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Applied Catalysis B: Environmental 13 (1997) 3.543

FYI-IRand EPR spectroscopic analysis of

La1 _,Ce,CoO3 perovskite-like catalysts
for NO reduction by CO
Lucia Fornia7*, Cesare Oliva, Tommy Barzettia, Elena Selli,
Alexej M. Ezeretsb, Anatoli V. Vishniakovb
aDipartimento di Chimica Fisica ed Elettrochimica, Universifb di Milano, Via Golgi 11.201339, Milano, Italy
h D. I. Mendeleev University of Chemical Technology of Russia, Miusskaja Sq. 9, Moscow, Russia

Received 6 May 1996; received in revised form 2 September 1996; accepted 9 September 1996

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.


NO reduction by CO; IT-IR; EPR analysis

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
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

position can be varied and their structure characterized

easily. So, they are particularly suitable for activitystructure correlation studies.
The catalytic activity of a series of oxides with
Lal_XCeXCoOj (x=04).20)
has been
investigated in a previous work [ 171. Two environmentally relevant redox reactions have been considered: the oxidation of CO with air and the reaction,
NO + CO -+ CO2 +1/2N2


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

L. Fomi et al./Applied CatalysisB: Environmental13 (1997) 3543






Fig. 1. Specific activity (accuracy of data = &lo%), defined as

percent CO (0) and NO (0) conversion per unit catalyst surface
area, and selectivity towards N20 (0) in reaction (1) over
catalysts at 573 K as a function of Ce stoichiometric coefficient, x.

CO as reductant,

a usual component

of exhaust gases

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
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
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,
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

presence of acrylic acid, as already described [ 171. A

limited amount of cerium could be inserted in the
perovskitic lattice. A careful XRD analysis showed
that less than 5% of La ions could be substituted by Ce
ions. The rest of cerium was present as CeOz in a
separate fee phase, so that a mixture of Lai_JZexCoOs
(x < 0.05) and CeOz was finally obtained [ 171.
The gases employed as probes in the FT-IR analysis
(purity>99.90 vol %,
O2<50 ppm,
C&<50 ppm, total HC<25 ppm, H,0<20 ppm) and
NO (purity>99.90 vol %), both purchased from SIAD
2.2. Procedure
IT-IR spectra were recorded by means of a Nicolet
Magna-IR 550 instrument, equipped with a quartz
sample holder with KBr windows, connected to high
vacuum ramp. Further details on the apparatus
employed can be found elsewhere [ 191.
The catalyst samples were first dehydrated
483 K, then finely ground in an agate mortar and
overnight with water vapour at room
temperature. 15-25 mg of the powder were pressed
into a self-supporting
wafer of 1 cm2 surface area,
which was then put in the sample holder and evacuated
for 2 h at 923 K. After cooling down to room temperature, the reference spectrum was recorded.
The adsorption of probe gases was carried out at
room temperature or at 473-673 K, by equilibrating
the catalyst wafer for 20 min and 1330 Pa of each gas,
either with pure CO, or with pure NO, or with a
mixture of CO and NO. The desorption of the probe
was successively monitored stepwise by evacuating
the sample at progressively
higher temperature
(AT=100 K), starting from 373 K, when adsorption
was carried out at room temperature, or from 50 K
below the adsorption temperature, when the adsorption was performed at higher temperature. The samples were always cooled down to room temperature
between each step, to record the IR spectrum. Adsorption, desorption and heat treatments were carried out
on the samples outside the infrared beam. The composition of the gas phase in contact with the catalysts
was also monitored by FT-IR analysis.
IR spectra, always recorded under a pressure of ca.
2.5 x 10e3 Pa in the sample holder, were the average of
60 records with a 2 cm- definition. They were

L.. Fomi et al. /Applied Catalysis B: Environmental 13 (1997) 3543

obtained in 2.2 min thereby excluding any significant

heating of the samples. The background spectrum,
recorded in the absence of the sample and under
identical operating conditions, was always automatically subtracted. When investigating
the change in
composition of probe gases in contact with the catalyst
at a given temperature, IR spectra were recorded in
only 11 s, as an average of 10 records with a 8 cm-
Most of the results are presented as differencespectra, i.e. as the difference between the absorption
spectra recorded after gas adsorption and the reference spectrum (vide supra). This procedure is very
useful for observing weak absorptions due to species
formed during heat treatment, although it can sometimes lead to artifacts [20].
Analysis by EPR was done ex-situ by means of a
Bruker ESP 300 instrument, as already described [ 171.
Both samples simply activated in air or in nitrogen and
samples which had been employed as catalysts for
reaction (1) were examined in the 135-293 K temperature range.

3. Results and discussion

3.1. Analysis

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











Fig. 2. Transmittance spectrum of x=0.10 sample evacuated (a) for

one night at room temperature and (b) for 2 h at 923 K (reference






1600 1500 1400 1300

navenumbers h-11




Fig. 3. Absorbance difference-spectra

(a. u.) recorded after (a) NO
on the x=0.10
sample at room temperature
successive 20 min evacuation at (b) 373 K, (c) 573 K and (d)
673 K.

sample evacuated at room temperature down to a

residual pressure of 2.67x 10e3 Pa is reported in
Fig. 2(a), whereas Fig. 2(b) shows the transmittance
spectrum of the same sample after a 2 h evacuation at
923 K (reference spectrum). Heat treatment causes
complete disappearance of the two absorption bands at
1050 and 852cm-,
which do not reappear after
of the sample with air. These bands
can be attributed to carbonates formed after atmospheric CO2 adsorption [21]. In particular, the band at
ca. 850 cm- 1s characteristic
of the out-of-plane
bending of the carbonate ion and it is always observed
in the presence of this species. The untreated oxide has
a rather low transmittance
(Fig. 2a) and only the
absorption bands due to vC@- appear in the spectrum
in the relatively more transparent
1200-800 cm-
3.1.2. NO adsorption
NO adsorption was carried out on catalysts at room
temperature (Fig. 3) and at 523 K. Almost the same
adsorption trend was observed for all the perovskite
oxides examined. The spectrum recorded after evacuation at 573 K following saturation at room temperature (Fig. 3c) still showed the absorption patterns
of NO (vide infra), whereas almost
complete desorption
occurred after evacuation
673 K (Fig. 3d). An identical behaviour was observed
when adsorption was carried out at 523 K. This indicates that the same species form after NO adsorption at
room temperature and at 523 K.


L. Forni et al. /Applied

Catalysis B: Environmental 13 (1997) 35-43

The bands at 1898 and 1832 cm-, appearing in the

room temperature spectrum (Fig. 3a), are characteristic of physically adsorbed, and thus slightly perturbed, NO. The presence of a double band results
from NO adsorption through either oxygen or nitrogen
atom. A small frequency difference with respect to the
gas phase vibration (1876 cm-) is observed in both
cases, as polar interactions are responsible for adsorption.
The spectrum at room temperature
(Fig. 3a) is
rather complex,
at frequencies
1600 cm-, due to the absorption of labile monoand bi-dentate nitrate species [22]. On the other hand,
there is no NO adsorption onto metal ions, as the
corresponding bands would appear at higher frequencies [23].
The difference-spectra
obtained after evacuation at
373-673 K (Fig. 3b-d) show only two neat absorption
peaks at 1471 and 1381 cm- and no absorption in the
1000-1200 cm- region. Species such as NO,,,,
NO,, or ONO& should generate at least one band
in this region, besides a couple of bands in the 13001500 cm- region [22,24-261. Hence, the band at
1381 cm- can be attributed to NO adsorbed in an
anionic vacancy, as observed by Shin et al. [27] in
analogous conditions, while the band at 1471 cm-
could be due to a similar species adsorbed onto a
different anionic vacancy.
The IR analysis of the gas phase during NO adsorption gives no evidence of NO2 formation. Thus, the
catalyst does not behave as an oxidant towards NO.
Taking into account that NO adsorption also leads to
the formation of N20 [17], we suggest, in agreement
with other authors [ 16,281, that the following reactions
occur after NO adsorption:
Co- -Co+NO+Co-0-Co+Nads


Nads + NO + N20


Nads + Nads + N2



a surface oxygen vacancy.

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

Fig. 4. (A) Absorbance difference-spectra

(a. u.) relative to CO
adsorption on the x=0.10 sample: spectrum recorded (a) after
adsorption at 623 K and (b) successive 20 min evacuation at
673 K, (c) after adsorption at room temperature and successive
20 min evacuation at (d) 373 K and (e) 573 K; (B) Gas phase
transmittance spectra recorded (a) at the beginning of CO contact
with the x=0.10
sample at room temperature
and (b) at
equilibrium; (c) at the beginning of CO contact with the x=0.10
sample at 573 K and (d) at equilibrium.

however detectable due to physically adsorbed CO.

Adsorption patterns were still observable after evacuation at 573 K (Fig. 4Ae), but disappeared after
at 673 K. However, when the sample
was saturated with CO at 623 K (Fig. 4Aa), evacuation at 773 K was needed, to desorb the species
for absorption. Thus, in contrast with
NO, the higher the adsorption temperature, the more
stable were the species generated by adsorption of CO.
When samples saturated at room temperature were
evacuated at 373 K (Fig. 4Ad), or when saturation was
carried out at 623 K (Fig. 4Aa), well resolved absorption bands appeared at 1470, 1399 cm- and 1471,
1389 cm-, respectively, together with a band around

L. Fomi et &./Applied

855 cm-. As the latter is typical of the bending in

plane of perturbed carbonate ions, we conclude, in line
with Tejuca et al. [29,30], that CO adsorption leads
exclusively to the formation of carbonate species. In
fact, the higher frequency double band can be attributed to a splitting of the 1415 cm- band due to the
asymmetric stretching of carbonate ions. Moreover, a
species should form [31]. In fact, the
frequency difference Av between the two splitted
100 cm-
(Fig. 4A).
Av=71 cm- for species formed after CO adsorption
at room temperature (Fig. 4Ad,e) and A~=82 cm-
after adsorption at 623 K (Fig. 4Aa,b). This confirms
the higher stability of carbonates obtained after CO
adsorption at 623 K, as Av should increase with
increasing the interaction strength [31]. No absorption
was ever observed
at frequencies
higher than
2000 cm- indicating that CO does not adsorb onto
metal ions.
Moreover, the IR analysis of the gas phase during
CO adsorption evidenced that no CO2 was produced at
room temperature (no bands at 2349 and 667 cm-
appear in Fig. 4Ba,b), while CO, which is responsible
for the 2143 cm- band, underwent oxidation when
adsorption was carried out at 573 K (Fig. 4Bc,d). It is
worth noting that no oxidant species was present in the
gas phase and consequently oxygen must have been
provided by the catalyst.
The following mechanism can thus be proposed for
the reactions occurring onto the catalyst after CO


Catalysis B: Environmental 13 (1997) 3543

0 -co


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.


2M)o 2400









navenuabers km-11

Fig. 5. (A) Transmittance spectra relative to the x=0.10 sample:

(a) reference spectrum, spectrum recorded (b) after CO adsorption
at 623 K and (c) successive regeneration with air (200-300 Torr) at
773 K. (B) Transmittance spectrum recorded after CO adsorption
(a) onto x=0 sample at 473 K, (b) onto x=0 sample at 523 K, (c)
onto x=0.05 sample at 573 K, and (d) onto x=0.10 sample at
573 K.

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
which presents


L. Fomi et &/Applied

Catalysis B: Environmental

defects. In fact, it is well known that oxygen

mobility increases with increasing concentration
cationic vacancies [33-351. Consequently, the substitution of Ce4+ for La3+ would reduce bulk oxygen
In order to verify this hypothesis, CO adsorption
onto the x=0.10 sample was compared with CO
adsorption onto the cerium-free x=0 sample and onto
the x=0.05 sample. The x=0.05 and x=0.10 samples
contain an equal amount of Ce4+ within the perovskite-type structure. Fig. 5B shows that the shape of the
spectrum relative to the Ce-free sample (x=0) changes
at relatively low temperatures (523 K, Fig. 5Bb). By
contrast, the spectrum of the Ce-doped samples keeps
the same shape upto higher temperatures
(573 K,
Fig. SBc,d). This means that in the x=0 sample, bulk
oxygen becomes available at lower temperature. This
is in line with an earlier observation [36] that kinetic
parameters of CO oxidation with air onto LaCo03
change considerably
between 473 and 523 K and
confirms that the presence of Ce4+ reduces the availability of bulk oxygen.
3.1.4. CO and NO co-adsorption
The results relative to CO and NO co-adsorption
onto the x=0.10 sample at 573 K are shown in
Fig. 6(a-c). Species were formed absorbing at frequencies both lower and higher than 1600 cm-.
These species disappeared at temperatures higher than
723 K. When co-adsorption was carried out at 673 K
(Fig. 6d), some species were still adsorbed at 973 K
(Fig. 6e). No absorption
appeared at frequencies
higher than 2200 cm-, confirming that no adsorbed
N20 species was formed.
The neat band at 2178 cm- can be attributed to a
isocyanate species Co@+)+ - NCO- generated from
the reaction between CO and Nads (vide infra, Eq. 8).
Other authors observed the same species onto perovskites [37], metal oxides [38], and supported noble
metals [39]. However, the isocyanate species should
not be a reaction intermediate, as it is stable even after
evacuation at 623 K (Fig. 6b). It rather appears to be a
surface by-product, which confirms the formation of
The weak absorption
band around 2000 cm-
(Fig. 6) is attributable to NO adsorbed onto Co, which
acts as an electron acceptor. This band exhibits an
increase in vibration frequency with respect to the

13 (1997) 3543

Fig. 6. Absorbance
NO co-adsorption
after co-adsorption
(b) 623 K and (c)
successive 20 min

(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.

corresponding gas phase absorption band (1876 cm-)

[23,37]. It may be recalled that this band was not
observed after adsorption of pure NO (vide supra).
However, we noticed that all our oxide mixtures are
much more transparent after co-adsorption of CO and
NO and consequently,
very weak absorption bands
may become observable.
The patterns appearing at frequencies lower than
1600 cm- consist of only a couple of bands peaking
at 1471 and 1399 cm- (A~=70 cm-) and of a band
at 850 cm-, due to adsorbed monodentate carbonate
species, for co-adsorption at 573 K (Fig. 6a). When
was performed at 673 K (Fig. 6d),
another couple of bands appeared, which were still
present at 1518 and 1345 cm- after desorption at
973 K (Fig. 6e). Since in this case A~=170 cm-, we
can assign this feature to a bidentate and therefore
more resistant carbonate species.
The change in composition of the gas phase was
always monitored during the co-adsorption process.
An example is reported in Fig. 7. CO*, and not N20,
formed as soon as the CO and NO mixture was put in
contact with the catalyst. The absorption due to NzO
1286 cm-)
(Fig. 7b-c) and constantly increased with time. This
confirms that N20 should not be an intermediate
species, but rather a product of a reaction parallel
to N2 formation.

L Fomi et al. /Applied







Catalysis B: Environmental 13 (1997) 3.543


00 2Boa 2600 2400 2200 2ooa 1m 1EAJa1400 12w iooo ml0


Fig. 7. Transmittance spectra of the gas phase at (a) the beginning,

(b) half-time of CO and NO co-adsorption and (c) at equilibrium.

All these results lead us to propose the following


? -?


Nads + NO --+ N20 (3)

Nads + Nads ---f N2 (4)
Nads + Co + NC&j,


The interaction of N20 with an oxygen surface

vacancy, in a way similar to that of NO in Eq. 2,
cannot be excluded on the basis of our experimental
results. Moreover, CO should react directly from the
gas phase, probably
to a Rideal-Eley
mechanism, as also suggested by Tascon et al. [37].
Finally, the fact that the catalytic efficiency of perovskite-type
oxides decreases with time-on-stream
[17] could be ascribed to the formation of stable
carbonate species. Furthermore,
when the rate of
reaction (5) slows down, as also suggested by our
EPR analysis (vide infra), it can become rate-determining.
3.2. Analysis

by EPR

Some preliminary
EPR results obtained
samples have been already reported
by us [17]. There we had observed that all fresh
samples gave no EPR signal. Furthermore,
x=0.05 sample remained EPR silent even after ther-


mal activation for 1 h at 723 K, unlike the x=0.10

sample. In fact, the latter showed an EPR line after
activation either in N2 or in air. That line was Lorentzian-shaped
and characterized
by a width AH
nearly independent
of temperature.
Therefore, the
product A = I. AH2 was proportional to the concentration of the paramagnetic species, Zbeing the peak-to
peak intensity of the first derivative. The following
results were obtained: A(293 K)/A( 135 K)=0.28 (activation in Nz), and A(293 K)/A(135 K)=O.33 (activation in air).
A different situation was observed for the samples
employed as catalysts in reaction (1) at 523 K. In fact,
in all these cases the Lorentzian-shaped
EPR line
broadened linearly with temperature (Fig. 8), while
the concentration
of the paramagnetic species again
A(293 K)/
A(135 K)=0.29 (for x=0.10) and =0.77 (for x=0.15).
In our opinion, Corv (t&e:) and Con (t6,sei) low-spin
paramagnetic states could be responsible [40] for all
the above mentioned EPR patterns. In fact, the Lorentzian shape of these lines indicates that they are due
to spin-spin exchange overcoming the dipolar spinspin interactions occurring between the two nearest
neighbour Co low-spin paramagnetic ions. With activated samples, less intense EPR lines were observed at
higher temperature, but with nearly unchanged AH
value. This indicates that in these cases the concentration of the EPR-active species should decrease at
higher temperature. Therefore, such species should be
The oxygen atom, in fact, would cause a
superexchange effect between the two metal atoms,
producing the observed exchange-narrowed
EPR line. At higher temperature
decrease of Co-O-Co
species would
be a consequence of the increased oxygen mobility.
However, the EPR results obtained with samples
after catalytic use (Fig. 8) cannot be interpreted only
on this basis. In fact, in these cases the Lorentzianshaped EPR band broadens at higher temperature.
The spin-spin exchange (or super exchange) interactions are strongly dependent on the spin-spin distance. Therefore,
they are modulated
by lattice
vibrations. However, it has been shown [41] that such
a modulation does not provide any spin-lattice relaxation pathway when the spin-spin exchange is isotropic. On the contrary, when the latter is anisotropic, the
interaction can shorten the spin-lattice

L. Fomi et al/Applied


Catalysis B: Environmental



13 (1997) 3543



Fig. 8. EPR spectra of x=0.10

293 K.

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)

relaxation time, causing a linearly temperature-dependent broadening of the Lorentzian-shaped

(exchangenarrowed) EPR line.
Anisotropies can arise in the spin-spin interactions
when the spin and orbit angular momenta are closely
coupled, so that a given component of the spin may be
associated with a given orbital wave-function having a
lobe extending in the direction of a neighbouring ion
[41]. This has been observed with layer-like crystals,
which closely approximate two-dimensional
antiferromagnets, in particular with systems formed of layers
of S = $Cuz+ sites [42-48] and other compounds

the interface region between the perovskite-like

cerium oxide phases, the latter would behave as a
sink of oxygen, favouring the conversion of CooCo sites into Co-O-Co sites. The stability of the CoO-Co surface plane would reduce the catalytic activity
of the sample, but at the same time it would also
decrease the crystal strains, thus leading to an increase
of catalyst duration.

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

L. Fomi et al. /Applied Catalysis B: Environmental 13 (1997) 3543

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 x>O.O5, due to the presence of a segregated cerium oxide phase.

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