, respectively [14].
As shown in Fig. 2, the Raman spectra of a-MnO2 feature four main
bands at 187, 391, 585 and 645 cm  1. The two sharp Raman bands
at 585 and 645 cm  1 are indicative of a well-developed tetragonal
structure with a (2  2) tunnel [15]. The g-MnO2 shows six Raman
peaks at 281, 496, 529, 584, 660 and 767 cm  1. The band at 584
cm  1 is indicative of a well-developed orthorhombic structure with Fig. 2. Raman spectra of the manganese oxides.
(1  2) tunnel [16]. The b-MnO2 displays three sharp peaks at 539,
664 and 767 cm  1. The Raman band at 767 cm  1 is attributed to
the antisymmetric Mn–O vibrations, and the band at 664 cm  1 is MnO2 or Mn2O3 to Mn3O4, while the high temperature peak is due
assigned to the A1g mode and is indicative of a well-developed to the reduction of Mn3O4 to MnO [12]. It can be seen from Fig. 4
rutile-type framework [16–18]. that reducibility of MnO2 is in the order: a-MnO2 4 g-MnO2 4
The surface properties of manganese oxides were studied by b-MnO2. The higher reducibility means the higher mobility of
the XPS technique (Supplementary data, Fig. s1). The binding oxygen species in a catalyst; therefore, a-MnO2 has the highest
energy for Mn 2p3/2 was around 642.3 eV, indicating the presence oxygen mobility.
of Mn(IV) ions in the oxide [19]. The O 1s spectra centered at The catalytic activities of manganese oxides for DME combus-
529.5 eV are ascribed to surface lattice oxygen [8]. tion are shown in Fig. 5. It is clear from Fig. 5 that a-MnO2
The MnO2 shows various shapes as displayed in Fig. 3. The displays the best catalytic performance with a light-off tempera-
a-MnO2 exhibits nanorod morphology with the length in the ture (T10, the temperature acquired for 10% DME conversion) at
range of 200–400 nm and the diameter between 15 and 30 nm, 167 oC and a full-conversion temperature (T90, the temperature
and its specific surface area is the largest (54.9 m2/g). The g-MnO2 acquired for 90%) at 180 oC. For g- and b-MnO2, the T10 are 205
has an urchinlike shape and consists of straight and radially and 250 oC; the T90 are 270 and 285 oC, respectively. Obviously,
grown nanorods with a surface area of 3.1 m2/g. The b-MnO2 the catalytic activities decrease in the following order: a- 4 g-
shows an irregular morphology with polyhedron particles and 4 b-MnO2, and this sequence is the same as the one of CO
short rod with the smallest surface area of 1.6 m2/g. oxidation result [8], but slightly different compared with the
H2-TPR experiments were used to explore the redox property reported electrochemical oxygen reduction activity [7]. As
of manganese oxide (Fig. 4). The TPR profile of a-MnO2 shows one reported [9], large surface area favors catalytic activity in com-
big overlapping peak with the lowest peak temperature. However, bustion, and a-MnO2 has the largest surface area; thus it exhibits
g-MnO2 has two separated reduction peaks centered at 254 and superior activity. Moreover, the channel dimensions decrease in
363 oC. The b-MnO2 presents similar TPR profile as g-MnO2 with a the following order: a-4 g-4 b-MnO2, and a-MnO2 has the
low temperature peak at 274 oC and a high temperature peak at largest tunnel size and thus may favor the DME absorption and
386 oC. The low temperature peak is caused by the reduction of reaction. Last but not the least, the mobility of oxygen species is
20 M. Sun et al. / Materials Letters 86 (2012) 18–20
Fig. 3. SEM images of the manganese oxides.
Fig. 4. H2-TPR profiles of the manganese oxides.
Fig. 5. Catalytic activities of manganese oxides for DME combustion.
important for combustion activity, and the order of the catalytic
combustion activity correlates fairly well with the reducibility
order. In summary, the crystalline phase of the MnO2 is a key
factor that dominates their catalytic activities for DME combustion.
4. Conclusions
Manganese oxides with different crystalline structures, a-, b-,
and g-MnO2, were successfully synthesized by a facile hydrother-
mal method. Their catalytic activities for DME combustion were
mainly dominated by the crystalline phase, which follow the order
of a-4 g-4 b-MnO2. The best catalytic activity of a-MnO2 for DME
combustion can be attributed to the larger channel dimension,
higher specific surface area and better oxygen mobility.
Acknowledgments
This work was supported by the Natural Science Foundation of
Guangdong (10251009001000003), the Scientific Program of
Guangzhou (2010Z1-E061) and the 211 Project of Guangdong
Province.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.matlet.2012.
07.011.
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