Applied Catalysis B: Environmental 43 (2003) 81–92

Perovskite-type oxides synthesized by reactive grinding

Part IV. Catalytic properties of LaCo1−x Fex O3
in methane oxidation
V. Szabo a , M. Bassir a , A. Van Neste b,c , S. Kaliaguine a,∗
a Department of Chemical Engineering, Laval University, Ste Foy, Que., Canada G1K 7P4
b Department of Mining and Metallurgy, Laval University, Ste Foy, Que., Canada G1K 7P4
c Nanox Inc., 335 St. Joseph E., Quebec, Que., Canada G1K 3B3

Received 27 March 2002; received in revised form 29 October 2002; accepted 31 October 2002

Abstract
In this part of the present work, the catalytic properties in methane oxidation of perovskite-type mixed-oxides, LaCo1−x Fex O3
prepared by reactive grinding of the component oxides were studied. A fine control of the nature and concentration of the
various sites active in oxido-reduction catalysis was performed by applying the comprehensive picture of the effects of ther-
mal pretreatment of the mixed-oxides generated by this technique, developed in part I of this contribution. These properties
which were previously illustrated by the kinetics of complete oxidation of n-hexane over five nanocrystalline LaCo1−x Fex O3
catalysts treated in parts II and III are now demonstrated by a kinetic study of methane oxidation over the same catalysts.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Perovskites; Methane oxidation; Kinetics; Reactive grinding

1. Introduction of perovskites for oxidation is a proven technology that

The interest for atmosphere VOC emission preven-
tion and clean-up augmented much during the last
decades in relation with the increasingly strict legis-
lations [1,2]. A variety of catalysts are used for this
purpose and in general precious metals are preferred
as total oxidation catalysts [3–6]. Transition metal ox-
ides are also utilized for this purpose and in particular,
the perovskite-type oxides are considered as poten-
tially significant [7–14]. These materials are cheaper,
showing thermal stability in atmospheres containing
oxygen and steam at high temperature (gas turbine,
catalytic burners) and resistance to poisoning. The use
∗ Corresponding author.
E-mail address: kaliagui@gch.ulaval.ca (S. Kaliaguine).
has reached commercial status in some instances [15].
The main limitations of the perovskite-type materials
are their low surface area typically around 20 m2 /g
[15,16]. Various preparation methods were proposed
in order to increase the specific surface area (SSA)
and, thus catalytic activity [15,17]. In the last decade,
mechanical alloying by high-energy ball-milling was
developed to produce novel oxide materials [18], in-
cluding nanophase of fluorite-structured CeO2 -ZrO2
catalysts and iron carbides catalysts synthesis [19,20].
This grinding method yielded gains in catalytic ac-
tivity when compared with traditional syntheses
[21–23] and was shown to be appropriate for prepar-
ing mixed-oxide catalysts with redox properties [19].
Moreover a beneficial effect of ball-milling would
be to increase specific surface area [23]. Reactive

0926-3373/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0926-3373(02)00308-9
82 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
grinding, a method which was demonstrated recently
in our laboratory, allows to increase SSA between 3
and 150 m2 /g in a controlled manner [24,25].
Methane can be taken as a reference compound
because it belongs to the most difficult to oxidize
class of VOCs [26]. As a consequence in the present
study, a detailed kinetic analysis of the catalytic
oxidation of methane on five LaCo1−x Fex O3 per-
ovskite catalysts was performed. In reporting this
work, the parameters of the kinetic model are dis-
cussed in relation with the results reported in parts I,
II and III of this contribution [25,27,28]. Part I deals
with a temperature-programmed desorption of oxy-
gen (TPDO) and X-ray photoelectron spectroscopy
(XPS) of LaCo1−x Fex O3 materials prepared by reac-
tive grinding. Parts II and III report a kinetic analysis
of the oxidation of n-hexane over the same materi-
als. The methane oxidation study presented in this
fourth part comprises an experimental analysis of the
poisoning effects of water vapor and sulfur dioxide.
2. Experimental procedures
2.1. Preparation of LaCo1−x Fex O3
Five LaCo1−x Fex O3 , with different specific surface
areas, were prepared by reactive grinding. Powders
of lanthanum oxide, La2 O3 (Alfa 99.99%), cobalt ox-
ide, Co3 O4 (Baker & Adamson, 97.49%) and Fe2 O3
(Strem Chemicals, 99.8%), in stoichiometric propor-
tions were ball-milled at high-energy. The La2 O3
powder was preliminarily calcined at 600 ◦ C for 24 h,
which makes it possible to eliminate any trace of lan-
thanum hydroxide. Perovskite sample 1 was prepared
in a tungsten carbide (WC) vial (39.4 cm3 ) with three
WC balls, rotated at 700 rpm using a SPEX labora-
tory grinder (SPEX is a trademark of SPEX Indus-
tries, Edison, NJ). The vial atmosphere was air. The
milling duration was 12 h and the perovskite quantity
obtained, 5 g. These conditions are not optimized to
obtain a high specific surface area.
Samples 2, 3 and 5 were synthesized in a tempered
steel (TS) vial (64.6 cm3 ) with three TS balls, using the
SPEX grinder rotated at 1100 rpm. Their preparation
was carried out over 24 h in an air atmosphere for 2 and
3 and in an oxygen atmosphere for 5. As discussed in
[25] additives were introduced in the mill in order to
increase the specific surface area. The powder quantity
obtained for each sample was 5 g.
Sample 4 was prepared in a larger tempered steel
vial (183.5 cm3 ) with nine balls made of the same
material. The same SPEX ball mill was rotated at
700 rpm. The grinding lasted for 28 h in an oxygen at-
mosphere with additive. The perovskite quantity syn-
thesized was 15 g.
For each preparation, the milling proceeds at room
temperature. When the synthesis used an additive, the
perovskite end product was thoroughly washed, in or-
der to free the sample from even traces of this additive.
2.2. Catalyst characterization
2.2.1. Powder XRD
Conversion into perovskite upon grinding and the
nature of product phases were determined by XRD us-
ing Cu K␣ radiation (λ = 1.54184 Å, Siemens D5000
or Philips diffractometer). The conditions of spectral
recording were in a 2θ angle step scanning from 10 to
80◦ , with a 2.4 s delay for each 0.05◦ step.
2.2.2. Nitrogen adsorption
The specific surface area, at different calcination
temperatures, for each LaCo1−x Fex O3 sample was
measured by nitrogen adsorption (BET method) at
−196 ◦ C using an Omnisorb Sorptometer 100 instru-
ment operated in the continuous mode. Samples of
about 1 g were outgassed at 200 ◦ C for approximately
24 h under vacuum before starting the adsorption–
desorption experiments. N2 adsorption measurements
were performed up to a relative pressure P/P0 = 0.1.
2.2.3. Atomic absorption
The chemical composition analyses (La, Co, Fe) of
the perovskite end products and the residual impurities
were performed by atomic absorption spectroscopy
using a Perkin-Elmer 1100B spectrometer. Samples
were dissolved in 10% HCl solution at 60 ◦ C.
In part I of this contribution, detailed studies of
these catalysts by XPS and TPDO were reported [25].
These studies have shown that the temperature of cal-
cination of LaCo1−x Fex O3 perovskites produced by
reactive grinding is a key factor in determining the na-
ture and the density of oxygen adsorption sites as well
as their energy of adsorption. Interactions with molec-
ular oxygen during calcination stabilize the surface
 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
oxygen vacancies responsible for adsorption of ␣ oxy-
gens and the doubly charged vacancies (Co2+ 䊐 Co2+ )
which are the desorption sites for ␤ oxygens during
the TPDO experiment. ␤ oxygens originate from the
bulk of the LaCoO3 lattice.
2.3. Oxidation reaction
The methane oxidation reaction was carried out in
a tubular fixed bed micro-reactor with a quartz reactor
tube (7 mm i.d.) at atmospheric pressure. A gas mix-
ture of oxygen, neon and methane (2.5% CH4 , 87.5%
O2 , 10% Ne, Praxair) and pure oxygen gas (100%
oxygen, Praxair) were used to prepare the feed mix-
ture of 0.25% CH4 , 98.75% O2 and 1% Ne, using
two mass flow controllers (Omega 0152 E, Matheson
Model 8240). In these conditions, the adiabatic tem-
perature rise at 100% CH4 conversion was calculated
to be 20 ◦ C.
The feed mixture stream passed through a catalyst
charge of about 100 mg, installed in the reactor and
secured by using plugs of quartz wool. The reactor
was placed in a furnace equipped with a temperature
programmer. The reaction temperature was controlled
with a K-type thermocouple placed inside the catalytic
bed. The total flow rate of the gas mixture was in
the range of 7.5–40 ml/min, resulting in a range of
gas hourly space velocity of 5625–30,000 h−1 (STP
ml/h ml catalyst). Before the catalytic tests the samples
were treated in He for 1 h at ambient temperature.
When the influence of water vapor partial pressure
on reaction rate was studied, the same gas mixture
of oxygen, neon and methane as above was bubbled
through a water containing saturator maintained at a
constant temperature between 33.1 and 54.3 ◦ C. This
allowed obtaining mole fractions of water vapor be-
tween 5 and 15% and the methane content was main-
tained at 0.25%.
For the SO2 poisoning study, the mixture of oxygen,
neon and methane (2.5% CH4 , 87.5% O2 , 10% Ne,
Praxair) was blended with another SO2 containing gas
mixture (26 ppm SO2 , 10% Ne, balance oxygen, Prax-
air) using the two mass flow controllers (Omega 0152
E, Matheson Model 8240) in order to obtain 0.25%
CH4 and 23 ppm SO2 .
Analyses of reactants and products were performed
using a gas chromatograph (GC, Hewlett Packard HP
6890 Series) equipped with a thermal conductivity de-
83
tector and two HayeSep DB (2 × 5 m, i.d. 1.0 mm)
columns.
2.4. Data treatment
The same procedure as in the second and third parts
of this contribution was used to perform the data treat-
ment. Methane steady state conversion results (main-
tained for at least 2 h) at the outlet of the reactor were
collected for the five LaCox Fe1−x O3 catalysts at dif-
ferent flowrates over a large range of temperature. It
was verified that the catalytic activity was not affected
by the series of tests provided the reaction temperature
does not exceed the calcination temperature. Because
the reaction was performed at higher temperature than
n-hexane oxidation [27,28] the kinetic data could be
represented using the simplified kinetic equation pro-
posed by Arai et al [29]. The mechanism consists in
only one surface Mars–Van Krevelen process involv-
ing ␤ oxygens.
Using the same procedure as in parts II and III of this
contribution, rate values were obtained by first cross-
plotting experimental conversions X as a function of
W/F (where W is the weight of the catalyst and F the
inlet molar flowrate of methane) at several selected
reaction temperatures. The resulting curves were thus
fitted using the following exponential expression:

  
W
X = a 1 − exp −b (1)
F
The derivatization of Eq. (1) led to obtaining point
values for the rate of reaction:
  
dX W
r= = ab exp −b (2)
d(W/F) F
where r represents the reaction rate in the conditions
prevailing at the outlet of the catalyst bed. Note that
Eqs. (1) and (2) are not kinetic equations but were
fitting of conversion data allowing to established
meaningful numerical estimations of reaction rates in
various conditions.
Then the values of r were represented using Arai
et al. simplified equation [29]:
r = kPCH4 (3)
This kinetic model (Eq. (3)) involves only the partici-
pation of one site (␤ oxygens) in the catalytic process.
In parts II and III for n-hexane total oxidation which
84 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
was performed at lower temperature [27,28] two kinds
of oxygen species (␣ and ␤) coexisted at the surface
of these LaCo1−x Fex O3 perovskite-type oxides. At
the temperatures where CH4 oxidation was performed
the coverage of ␣ sites, and therefore the correspond-
ing oxidation rates, are negligible. Thus the methane
oxidation reaction is believed to involve a Mars–Van
Krevelen mechanism using oxygen atoms originating
from the bulk. These are identical with the oxygen
atoms that desorb as ␤ molecular oxygen in TPDO
experiments.
3. Experimental results
The X-ray diffraction patterns of the five samples
(1–5) were reported in part III of this communica-
tion [28]. These samples which were studied here for
their activity in methane oxidation were essentially
crystallographically pure nanocrystalline perovskites
LaCo1−x Fex O3 . The crystal size as determined by
X-ray line broadening was indeed found to be in the
9.5–16.5 nm range.
Table 1 gives values of the BET specific surface area
measured after calcination at various temperatures and
the elemental composition of these five samples. It was
verified that these calcinations had no effect on the
XRD pattern of the solids. In this work, the calcination
temperatures were higher than in the n-hexane study
reported in part III [28] due to the higher reaction
temperatures reached in methane oxidation.
Fig. 1A shows the methane conversion data obtained
at steady state for various reactor temperatures and
at various GHSV, using catalyst 4 calcined at 600 ◦ C.
Complete oxidation was reached between the temper-
atures of 470–500 ◦ C, which shows the high activity of
these materials. The data in Fig. 1A are cross-plotted in
Table 1
Kinetic parameters established for the different samples
Samplea Elemental composition Calcination temperature (◦ C)
1 La1.0 Co0.96 Fe0.003 O3−∆ 700
5 La0.99 Fe1.01 O3−∆ 600
2 La0.88 Co0.95 Fe0.17 O3−∆ 500
3 La0.91 Co0.92 Fe0.17 O3−∆ 500
4 La0.96 Co0.7 Fe0.34 O3−∆ 600
a According to the notation used in parts II and III of this communication [27,28].
Fig. 1B yielding a set of isothermal curves for methane
conversion as a function of the pseudo-contact time
W/F. Then, these isothermal curves are fitted with ex-
ponential Eq. (1). Numerical estimates of the local re-
action rate (2) were obtained by derivatizing of these
fitting lines analytically. The numerical estimates of r
were fitted to Eq. (3) by linear regression [30] and the
lines shown in Fig. 1A were obtained by numerical
integration over the length of the reactor
 XE
W dX
= (4)
F 0 r
assuming isothermal reaction. The hypothesis of an
isothermal reactor was thought acceptable as the dif-
ference in measured temperatures at bed inlet and
outlet was found to be lower than 5 ◦ C at complete
conversion. The observed agreement between the ex-
perimental X data and calculated curves in Fig. 1A,
is a test of validity for the values of the rate constant
k obtained by the fitting procedure.
Figs. 2–5 show the methane conversion in catalytic
tests of catalyst 2 (Fig. 2), catalyst 3 calcined at 500 ◦ C
(Fig. 3), catalyst 1 calcined at 700 ◦ C (Fig. 4) and
catalyst 5 calcined at 600 ◦ C (Fig. 5). The Arrhenius
plots for the rate constant k in Eq. (3) are shown in
Fig. 6:
k = k0 e−E/RT (5)
The pre-exponential factors (k0 ) and activation ener-
gies (E) were obtained by linear regression of these
lines. These constants are recapitulated in Table 1. The
data for sample 1 reported in Table 1 and Fig. 4 were
obtained after calcination of this sample to 700 ◦ C. In
parts II and III of this work, the sample 1 was only
calcined at 400 ◦ C which was sufficient to obtain some
activity in n-hexane oxidation over ␣ oxygen sites.
Sample 1 (designated as N1 in [25]) calcined at this
Specific surface area (m2 /g) EA (kcal/mol) k0 (mol/s g atm)
2.4 24.5 1.97 × 102
13 22.4 3.14 × 102
21.4 25.5 5.08 × 103
29 25.5 4.28 × 103
37.8 26.3 1.32 × 104
 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92 85

Fig. 1. (A) Methane oxidation conversion over sample 4 calcined at 600 ◦ C: (䊉) 5625 h−1 , (䊏) 11,250 h−1 , (䉱) 16,875 h−1 , (䉲) 22,500 h−1 ,
(䊊) 30,000 h−1 . Reaction conditions: 0.25% CH4 , 98.75% O2 , 1% Ne and 100 mg of catalyst. The lines are calculated by integrating
Eq. (3) over the length of the reactor. (B) Values of methane conversion over sample 4 calcined at 600 ◦ C as function of pseudo-contact
time (W/F). Points are experimental data, lines are calculated using Eq. (1): () 355 ◦ C, (䉭) 375 ◦ C, (䊐) 394 ◦ C, (䊊) 412 ◦ C, (䉲) 442 ◦ C,
(䉱) 471 ◦ C, (䊏) 486 ◦ C, (䊉) 504 ◦ C.

temperature showed no activity in methane oxidation. Methane oxidation rate values obtained using cata-
A similar situation was met with sample 3, which dis- lyst 3 calcined at 500 ◦ C derived from the conversion
played no activity in methane oxidation, when cal- data reported in Fig. 3, are reported in Fig. 7. In this
cined at 300 ◦ C. figure, reaction rates at given temperatures are plotted
86 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92

Fig. 2. Methane oxidation conversion over catalyst 2 calcined at 500 ◦ C: (䊉) 5625 h−1 , (䊏) 11,250 h−1 , (䉱) 16,875 h−1 , (䉲) 22,500 h−1 ,
(䊊) 30,000 h−1 . Reaction conditions: 0.25% CH4 , 98.75% O2 , 1% Ne and 100 mg of catalyst. The lines are calculated by integrating
Eq. (3) over the length of the reactor.

Fig. 3. Methane oxidation conversion over catalyst 3 calcined at 500 ◦ C: (䊉) 5625 h−1 , (䊏) 11,250 h−1 , (䉱) 16,875 h−1 , (䉲) 22,500 h−1 ,
(䊊) 30,000 h−1 . Reaction conditions: 0.25% CH4 , 98.75% O2 , 1% Ne and 100 mg of catalyst. The lines are calculated by integrating
Eq. (3) over the length of the reactor.
 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92 87

Fig. 4. Methane oxidation conversion over sample 1 calcined at 700 ◦ C: (䊉) 5625 h−1 , (䊏) 11,250 h−1 , (䉱) 16,875 h−1 , (䉲) 22,500 h−1 ,
(䊊) 30,000 h−1 . Reaction conditions: 0.25% CH4 , 98.75% O2 , 1% Ne and 100 mg of catalyst. The lines are calculated by integrating
Eq. (3) over the length of the reactor.

Fig. 5. Methane oxidation conversion over sample 5 calcined at 600 ◦ C: (䊉) 5625 h−1 , (䊏) 11,250 h−1 , (䉱) 16,875 h−1 , (䉲) 22,500 h−1 ,
(䊊) 30,000 h−1 . Reaction conditions: 0.25% CH4 , 98.75% O2 , 1% Ne and 100 mg of catalyst. The lines are calculated by integrating
Eq. (3) over the length of the reactor.
88 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92

Fig. 6. Arrhenius plots of constant k in Eq. (3) for the different catalysts.

Fig. 7. Linearity test for the rate of methane oxidation over catalyst 3 (designated as V1 in [25]) calcined at 500 ◦ C.
 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
against the partial pressure of methane as a test of
Eq. (3).
4. Kinetic analysis and discussion
The confirmation that the rate data follow Eq. (3)
allows to conclude that on these catalysts, the active
oxygen species for methane total combustion is ␤ oxy-
gen with rate r (or r2 in parts II and III [27,28]). This
is in agreement with the results in the TPDO and O 1s
XPS studies reported in the first part of this article [25]
which showed that ␣ oxygens are in very low surface
concentrations for samples calcined at temperatures
exceeding 500 ◦ C. Fig. 8 allows a comparison between
the rate constants k in Eq. (3) and k2 the rate constant
derived in [28] for the specific rate of n-hexane oxi-
dation over ␤ oxygens. In spite of the different tem-
perature ranges at which the two processes occur, an
obvious similarity is observed between the two rate
constants. Not only the energies of activation E and
E2 appear essentially equal (24.6 ± 1.1 kcal/mol for
E2 compared to 25.8 ± 0.3 kcal/mol for E2 in Co con-
taining catalysts), but very close values are observed
in both cases for the most active catalysts (2, 3–300
Fig. 8. Comparison between rate constants k and k2 of the two reactions: methane oxidation and n-hexane oxidation respectively (k2 values
are from [28]).
89
and 3–500) whereas the least active sample 1 catalyst
yields clearly lower values of k and k2 . This similarity
seems to confirm the hypothesis that these two reac-
tions occur on the same sites.
The data for k are considered more reliable due to
the lower number of adjustable constants in the rate
equation (Eq. (3)) for methane oxidation.
In Table 1, the catalysts are in increasing order of
specific surface area and it is seen that this is also
essentially the increasing order of k0 values. Since
the activation energy is almost the same for all cata-
lysts (with the exception of sample 5) this is also the
order of increasing reaction rate. The specific surface
area is therefore a very significant factor determining
the rate of methane oxidation. Obviously, the effects
of the composition and calcination temperature are
also significant. In particular, catalyst 5 having no
Co (LaFeO3 ) is clearly less active than the cobalt
containing catalysts.
It is interesting to note in Fig. 6 that the data ob-
tained with catalyst 5 which contains no Co show
a sudden change in slope as temperature exceeds
530 ◦ C. Such a drop in the slope of the Arrhenius plot
is usually indicating the onset of a regime where in-
ternal diffusion becomes rate limiting. It is probably
90 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
meaningful that this behavior is obtained with the all
Fe perovskite. It may be that the diffusional process
which becomes rate limiting is the outward diffu-
sion of oxygen ions O2− involved in the Mars–Van
Krevelen process. The results in Fig. 6 therefore sug-
gest that the mobility of the oxygen ions is lower in
LaFeO3 than in the cobalt containing perovskites.
Fig. 9 represents the values obtained for k0 /SSA
which pictures the specific reaction rate per unit sur-
face area, as a function of the catalyst calcination
temperature. It is interesting to note that no rate is ob-
served at calcination temperatures lower than 500 ◦ C
which is exactly the range of calcination temperature
at which TPDO experiments [25] indicated no forma-
tion of the surface sites responsible for the release of
␤ oxygens. Then increasing the calcination temper-
atures up to 600 ◦ C yields a continuous increase in
reaction rate. This would correspond to an increased
surface concentration of these sites due to an increased
surface Co2+ stabilization process by interaction with
oxygen during calcination as determined by XPS and
TPDO (see the mechanism described in [25]). At cal-
cination temperatures above 600 ◦ C, the defect healing
process starts diminishing the surface defects con-
centration leading to a decreased methane oxidation
rate.
The data point for catalyst 5 is not shown in Fig. 9.
As the activation energy E is different for this cat-
alyst (see Table 1), the pre-exponential factor k0
Fig. 9. Effect of the calcination temperature on the specific frequency factor for methane oxidation.
should not be compared with the values for the other
catalysts.
Fig. 10 shows the influence of water vapor at dif-
ferent partial pressures (5, 10 and 15% of water) for
methane oxidation at 11,250 h−1 over catalyst 3 cal-
cined at 500 ◦ C. The methane conversion is essentially
not further affected as the partial pressure of water
exceeds 0.05 atm. This result seems to show that al-
ready for a partial pressure of 5%, perovskite surface
sites are saturated. Moreover, after each experiment
performed in the presence of water vapor, the catalyst
is calcined again at 500 ◦ C for 2 h in air, the initial ac-
tivity measured in absence of water vapor is restored.
The deactivation by H2 O is therefore reversible.
Fig. 11 was obtained with a catalyst produced in
conditions similar to catalyst 1 except that the calci-
nation temperature was 500 ◦ C (compared to 700 ◦ C
for catalyst 1) and that the specific surface area was
slightly higher (3.5 m2 /g). This Figure compares the
methane conversion obtained as a function of time
at 500 ◦ C and GHSV of 5625 h−1 in two situations.
Curve a was obtained with the standard feed (0.25%
CH4 , 1% Ne, balance O2 ) and shows no deactiva-
tion over 3 days. Curve b was for a similar experi-
ment with 23 ppm SO2 in the feed. It shows that the
LaCoO3 catalyst is not resistant to sulfatation. Cur-
rent work in our laboratory is examining the possibil-
ity to substitute La by a cation which yields less stable
sulfates.
 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92 91

Fig. 10. Study of the influence of PH2 O at 11,250 h−1 over catalyst 3 calcined at 500 ◦ C: (䊉) without water, (䊊) 5% H2 O, (䉲) 10%
H2 O, () 15% H2 O and (䊐) after catalyst regeneration at 500 ◦ C.

Fig. 11. Effect of SO2 poisoning over a LaCoO3 perovskite at 5625 h−1 and 500 ◦ C: (䊏) without SO2 , (䊉) with 23 ppm SO2 .

5. Conclusions the kinetic parameters of the various materials syn-

This work makes it possible to relate the prepara-
tion and pre-treatment conditions of nanocrystalline
LaCo1−x Fex O3 perovskites obtained by reactive
grinding to their catalytic activity in methane oxida-
tion. A detailed kinetic analysis allowed to compare
thesized. In particular, it was shown in part I of this
contribution that controlling the calcination tempera-
ture allows to modify the surface concentration, the
heat of oxygen adsorption, and the nature of a vari-
ety of surface defects associated with two types of
adsorbed oxygens. It was proposed in parts II and III
92 V. Szabo et al. / Applied Catalysis B: Environmental 43 (2003) 81–92
that these two surface oxygens are ion radicals O2 −
and O− . The respective roles of these two species in
the oxidation of n-hexane was clarified in part III by
means of a detailed kinetic study. In the present paper
it was established that owing to the higher reaction
temperature of methane oxidation, only the O− ion
radical formed at the surface sites which allow the
thermal desorption of ␤ oxygens are utilized. This
was indeed indicated both by the simple rate Eq. (3)
which reflects the Mars–Van Krevelen mechanism
and by the fact that no catalytic activity was observed
for catalysts treated in conditions which do not allow
the formation of the surface defects associated with
the evolution of ␤ oxygens in TPDO experiments.
The present part IV confirms that reactive grinding
is a perovskite synthesis technique which permits to
reach high catalytic activities in oxidation reactions,
not only by enhancing the specific surface area but
also by controlling the surface density of specific sur-
face defects through a proper choice of calcination
conditions.
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