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-1-
Low-temperature catalytic combustion of methane over
MnO
x
-CeO
2
mixed oxide catalysts: Effect of preparation
method
1
Shi Limin
1
, Chu Wei
1
, Qu Fenfen
2
, LuoShizhong
1
1 School of Chemical Engineering, Sichuan University, Chengdu (610065)
2 Department of Environment, Sichuan University, Chengdu (610065)
E-mail:chuwei65@yahoo.com.cn
Abstract
The effect of preparation method on MnO
x
-CeO
2
mixed oxide catalysts for methane combustion at low
temperature was investigated by means of BET, XRD, XPS, H
2
-TPR techniques and methane oxidation
reaction. The catalysts were prepared by the conventional coprecipitation, plasma and modified
coprecipitation methods, respectively. It was found that the catalyst prepared by modified
coprecipitation was the most active, over which methane conversion reached 90% at a temperature as
low as 390℃. The XRD results showed the preparation methods had no effect on the solid solution
structure of MnO
x
-CeO
2
catalysts. More Mn
4+
and richer lattice oxygen were found on the surface of
the modified coprecipitation prepared catalyst with the help of XPS analysis, and its reduction and BET
surface area were remarkably promoted. These factors could be responsible for its higher activity for
methane combustion at low temperature.
Keywords: MnO
x
-CeO
2
mixed oxide; solid solution; methane combustion; low-temperature activity.
1. Introduction
For the environment and energy consideration, complete oxidation of methane into harmless
CO
2
and H
2
O has been paid much attention in catalytic combustion field. Among the
heterogeneous catalysts, the supported noble metal Pd-based catalysts show excellent activity at
low temperature [1-3]. The temperature corresponding to 90% methane conversion (T
90
) over
Pd/SnO
2
catalyst is 440 ℃ [2]. Pd/Sn
x
Zr
1-x
O
2
catalyst has been also reported to possess high
activity at low temperature for methane complete oxidation, over which T
90
is 378 ℃ [3]. However,
poor thermal stability and expensive cost of noble metals prevent the widespread application of
these catalysts. Recently, the transition metal mixed oxides are attractive due to the relatively low
price and as high as or slightly higher catalytic activity toward methane combustion at low
temperature than supported noble metals [4, 5].
Among the transition metal mixed oxides of interest for oxidation reactions, MnO
x
-bases
mixed oxide catalysts exhibit great potential. It is generally believed that MnO
x
are compounds
with a typical berthollide structure and contain labile lattice oxygen. Their catalytic properties are
attributed to the ability for manganese to form oxides with variable oxidation states (MnO
2
,
Mn
2
O
3
, Mn
3
O
4
, or MnO) and to their oxygen storage capacity in the crystalline lattice [6, 7]. For
methane oxidation reaction, the Mn
4
+
sites are stronger catalytic active sites than the Mn
3
+
sites [6,
8]. The active site on supported MnO
x
is mainly identified as being Mn
4+
of MnO
2
in other
oxidation processes [7, 9]. In addition, CeO
2
has been widely used as a promoter and an oxidation
catalyst owing to its unique redox properties and high oxygen storage capacity [10, 11]. Compared
with pure MnO
x
and CeO
2
, MnO
x
-CeO
2
mixed oxides showed higher catalytic activities because
manganese and cerium oxides formed solid solution in which oxygen reservoir of CeO
2
and the
mobility of oxygen species were greatly enhanced [12, 13].
The catalytic performance of MnO
x
-CeO
2
mixed oxides is notably affected by the preparation
1
This work was supported by the National Natural Science Foundation of China (205903603) and by the 973
project of the Ministry of Science and Technology of China (2005CB221406).