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ELSEVIER
Received 6 May 1996; received in revised form 2 September 1996; accepted 9 September 1996
Abstract
A IT-IR and EPR spectroscopic investigation has been carried out on a series of Lal_,Ce,CoO? (x=0-0.15) perovskite-type
catalysts, which are quite active for the reduction of NO by CO, and a mechanism has been proposed for this reaction. The first
step involves the oxidation of CO by the catalyst, followed by the dissociative adsorption of NO onto the catalyst surface.
Finally, adsorbed nitrogen (Nads) yields N20, N2 and NCO,d, along three parallel paths. Thus, oxygen exchange between NO
and CO seems to occur indirectly and involves a surface oxygen vacancy. The catalytic activity is decreased by the substitution
of Ce4+ for La3+ in the perovskite-type structure, which reduces the mobility of bulk oxygen. Activity is partially restored for
s>O.O5 due to the presence of a segregated cerium oxide phase.
Keywords:
Perovskites;
1. Introduction
LaM03 oxide mixtures with perovskite-type
structure (M=element
of the first transition series) have
been thoroughly investigated in recent years [l-7].
The main interest concerned their peculiar solid-state
characteristics
and their potential use as catalysts,
particularly in exhaust gas depollution processes [8151. In fact, they can be regarded as valuable catalysts
alternative to supported noble metals, which are easy
to synthesize [16] with lower cost and having a great
stability upto high temperatures. Moreover, their com*Corresponding author. Fax: (+39-2) 70638129.
0926-860X/97/$17.00 0 1997 Elsevier Science B.V. All rights reserved.
PII SO926-3373(96)00089-6
(1)
The latter leads to NO abatement with some advantages with respect to the more popular selective
catalytic reduction
(SCR) by NH3, as it is not
affected by possible slipping of NH3, since it employs
36
0.05
0.1
0.15
0.2
CO as reductant,
a usual component
of exhaust gases
[181.
N20 was shown to form in parallel with reaction
(1). Moreover, the specific activity of the catalysts
employed in NO and CO conversion, referred to unit
time and unit surface area of Lai_,Ce,CoOs
oxide,
was shown to depend on x value [17], i.e. on the
percent substitution of cerium for lanthanum. A typical trend is reported in Fig. 1. While lanthanum
cobaltate (x=0) proved a good catalyst, specific activity decreased after introducing Ce ions in the oxide,
with a minimum for x=0.05. However, activity was
partly restored for higher degrees of Ce substitution,
levelling out for x>O.l.
In the present work, we report an IT-IR and EPR
spectroscopic investigation on Lat-JZexCoOs
oxides,
aimed at elucidating the influence of cerium on the
catalytic activity of the oxides and at getting information on the mechanism of the heterogeneous reduction
of NO by CO. In particular, we carried out a FT-IR
analysis of CO and NO separately or simultaneously
adsorbed on series of oxides, aswellasanEPRanalysis,
bothbeforeandaftertheiruseascatalystsinreaction(1).
2. Experimental
2.1. Materials
The oxide series Lai_JJe&oOs
(x=0, 0.05, 0.10,
0.15) was prepared by the sol-gel technique in the
by FT-IR
3.1.1. Pretreatments
The effect of sample pretreatment at 923 K is shown
in Fig. 2. The transmittance IR-spectrum of a x=0.10
2400
2200
2000
1600
1600
1400
1200
1000
BOO
600
31
An
1900
1800
1700
1200
1100
1000
38
(2)
Nads + NO + N20
(3)
Nads + Nads + N2
(4)
representing
3.1.3. CO adsorption
The IR analysis was also carried out at various
temperatures in the case of CO adsorption on different
oxide samples. A large number of bands appeared, as
expected, after CO adsorption at room temperature
(Fig. 4Ac). No absorption around 2150 cm- was
L. Fomi et &./Applied
39
0 -co
(5)
(6)
(7)
Reaction (7) should have a high activation energy, as
carbonates are formed at room temperature onto the
catalyst surface, but no COz is detected in the gas
phase. This mechanism is in line with the fact that we
never observed the presence of steadily adsorbed CO
by IR analysis. TDP-MS investigations
also showed
[17] that only COa desorption occurs independent of
the CO adsorption temperature.
[b)
2M)o 2400
2200
2000
ied0
1600
1400
1200
1000
800
navenuabers km-11
The system under investigation presented a completely different behaviour when CO was adsorbed
onto the oxides at higher temperature.
Fig. 5Ab,
reporting the transmittance
spectrum recorded after
CO adsorption onto the x=0.10 sample at 623 K,
evidences a change of the whole spectral shape with
respect to the reference spectrum (Fig. 5Aa). However, a spectrum identical to the latter could be
obtained after the regeneration
of sample in air
(200-300 Tort-) at 773 K (Fig. 5Ac). A similar behaviour was observed in analogous conditions for CO/
ZnO system [32].
A possible explanation
is that at higher temperature also bulk oxygen becomes available for
oxidation, in view of its rather high mobility in the
perovskite-type
structure,
which presents
many
40
L. Fomi et &/Applied
Catalysis B: Environmental
13 (1997) 3543
Fig. 6. Absorbance
NO co-adsorption
after co-adsorption
(b) 623 K and (c)
successive 20 min
difference-spectra
(a. u.) relative to CO and
onto the x=0.10 sample: spectrum recorded (a)
at 573 K and successive 20 min evacuation at
723 K; (d) after co-adsorption at 673 K and (e)
evacuation at 973 K.
!..
,,,
___
_,,
,.,
,,,I,,_,,
,,,,,
? -?
Co+NO-+Co-0-Co+Nads
(5)
(2)
(8)
by EPR
Some preliminary
EPR results obtained
with
Lai_,Ce,CoOs
samples have been already reported
by us [17]. There we had observed that all fresh
samples gave no EPR signal. Furthermore,
the
x=0.05 sample remained EPR silent even after ther-
41
L. Fomi et al/Applied
1000
Catalysis B: Environmental
2000
3000
13 (1997) 3543
4000
5000
[Gl
sample, after use as catalyst in reaction (1) at 523 K, recorded at (a) 150 K, (b) 180 K, (c) 210 K, (d) 240 K, (e)
1491.
The fact that at higher detection temperature an
EPR line-broadening
is observed with the used samples in the presence of cerium ions would suggest that
in the present case also a layer-like structure forms,
with oxygen-richer planes alternating with planes in
which Co-a-Co
structures prevail. This layer-like
structure, in which electrostatic interactions favour the
insertion of Co-Cl-Co planes, would be stabilized by
the presence of the segregated CeOZ phase. In fact, in
The present IT-IR and EPR spectroscopic investigation allows us to propose the following mechanism
for the reduction of NO by CO over these perovskitetype catalysts. The first step involves the oxidation of
CO by the catalyst, followed by the dissociative
adsorption of NO onto the catalyst surface. Finally,
adsorbed nitrogen (Nads) yields NzO, N2 and NCO,d,
along three parallel paths. Thus, oxygen exchange
between NO and CO seems to occur indirectly and
involves a surface oxygen vacancy. The catalytic
4. Conclusions
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