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Cite this article as: Chin J Catal, 2010, 31: 747–750. RESEARCH PAPER
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.
Volatile organic compounds (VOCs) may undergo photo- and can be described by the general formula ABO3. Perovskites
chemical reactions with nitrogen oxides in the presence of have previously been investigated for VOC combustion. Chang
sunlight yielding even more hazardous compounds such as et al. [6] found that La0.8Sr0.2CoO3 was highly effective for the
tropospheric ozone or organic peroxides (so-called photo- deep oxidation of toluene and methyl ethyl ketone. Lintz et al.
chemical smog) [1]. Automobiles and industrial processes are [7] studied the combustion of several VOCs over LaMnO3.
mainly responsible for VOC emissions. VOCs such as hydro- Arai et al. [8] found a very high activity for the deep oxidation
carbons, alcohols, ketones, and aldehydes [2,3] are readily of methane with Sr-doped LaMnO3. At conversion levels be-
oxidized. When the recovery of these compounds is not de- low 80%, Sr-doped LaMnO3 was more active than Pt/Al2O3.
sired, they are usually destroyed via deep oxidation. Catalytic High oxidation activities for La0.75Sr0.25MnO3+x and La0.8Sr0.2-
combustion is regarded as an effective and economic way for MnO3 have also been reported by McCarty et al. [9]. It has been
air pollution control [4]. Improved catalytic combustion per- asserted that a correlation exists between VOC oxidation rate
formance would thus lead to considerable energy saving. The and the bond dissociation energy of the weakest C–H bond
catalysts currently used for environmental purposes are either [10,11].
noble metals or metal oxides. Although noble metals are the The main challenge in developing perovskite catalysts is to
most active and effective catalysts for VOC decomposition, determine their structures while preserving sufficiently high
they lack a high sintering rate, are volatile and are expensive surface areas. The preparation of a perovskite oxide involves a
[5]. Under these circumstances oxides appear to be a tempting solid-state reaction of its precursor oxide to form the charac-
solution, especially with regards to price and easier prepara- teristic ABO3 structure. This requires significant exposure of
tion. the precursor oxide to high temperatures leading to a low spe-
Perovskites are mixed oxides with a specific cubic structure cific surface area for the catalyst. To circumvent this limitation,
a number of alternative preparation methods have been evalu- furnace working under atmospheric pressure. In each run, 0.2 g
ated in an attempt to lower the firing temperature for perovskite of catalyst was used for the catalytic test. The VOC concen-
synthesis. Fe and Zn are transition metals that have been used tration in the feed gas was 0.2 mol%, the gas hourly space
as catalysts of VOC because of their role in the improvement of velocity (GHSV) was 15 000 h−1 and the reaction temperature
catalyst activity [12,13]. ranged from 150 °C to 400 °C. The reactants and products
The objectives of this work are to synthesize LaZnxFe1-xO3 (x were analyzed using a gas chromatograph (Shimadzu 2010)
= 0, 0.01, 0.05, 0.1, 0.2, 0.3) perovskites in the form of equipped with a flame ionization detector. The conversion was
nanoparticles by the sol-gel combustion method and also to obtained by calculating the reactant concentration (in the inlet
evaluate their volatile organic compound combustion activi- and the outlet of the reactor) at different temperatures.
ties. The perovskites were characterized using X-ray diffrac-
tion (XRD), scanning electron microscopy (SEM), BET sur- 2 Results and discussion
face area measurements, and Fourier transmission infrared
spectroscopy (FT-IR). Toluene was chosen as a VOC model 2.1 Characterization of perovskites
compound because of its application as an industrial solvent.
Toluene is considered to be one of the main VOC compounds. The XRD patterns of the perovskites are shown in Fig. 1.
Figure 1(1) shows a pure perovskite-type oxide of LaFeO3 with
1 Experimental 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
1.1 Synthesis of perovskites
distinguishable difference between the XRD patterns of La-
FeO3 and LaZnxFeO3 (x ≤ 0.1). Some segregation occurs for x >
Analytical grade Fe(NO3)3·9H2O, La(NO3)3·6H2O,
0.1 indicating a ZnO single phase (2θ = 34.43° and 36.24°).
Zn(NO3)2·6H2O, and C6H8O7·H2O were used as raw materials Furthermore, using the Scherrer equation, the average particle
for the stoichiometric preparation. Specific amounts of sizes of the perovskites were determined to be 30–50 nm.
Fe(NO3)3·9H2O, La(NO3)3·6H2O, and Zn(NO3)2·6H2O were The FT-IR spectra of LaZnxFe1-xO3 calcined at 800 °C for 3 h
dissolved in a citric acid solution as the sol to obtain substituted are shown in Fig. 2. Strong absorption bands are present at
LaZnxFe1-xO3 (x = 0, 0.01, 0.05, 0.1, 0.2, 0.3). The molar ratio 547.6 and 446.9 cm–1 indicating the formation of lanthanum
of citric acid to the total metal nitrates in the solution mixture orthoferrite. The band at 547.6 cm–1 is attributed to the Fe–O
was kept at 1. The solutions were stirred vigorously and stretching vibration (ν1 mode) and the band at 446.9 cm–1 cor-
evaporated by heating at 80 °C for 2 h and then at 100 °C while responds to the O–Fe–O deformation vibration (ν2 mode) [16].
the slurry gradually burned and turned into a brown powder. 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
The brown powders obtained were calcined at 600 °C for 1 h
Fe by Zn. This band seems to consist of two overlapped bands
and subsequently at 800 °C for 3 h.
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
1.2 Characterization of the perovskites characteristic of the rapid absorption of moisture by KBr [17].
Furthermore, the morphology and particle size of the
The phases of the synthesized catalysts were characterized perovskites were examined using SEM. SEM images of La-
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 (6)
Scherrer equation [14], D = kλ/βcosθ, where k = 0.89, λ =
(5)
Intensity
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
(a) (b)
10 μm 1 μm
(c) (d)
10 μm 1 μm
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 (%)
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.
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