CHINESE JOURNAL OF CATALYSIS

Volume 31, Issue 7, 2010

Online English edition of the Chinese language journal

Cite this article as: Chin J Catal, 2010, 31: 747–750. RESEARCH PAPER

Synthesis, Characterization, and Performance of

LaZnxFe1-xO3 Perovskite Nanocatalysts for
Toluene Combustion
Seyed Ali HOSSEINI1,*, Mohammad Taghi SADEGHI2, Abdolali ALEMI2, Aligholi NIAEI1, Dariush
SALARI1, Leila KAFI-AHMADI2
1
Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
2
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran

Abstract: Nanostructured LaFeO3 and substituted LaZnxFe1-xO3 (x = 0.01, 0.05, 0.1, 0.2, and 0.3) perovskites were synthesized by the
sol-gel auto-combustion method and used in the catalytic combustion of toluene. Their structures and surface properties were investigated
by X-ray diffraction, Fourier transmission infrared spectroscopy, BET surface area, and scanning electron microscopy. Characterization
data revealed that the total insertion of zinc into LaFeO3 takes place when x ≤ 0.1. However, ZnO segregation occurs to some extent, es-
pecially at x > 0.1. The performance of these perovskites was evaluated by toluene combustion. The catalytic activity of the catalysts in-
creased substantially with an increase in zinc substitution. These results can be attributed to the cooperative effect between LaZnxFe1-xO3 and
the zinc oxide phases. The relative concentration of these phases determines their oxygen activation ability and reactivity.

Key words: sol-gel auto-combustion; perovskite; toluene; catalytic oxidation; LaZnxFe1-xO3

Volatile organic compounds (VOCs) may undergo photo-
chemical reactions with nitrogen oxides in the presence of
sunlight yielding even more hazardous compounds such as
tropospheric ozone or organic peroxides (so-called photo-
chemical smog) [1]. Automobiles and industrial processes are
mainly responsible for VOC emissions. VOCs such as hydro-
carbons, alcohols, ketones, and aldehydes [2,3] are readily
oxidized. When the recovery of these compounds is not de-
sired, they are usually destroyed via deep oxidation. Catalytic
combustion is regarded as an effective and economic way for
air pollution control [4]. Improved catalytic combustion per-
formance would thus lead to considerable energy saving. The
catalysts currently used for environmental purposes are either
noble metals or metal oxides. Although noble metals are the
most active and effective catalysts for VOC decomposition,
they lack a high sintering rate, are volatile and are expensive
[5]. Under these circumstances oxides appear to be a tempting
solution, especially with regards to price and easier prepara-
tion.
Perovskites are mixed oxides with a specific cubic structure
and can be described by the general formula ABO3. Perovskites
have previously been investigated for VOC combustion. Chang
et al. [6] found that La0.8Sr0.2CoO3 was highly effective for the
deep oxidation of toluene and methyl ethyl ketone. Lintz et al.
[7] studied the combustion of several VOCs over LaMnO3.
Arai et al. [8] found a very high activity for the deep oxidation
of methane with Sr-doped LaMnO3. At conversion levels be-
low 80%, Sr-doped LaMnO3 was more active than Pt/Al2O3.
High oxidation activities for La0.75Sr0.25MnO3+x and La0.8Sr0.2-
MnO3 have also been reported by McCarty et al. [9]. It has been
asserted that a correlation exists between VOC oxidation rate
and the bond dissociation energy of the weakest C–H bond
[10,11].
The main challenge in developing perovskite catalysts is to
determine their structures while preserving sufficiently high
surface areas. The preparation of a perovskite oxide involves a
solid-state reaction of its precursor oxide to form the charac-
teristic ABO3 structure. This requires significant exposure of
the precursor oxide to high temperatures leading to a low spe-
cific surface area for the catalyst. To circumvent this limitation,

Received date: 12 January 2010.

*Corresponding author. Tel: +98-411-3393163; Fax: +98-411-3340191; E-mail: s_ali_hosseini@yahoo.com
Copyright © 2010, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved.
DOI: 10.1016/S1872-2067(09)60083-8
 Seyed Ali HOSSEINI et al. / Chinese Journal of Catalysis, 2010, 31: 747–750
a number of alternative preparation methods have been evalu-
ated in an attempt to lower the firing temperature for perovskite
synthesis. Fe and Zn are transition metals that have been used
as catalysts of VOC because of their role in the improvement of
catalyst activity [12,13].
The objectives of this work are to synthesize LaZnxFe1-xO3 (x
= 0, 0.01, 0.05, 0.1, 0.2, 0.3) perovskites in the form of
nanoparticles by the sol-gel combustion method and also to
evaluate their volatile organic compound combustion activi-
ties. The perovskites were characterized using X-ray diffrac-
tion (XRD), scanning electron microscopy (SEM), BET sur-
face area measurements, and Fourier transmission infrared
spectroscopy (FT-IR). Toluene was chosen as a VOC model
compound because of its application as an industrial solvent.
Toluene is considered to be one of the main VOC compounds.
1 Experimental
1.1 Synthesis of perovskites
Analytical grade Fe(NO3)3·9H2O, La(NO3)3·6H2O,
Zn(NO3)2·6H2O, and C6H8O7·H2O were used as raw materials
for the stoichiometric preparation. Specific amounts of
Fe(NO3)3·9H2O, La(NO3)3·6H2O, and Zn(NO3)2·6H2O were
dissolved in a citric acid solution as the sol to obtain substituted
LaZnxFe1-xO3 (x = 0, 0.01, 0.05, 0.1, 0.2, 0.3). The molar ratio
of citric acid to the total metal nitrates in the solution mixture
was kept at 1. The solutions were stirred vigorously and
evaporated by heating at 80 °C for 2 h and then at 100 °C while
the slurry gradually burned and turned into a brown powder.
The brown powders obtained were calcined at 600 °C for 1 h
and subsequently at 800 °C for 3 h.
1.2 Characterization of the perovskites
The phases of the synthesized catalysts were characterized
by XRD using a Siemens D500 X-ray powder diffractometer
equipped with a position-sensitive detector allowing all angles
between 4° and 70° to be read simultaneously at a scan rate of
2°/min. Monochromatic Cu Kα was used as the radiation
source. The mean crystal sizes were estimated using the
Scherrer equation [14], D = kλ/βcosθ, where k = 0.89, λ =
0.154 18 nm (Cu), β is the half peak width of the X-ray reflec-
tion, and θ is the diffraction angle. The FT-IR transmission
spectra from 400 cm−1 to 4 000 cm−1 were recorded for all the
samples using a FT-IR Nexus 670 instrument by the KBr pellet
technique. SEM images were obtained using a JEOL JEM-100
CXII microscope.
1.3 Catalytic activity
The activity of the catalysts was evaluated by toluene
combustion in a U-shape quartz tube placed in an electric
furnace working under atmospheric pressure. In each run, 0.2 g
of catalyst was used for the catalytic test. The VOC concen-
tration in the feed gas was 0.2 mol%, the gas hourly space
velocity (GHSV) was 15 000 h−1 and the reaction temperature
ranged from 150 °C to 400 °C. The reactants and products
were analyzed using a gas chromatograph (Shimadzu 2010)
equipped with a flame ionization detector. The conversion was
obtained by calculating the reactant concentration (in the inlet
and the outlet of the reactor) at different temperatures.
2 Results and discussion
2.1 Characterization of perovskites
The XRD patterns of the perovskites are shown in Fig. 1.
Figure 1(1) shows a pure perovskite-type oxide of LaFeO3 with
an orthorhombic structure. The diffraction data are in good
agreement with LaFeO3 (JCPDS 37-1493) [15]. The XRD
patterns of LaZnxFe1-xO3 are shown in Fig. 1(2–5). There is no
distinguishable difference between the XRD patterns of La-
FeO3 and LaZnxFeO3 (x ≤ 0.1). Some segregation occurs for x >
0.1 indicating a ZnO single phase (2θ = 34.43° and 36.24°).
Furthermore, using the Scherrer equation, the average particle
sizes of the perovskites were determined to be 30–50 nm.
The FT-IR spectra of LaZnxFe1-xO3 calcined at 800 °C for 3 h
are shown in Fig. 2. Strong absorption bands are present at
547.6 and 446.9 cm–1 indicating the formation of lanthanum
orthoferrite. The band at 547.6 cm–1 is attributed to the Fe–O
stretching vibration (ν1 mode) and the band at 446.9 cm–1 cor-
responds to the O–Fe–O deformation vibration (ν2 mode) [16].
All these spectra are similar in shape. The intensity of the band
at 446.9 cm–1 decreased with an increase in the substitution of
Fe by Zn. This band seems to consist of two overlapped bands
especially for x > 0.2, which is due to the appearance of ZnO.
The weak (very broad) band between 3 600 and 3 200 cm–1 is
characteristic of the rapid absorption of moisture by KBr [17].
Furthermore, the morphology and particle size of the
perovskites were examined using SEM. SEM images of La-
(6)
(5)
Intensity
(4)
(3)
(2)
(1)
10 20 30 40 50 60 70
2θ/( o )
Fig. 1. XRD patterns of the LaZnxFe1-xO3 nanocatalysts. (1) x = 0 (La-
FeO3); (2) x = 0.01; (3) x = 0.05; (4) x = 0.1; (5) x = 0.2; (6) x = 0.3.
 Seyed Ali HOSSEINI et al. / Chinese Journal of Catalysis, 2010, 31: 747–750

Table 1 Specific BET surface area for the LaZnxFe1-xO3 perovskites

x = 0.3
Perovskite ABET (m2/g)
x = 0.2
LaFeO3 30.1
LaZn0.01Fe0.99O3 29.8
x = 0.1
Transmittance

LaZn0.05Fe0.95O3 26.4
x = 0.05 LaZn0.1Fe0.9O3 22.6
x = 0.01 LaZn0.2Fe0.8O3 15.2
LaZn0.3Fe0.7O3 13.7

x=0
was obtained for the LaFeO3 perovskite. The partial substitu-
tion of iron by zinc results in a progressive decrease in the BET
3500 3000 2500 2000 1500 1000 500 surface area and the lowest value (13.7 m2/g) was obtained for
Wavenumber (cm )−1 LaZn0.3Fe0.7O3.
Fig. 2. FT-IR spectra of the LaZnxFe1-xO3 nanocatalysts calcined at 800
°C in air for 3 h. 2.2 Catalytic activity of perovskites

The oxidation activity of the six perovskites under study was

FeO3 and LaZn0.01Fe0.99O3 (as examples of the LaZnxFe1-xO3
perovskites) are shown in Fig. 3. These images show a uniform
grain size distribution, a fine powder size, and homogenous
nanostructures for the material obtained by the sol-gel
auto-combustion method. A similar morphology and nanos-
tructures were observed for the other perovskites and these are
not shown. The mean particle size is within the nanoscale (≤
100 nm). This value is in accordance with the results obtained
by the measurement of X-ray peak broadening.
The specific BET surface areas of these samples are sum-
marized in Table 1. The largest BET surface area (30.1 m2/g)
evaluated using the toluene oxidation reaction. A control test
without catalysts (thermal oxidation) was performed under the
same conditions. The maximum conversion of toluene (35%)
was obtained at 400 °C. In the control test, toluene was not
oxidized below 150 °C. The activities of LaFeO3 and
LaZnxFe1-xO3 for the oxidation of toluene are shown in Fig. 4.
The catalysts apparently lowered the activation energy as the
oxidation of toluene required a lower initial burning tempera-
ture. We observed that compared to LaFeO3, the LaZnxFe1-xO3
catalysts were more active in the oxidation of toluene.

(a) (b)

10 μm 1 μm

(c) (d)

10 μm 1 μm

Fig. 3. SEM images of LaFeO3 (a,b) and LaZn0.01Fe0.99O3 (c,d).

 Seyed Ali HOSSEINI et al. / Chinese Journal of Catalysis, 2010, 31: 747–750

100 single oxides was found for substitutions where x > 0.1. A
Thermal oxidation significant increase in catalytic activity with zinc substitution
x=0
80
was found. Thus, the modulation of oxygen adsorption and the
x = 0.01
Conversion of toluene (%)

x = 0.05 modulation of the release properties by the insertion of zinc

x = 0.1 into the LaZnxFe1-xO3 structure while maintaining a separate
60 x = 0.2 ZnO phase is crucial in increasing the performance of toluene
x = 0.3
combustion reactions. We conclude that the specific surface
40 area of the catalyst does not directly affect catalyst activity.

20 Acknowledgments

0
The authors thank the Iranian Nanotechnology Initiative for
150 200 250 300 350 400 financial support. Furthermore, we are grateful to Mr. Bahrami
Temperature (oC) from the Physics faculty for the XRD tests and M. Safi for his
Fig. 4. Catalytic activity of LaFeO3 and LaZnxFe1-xO3 for toluene com- assistance in GC and FT-IR analysis.
bustion.

Table 2 Reaction temperatures for 50% and 96% toluene conversion
Catalyst T50%/oC
LaFeO3 268
LaZn0.01Fe0.99O3 235
LaZn0.05 Fe0.95 O3 233
LaZn0.1Fe0.9O3 230
LaZn0.2Fe0.8O3 226
LaZn0.3Fe0.7O3 222
The activity of LaZnxFe1-xO3 increased with an increase in
zinc insertion. The ignition temperature T50% defined as the
temperature required for a 50% conversion of toluene over the
catalysts is shown in Table 2. It is clear that T50% decreased with
an increase in zinc insertion. A similar trend is also observed
for T96%. Taking the reaction temperature and conversion into
account, it is apparent that the catalytic activity of LaZnxFe1-xO3
is higher than that of LaFeO3 under the same reaction condi-
tions used for the oxidation of toluene. Substitution modifies
the surface structure of the catalysts by greatly increasing the
oxygen valances in the surface regions, which results in higher
catalytic activity. It has been reported that the catalytic activity
of perovskite type ABxB′1-xO3 is related to the metal-oxygen
bond and the free energy of reduction of the cations at B and B′
sites [14,18,19]. No relationship exists between the BET sur-
face area and catalyst activity.
3 Conclusions
Nanostructured LaFeO3 and LaZnxFe1-xO3 (x = 0.01, 0.05,
0.1, 0.2 and 0.3) perovskites were successfully synthesized
using the sol-gel combustion method. Some segregation of
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