451

Topics in Catalysis Vols. 30/31, July 2004 (
2004)

Deactivation on vehicle-aged diesel oxidation catalysts

F. Cabello Galisteoa, C. Laresea, R. Mariscala,*, M. Lopez Granadosa, J.L.G. Fierroa, R. Fernandez-Ruizb,
and M. Furiob
a

Instituto de Catalisis y Petroleoqumica (CSIC). C/ Marie Curie 2. Cantoblanco, 28049 Madrid, Spain
Servicio Interdepartamental de Investigacion. Facultad de Ciencias. Universidad Autonoma de Madrid. Cantoblanco, 28049 Madrid, Spain

This paper studies oxidation catalytic converters that were vehicle-aged in a diesel automobile. The deposition of several atoms
(S, P, C, Si, Ca, Zn and Fe) was detected by several chemical analysis techniques. Moreover, AlPO4 and Al2(SO4)3 were identied
by XRD. The catalytic performance of the aged catalysts with dierent mileages showed a similar degree of deactivation for CO
and C3H6 oxidation. By contrast, laboratory sintering carried out on fresh catalysts revealed that it may have certain impact in the
deactivation of diesel catalysts. Nevertheless, the possibility that the impact of chemical deposition on deactivation has a threshold
value cannot be discarded.
KEY WORDS: diesel oxidation catalysts; deactivation; platinum sintering; chemical depositions.

1. Introduction
The installation of catalytic converters in the exhaust
pipes of gasoline and diesel cars is now a common
practice adopted by automobile manufactures to comply
with current legislation. In the case of diesel cars, the
current commercial catalyst is an oxidation-type catalyst
based on platinum [1]. It aims at depleting the gaseous
emissions of CO, unburned hydrocarbons (HC), and the
liquid fraction of solid particles, known as the soluble
organic fraction (SOF), by total oxidation to CO2 and
H2O [2].
Most studies on this kind of catalyst have been
directed to gaining insight into the reaction mechanisms
and to improving the catalytic properties [3], whereas
deactivation has received much less attention. Some
work oers information about the causes of deactivation
on three way catalysts (TWCs), which are installed in
gasoline-driven cars [4,5]. The aim of the present work is
to shed light on the causes of deactivation on current
diesel oxidation catalysts (DOCs), a key aspect when
considering the search for new technologies for more
ecient and more resistant catalytic converters. Moreover, identication of the causes of the deactivation of
DOCs that can be reverted may allow the implementation of procedures that reactivate aged catalysts.
Although the technology of the rst catalytic converters installed in gasoline vehicles in the seventies was
based on oxidation catalysts [6], the information and the
conclusions derived in the early days of their implementation, although valuable, cannot be directly applied to
current DOCs. Firstly, the type of engine and operation
conditions are dierent, whose consequence for catalysts
is the lower temperature to which the converter is
subjected. Second, because the formulation of diesel fuel
*To whom correspondence should be addressed.
E-mail: r.mariscal@icp.csic.es

(and its current additives) is not related to that of

gasoline.
The present work aims at identifying the eects that
functioning under real vehicle conditions has on DOCs.
The following techniques were used with the purpose of
to detect chemical deposition as a potential cause of
deactivation: total reection X-ray uorescence
(TXRF), energy dispersive X-ray spectroscopy (EDS)
and X-ray photoelectron spectroscopy (XPS). Characterization by evolved gas analysis coupled to a mass
spectrometer (EGA-MS) and XRD was also carried out.
Moreover, the catalytic activity of samples extracted
from the monolith catalyst was measured in a microreactor. This research was carried out in the hope that a
cross comparison between the information derived from
the physico-chemical characterization and that derived
from the catalytic properties might give some clues
about the causes of deactivation on DOCs.

2. Experimental
Monolith catalysts were extracted from the same
model of vehicle diesel, a Ford Galaxy 1.9 TDI. The
vehicle belonged to the eet of the Department of
Homologation of Ford Spain that kindly supplied the
converters. It guaranteed controlled maintenance of the
cars and statistically similar driving conditions. This
Department veried that the monoliths were supplied by
the same manufacturer and that the specications of the
catalyst were similar in all the catalytic cartridges. One
was dismantled from an automobile with 0 km (fresh
catalyst) and used as reference. The used catalytic
converters were dismantled after running for ca.
48 000 km and ca. 77 000 km. Fresh samples will be
referred to as D00 and aged samples as D48 and D77.
Aliquots from the beginning (rst millimeters) of the
monoliths were sampled for the study. Small pieces of
1022-5528/04/07000451/0
2004 Plenum Publishing Corporation

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F. Cabello Galisteo et al./Deactivation on diesel oxidation catalysts

the ceramic wall with the adhered washcoat were

obtained by gently breaking the monolith structure.
Particles with sizes between 0.60.8 mm were sieved for
the assays on catalytic activity. The other fragments
were used for the characterization studies.
TXRF analysis was performed on a Seifert EXTRAII spectrometer (Rich Seifert & Co, Ahrensburg,
Germany). Further details of the equipment used and
procedure followed are described elsewhere [7]. The
SEM-EDS analyses were obtained on a Philips XL30
scanning electron microscope coupled to an EDAX
DX4i analyzer for energy-dispersive X-ray analysis. The
chemical composition of the outermost layer (ca. 1 lm)
was analyzed by placing the pieces in the sample holder
with the washcoat exposed to the electron beam; for the
analysis a window with dimensions of 450 500 lm was
used. This analysis was repeated several times on
dierent regions in the washcoat. Au was deposited by
a Sputter Coater SC502 device in order to avoid
charging phenomena during analysis. X-ray photoelectron spectroscopy (XPS) experiments were accomplished with a VG Escalab 200 R spectrometer
equipped with a hemispherical electron analyzer and
an Mg Ka (hm 1253.6 eV, 1 eV 1.6022 10-19 J) Xray source. Powdered samples were mounted on a
sample rod and the pressure in the ion-pumped analysis
chamber was below 3 10-9 Torr during data acquisition. EGA-MS studies were performed on an experimental device coupled to a Baltzer PrismaTM
quadrupole mass spectrometer (QMS 200) under
50 mL/min of 20% O2/Ar heating at 5 K/min. Hundred
milligram of sample sieved between 0.600.80 mm was
loaded into a U-shaped reactor. Ar was selected as
internal standard and each signal was divided by the
signal of the main fragment of Ar (m/z 40). Powder
X-ray diraction (XRD) patterns were recorded by
scanning between 10 and 80 in the scan mode (0.02,
2 s), using a Seifert 3000 XRD diractometer equipped
with a PW goniometer with a BraggBrentano h/2h
geometry, an automatic slit, and a bent graphite
monochromator.
Catalytic activity tests were performed using a
conventional xed-bed ow reactor at atmospheric
pressure described in detail elsewhere [5]. A gas mixture
made up to resemble the composition of diesel exhaust
gas: CO2 (10%), H2O (10%), O2 (6%), NO (300 ppm),
C3H6 (300 ppm), CO (400 ppm), H2 (133 ppm), and Ar
(balance) was used [8]. The space velocity in the light-o
mode experiments was 105 h-1, and temperature was
increased from 373 to 773 K at a rate of 5 K/min.

3. Results and discussion

Figure 1 displays the relative concentrations (mass
concentration relative to Si 100) of the main elements
detected by TXRF in fresh and used samples. Si is

Figure 1. Mass concentration (relative to Si 100) of main elements

detected in fresh and used samples (standard deviation is also
included).

present in the cordierite support and its average concentration is expected to be constant in all samples. Pt is
the active element of the washcoat, which main component is c-Al2O3. No loss of the main washcoat components (Al and Pt) seemed to occur since their
concentration values did not decrease with mileage (Al
concentration is not shown here for the sake of
simplicity). The presence of some elements in the used
samples that were not detected or detected at lower
concentration in the fresh sample was evidenced by the
TXRF analysis. They can be considered as contaminants of the used DOC catalysts. The main contaminants detected were S (present in the fuel and in one of
the additives of the lubricant oil) together with P and Ca
(arising from the lubricant oil) [3,9] and nally Fe that
must arise from corrosion of the metallic part of the
engine. It is remarkable that the concentration of S is
very high with respect to the other contaminants found
in the catalytic converters. Zn also takes part of the
molecule added to the lubricant oil to improve its
stability along with Ca, P and S. However, the chemical
analysis by TXRF showed that the Zn concentration in
the used samples was not higher than in the D00 sample,
very likely because the Zn concentration in the fresh
sample (impurity of the cordierite) was higher than the
Zn deposit on the used sample. TXRF analysis showed
that P deposition increased with mileage whereas the
trend of S, Ca, Fe concentrations showed a maximum
for medium mileage. This suggests that the accumulation mechanism of P on the monolithic catalyst is
dierent to that of S, Ca and Fe.
Figure 2 shows the most representative X-ray uorescence spectra obtained with the SEM-EDS probe on
the washcoat of the fresh and used samples according to
the procedure indicated in the experimental part. This
experimental procedure facilitates detection of the
deposition of contaminants on the outer part of the
washcoat. It is important to stress that the SEM-EDS

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F. Cabello Galisteo et al./Deactivation on diesel oxidation catalysts

Figure 2. EDS spectra of fresh (D00) and used (D48 and D77) samples.

analysis was only used for detection purposes. Quantication of contaminant deposition cannot be accomplished by this technique because of its intrinsic
limitation concerning not only the physical basis but
also the experimental methodology used for the analysis.
The detection of Au was a consequence of the metallization process. The remarkable accumulation of Si in
this part of the washcoat during ageing was evident not
only because its concentration increased with mileage
but also because the Al2O3 of the washcoat was being
covered, as deduced by the decrease in the Al signal. Si
can thus be considered as a contaminant present in the
vehicle-aged diesel catalysts. It may arise from the
foaming inhibitors added to the fuel (to facilitate
refueling) or the silicone elastomers used in metallic
parts as a sealant [10]. SEM-EDS analysis also revealed
that Ca seemed to be concentrated on the outermost
layer of the washcoat and Zn and Fe deposition was
clearly detected in the used DOC.
Table 1 reports the binding energy (BE) of the core
electrons and the atomic ratios of some of the most
important components and contaminants detected by

XPS at the surface of the DOCs: Si 2p, Al 2p, Pt 4d, P

2p and S 2p. Other contaminants such as Ca, Fe and Zn
could not be detected by XPS, perhaps because they
were not located on the surface of the washcoat grains.
The high BE value for P and S indicated the presence of
sulfates and phosphates for aged catalysts. It was also
observed that the Si/Al ratio increased with mileage,
suggesting that Si was being deposited on the washcoat
component during use and that the concentration of this
external Si is larger at higher mileage (Al and Si are also
present in the cordierite but the contribution of the Si
and Al from cordierite to XPS signals is expected to be
low due to the lower surface area of cordierite in
comparison with those from the washcoat). XPS analysis detected a higher level of S deposition in the
medium-mileage used DOC and a higher P concentration in the high-mileage sample. These conclusions are
consistent with the results of the TXRF and EDS
analyses. Regarding the Pt/Al ratio, the similar value
found for the fresh and used DOCs suggests that Pt
sintering was not very intense, unless Pt and Al2O3
underwent a similar sintering degree (which is very

Table 1
Binding Energy (BE) of core electrons and atomic ratios (values in brackets) of washcoat components and the most important contaminants
determined by XPS on fresh and used DOCs
Catalysts
D00
D48
D77

Al 2p

Si 2p (Si/Al)

Pt 4d5/2 (Pt/Al)

S 2p (S/Al)

P 2p (P/Al)

75.4
75.3
75.3

103.4 (0.206)
103.4 (0.422)
103.4 (0.706)

316.0 (0.0027)
314.4 (0.0028)
314.7 (0.0027)

170.0 (0.152)
169.9 (0.103)

135.0 (0.067)
134.9 (0.099)

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F. Cabello Galisteo et al./Deactivation on diesel oxidation catalysts

unlikely). Another possibility is that although sintering

may be occurring, the covering of both components by
the high level of contamination (the formation of a layer
of phosphates over the outer surface of the washcoat has
been detected [11] in used TWC catalysts) could decrease
the Pt and Al XPS signals and could prevent the
detection of the sintering of Pt.
EGA-MS analyses were conducted with a dual aim:
rst, to detect the main species evolving from the
catalysts while calcining and, second, to obtain semiquantitative information about their accumulation.
(Moreover, EGA-MS analysis indicated the temperature
of elimination of those deposits, which could be useful
for re-activation of the catalysts). Figure 3 shows the
traces of m/z 44 (CO2) and 18 (H2O) fragments. The
evolution of H2O and CO2 was detected in the fresh
sample; these signals may arise from the decomposition
of some of the precursors of the washcoat components
or from the calcination of unavoidable grease or
hydrocarbons adsorbed during storage of the fresh
exhaust pipe. However, this cannot be the origin of the
H2O and CO2 signals observed in the used DOCs
because they were subjected to high temperatures (673
773 K) for long times. The burning of hydrocarbon
residues left on the surface of the catalysts during

Figure 3. CO2 (dotted line) and H2O (solid line) proles from EGAMS analysis of fresh (D00) and used (D48 and D77) catalysts.

functioning under driving conditions must be the

explanation. The simultaneous detection of CO2 and
H2O at low temperature (between RT and 673 K) can be
assigned to the combustion of hydrocarbons. However,
the evolution of CO2 at high temperatures (673873)
that occurred without H2O formation must be assigned
to the burning of coke with a low H/C ratio that was
accumulated during DOC use. This coke accumulation
was larger in the high-mileage sample. The evolution of
SO2 (m/z 64) was also followed and a peak at 1030 K
was detected, indicating that sulfates were decomposed
at this high temperature. Moreover, the SO2 signal was
more intense in the medium mileage used catalyst,
indicating that S deposition was higher in this catalyst,
in agreement with the chemical and XPS analyses.
Figure 4 shows the XRD of the fresh and used
samples. The Al2(SO4)3 peaks were detected in the D48
pattern whereas in the D77 pattern, besides Al2(SO4)3
peaks reections assigned to amorphous AlPO4 [11]
were observed. It has been reported that alumina shows
a strong capacity to adsorb SO2 in sulphate form [12].
The relevance of theses phases, aluminum phosphates
and sulfates, is related to the fact they are able to alter
the surface chemical properties of the support and
modify the electronic properties of the Pt particles,
which may result in deactivation of catalytic activity
[13]. The presence of other amorphous phases not visible
by XRD cannot be discarded. Actually, the presence of
calcium or zinc phosphates has been reported by other
authors [11]. These phosphates form an impervious
glaze-like layer that can inhibit the diusion of reactant
to the active surface.
With respect to catalytic activity, gure 5 shows the
light-o curves for the oxidation of C3H6 and CO.
Deactivation in C3H6 oxidation was evident in the shift
of T50 to higher temperatures for D48 and D77 with
respect to the fresh catalyst (from 503 K in the fresh

Figure 4. XRD diractograms of fresh (D00) and used (D48 and D77)
samples, where the phases identied are (s) cordierite (n) Al2(SO4)3
and (r) AlPO4.

F. Cabello Galisteo et al./Deactivation on diesel oxidation catalysts

Figure 5. CO and C3H6 conversions on fresh catalyst D00 (s) and

aged catalysts (n) D48 and (m) D77.

sample to 535 and 548 K for D48 and D77, respectively). The oxidation of CO was also deactivated (T50
passed from 471 K in the fresh sample to 522 and
536 K). The rate of deactivation seemed to slow down in
the high-mileage sample. Although the D77 catalyst had
running life of ca. 30 000 kms more than D48, it was
only slightly more deactivated than D48. The deposition
of contaminants did not appear to be the cause of
deactivation with the highest impact on deactivation.
For most of the contaminants deposited on the catalyst
(including coke), the accumulation increased with mileage at a constant rate whereas deactivation did not. The
inverse trend to that of deactivation was observed for S
deposition.
In an attempt to explore the possibility that sintering of the washcoat components might underlie the
deactivation of the catalysts, the fresh sample was
subjected to the consecutive high-temperature (HT)
treatments shown in gure 6 (see captions for descriptions of the HT treatments) with the aim of producing
sintering of the washcoat components. Treatment at
873 K for 10 h resulted in deactivation of the catalytic
behavior of the catalyst. Calcination at 873 K for
longer times did elicit a stronger degree of deactivation.

455

Figure 6. CO and C3H6 conversions on fresh D00 sample (s), after

calcination in air at 873 K for 10 h (4), for additional 10 h (() and
wet air for an additional 10 h (m).

However, wet calcination at 873 K did increase the

degree of deactivation slightly, in particular CO conversion. These results suggest that sintering may have
certain impact in the deactivation of DOC catalysts,
although with smaller eect on CO oxidation [14].
However, the possibility that the impact of contaminant deposition on deactivation might have a threshold
value cannot be discarded.

4. Conclusions
It is not easy to give a relative ranking of the impact
of each chemical poisoning elements on the capacity of
CO/HC catalytic oxidation. However, and according
with our data, mainly sulphur and phosphorous as well
could be responsible of deactivation shown in the
studied DOC catalytic converts. They are present in
higher concentration than other poisons, which makes
ease their interaction with the component of catalytic
converters (Al2O3). For the rest of contaminants (C, Si,
Ca, Zn and Fe) found in the samples no interaction with
the component of the catalyst was detected. Since the
temperature reached by DOC catalysts in this type of

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F. Cabello Galisteo et al./Deactivation on diesel oxidation catalysts

engine is only moderate (lower than 550 C), thermal

ageing eect on noble metal sintering is not important
although a small contribution to DOC deactivation can
not be completely ruled out. Therefore, to avoid DOC
vehicle ageing a decrease of the sulphur content in diesel
and oil lubricant will be very convenient, because they
reached the highest concentration and seems to be the
main responsible of the observed deactivation.

Acknowledgments
Financial support by European Commission (G5RDCT-2000-00376), Ministerio de Ciencia y Tecnolog a
(MAT2000-2004-C02-01) and Comunidad de Madrid
(07M/0081/2002) is greatfully acknowledged. F.C.G.
wishes to thank the Ministerio de Educacion y Cultura
for his grant.

References
[1] H.J. Stein, Appl. Catal. B: Environ. 10 (1996) 69
[2] R.J. Farrauto, K.E. Voss and R. Heck, SAE Paper 932720 (1993)

[3] E.S.J. Lox and B.H. Engler, in: Environmental Catalysis, eds.
G. Ertl, H. Knozinger and J. Weitkamp (Wiley-VCH, New York,
1999) ch. 1.
[4] T.N. Angelidis and S.A. Sklavounos, Appl. Catal. A: Gen. 133
(1995) 121.
[5] F. Cabello Galisteo, C. Larese, M. Lopez Granados, R. Mariscal,
J.L.G. Fierro, R. Fernandez-Ruiz and M. Furio, Appl. Catal. B:
Environ. 40 (2003) 305.
[6] L.L. Hegedus and K. Baron, J. Catal. 37 (1975) 127.
[7] R. Fernandez-Ruiz, M. Furio, F. Cabello Galisteo, C. Larese,
M. Lopez Granados, R. Mariscal and J.L.G. Fierro, Anal. Chem.
74 (2002) 5463.
[8] D. Schmitt, H. Fuess, H. Klein, U. Neuhausen and E.S. Lox, Top.
Catal. 16 (2001) 355.
[9] R.J. Farrauto and K.E. Voss, Appl. Catal. B: Environ. 10 (1996)
29.
[10] J.C. Guibet, Fuels and Engines (Institute Francais du Petrole
Publications, Paris, 1999) ch. 1.
[11] M.J. Rokosz, A.E. Chen, C.K. Lowe-Ma, A.V. Kucherov,
D. Benson, M.C.P. Peck and R.W. McCabe, Appl. Catal. B:
Environ. 33 (2001) 205.
[12] D.J. Ball and R.G. Stack, in: Catalysis and Automotive Pollution
Control II, ed. A. Crucq (Elsevier Science Publishers B.V.,
Amsterdam, 1991) p. 337.
[13] G. Ramis, P.F. Rossi, G. Busca, V. Lorenzelli, A. La Ginestra,
P. Patrono, Langmuir 5 (1989) 917.
[14] G. Smedler and S. Lundgren, SAE Paper 9101173 (1991).