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SAE TECHNICAL
PAPER SERIES 931034

The Role of Ceria

in Automotive Exhaust Catalysis
and OBD-II Catalyst Monitoring

Galen B. Fisher
General Motors Research

Joseph R. Theis, Mark V. Casarella, and Stephen T. Mahan

AC Rochester

International Congress & Exposition

Detroit, Michigan
March 1-5, 1993

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931034

The Role of Ceria in Automotive Exhaust Catalysis

and OBD-II Catalyst Monitoring
Galen B. Fisher
General Motors Research

Joseph R. Theis, Mark V. Casarella, and Stephen T. Mahan

AC Rochester

ABSTRACT oxygen storage/release capacity of a catalyst system and

its HC conversion activity, methods that use oxygen
Ceria has become an increasingly important compo- storage to determine catalyst activity, particularly for
nent in automotive exhaust catalysts over the past warm-up catalysts, will not provide the level of accuracy
decade. Recently, with the proposal that measurements required for reliable on-board monitoring of catalyst
of oxygen storage be used for the on-board evaluation of performance.
catalyst performance for both low emission vehicles (LEV)
and non-LEV vehicles, understanding the role of ceria INTRODUCTION
and its deterioration with catalyst aging has become even
more important. It is well established that ceria in an In this paper we wish to review the role of ceria in
alumina support promotes oxygen storage/release by automotive exhaust catalysis and to examine how the
automotive catalysts under cycled air/fuel conditions, deterioration of ceria's beneficial properties may affect
which in turn promotes the catalyst's conversion perfor- proposed methods of catalyst monitoring to meet OBD-II
mance under those conditions. Another benefit of ceria is regulations. The deterioration of ceria's benefits is largely
its enhancement of the catalytic activity for other reac- caused by the negative impact of high temperatures on
tions, such as the water-gas shift reaction under rich the catalyst's conversion performance and oxygen
conditions. In addition, ceria may help catalyst durability storage capacity.
by promoting precious metal dispersion and playing some Although ceria's role in automotive catalysis had been
role as a stabilizer of the support. studied since the mid-1970's [1,2], ceria only began to be
To examine, in part, how these benefits of ceria used extensively in automotive exhaust catalysts in the
persist in aged catalysts, we have carried out emission mid-1980's. It was first used at levels near or below 10
measurements on catalysts with varying cerium levels in the washcoat of three-way catalysts [3]. The ceria
(0-50 ) that have received increasing amounts of content of present three-way catalysts is generally
accelerated aging. We find that for the washcoat formula- between 10 and 40 , although some formulations are
tion investigated, catalysts with a ceria content of about outside this range. Ceria is added to the alumina
30 provide the highest conversion efficiencies for HC, washcoat of monolithic catalysts because of four main
CO, and NOx after extensive high temperature treatments factors which beneficially improve the catalyst's perfor-
designed to mimic up to 100,000 miles of vehicle aging. mance. Much of the understanding of the role of ceria is
We have also measured conversion efficiencies for based on laboratory experiments and, while it is difficult to
catalysts, including warm-up catalysts in front of the assess the exact contribution of ceria in all phases of
underfloor location, which have been exposed to high exhaust catalysis, the main effects are as follows:
temperatures and suffered loss of oxygen storage capac-
ity, as measured using a multiple oxygen sensor ap- • By increasing the ability of the catalyst to store and
proach to meet OBD-II regulations. These catalysts still release oxygen under cycled air/fuel ratio conditions,
provide high conversion efficiencies on powertrains which ceria promotes reactions catalyzed by noble metals
have well controlled A/F ratios. Presumably the oxygen important for automotive exhaust emissions control
storage capacity of ceria can decrease after high tem- (e.g., CO oxidation and NO reduction);
perature exposure, due to the decreased surface area of • Ceria also appears to promote other reactions
the ceria and the precious metal particles and their catalyzed by noble metals that are not so dependent
decreased interaction with each other, while the precious on the cycled nature of exhaust gas composition.
metal surface area is still sufficient for good performance. Among these reactions whose kinetics are modified
To the extent that there is little correlation between the by the presence of ceria is the water-gas shift (WGS)
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2 931034
reaction, which occurs predominantly at rich A/F
ratios and provides another pathway for CO removal STORAGE (Lean A/F Ratios):
using the water already present in the exhaust;
Ceria may also help maintain the high surface area
or dispersion of the catalyst's noble metal particles;
There is also evidence that ceria stabilizes the RELEASE (Rich A/F Ratios):
surface area of the catalyst's alumina support, and
thereby increases its durability against high tempera­
ture excursions.
The actual oxidations and reductions may occur with
In this paper we will review some of the evidence for several constituents of the exhaust gases, but, in
these key contributions of ceria. We then present data general, results in the gain or loss of oxygen by some
showing there is an optimum amount of ceria centered component in the gas phase [8].
near 30% ceria content to achieve most favorable Oxygen storage/release occurs predominantly under
emissions performance. In relation to OBD-II diagnos­ closed-loop stoichiometric operation where the air/fuel
tics for catalysts, we also report data taken on vehicles ratio is oscillating between rich and lean conditions.
for catalysts which have lost their oxygen storage Under lean A/F ratios, the ceria takes up oxygen from
capacity, but still have high hydrocarbon conversion the exhaust according to reaction (1) above. Following a
efficiencies. We conclude that there are a range of transition from a lean to a rich condition, the ceria is
catalysts for which methods that use oxygen storage to reduced (e.g., by Eq. 2) and releases the oxygen which
determine catalyst activity will not provide the level of is used for oxidizing CO and hydrocarbons to CO2. It
accuracy required for reliable, on-board monitoring of then contributes to CO conversion at a time when there
catalyst performance. is insufficient oxygen in the gas phase to react all of the
CO present. When the air/fuel ratio shifts back to a lean
BACKGROUND condition, the ceria again stores oxygen by absorbing or
reacting with the excess O2 present in the exhaust [3].
Preparation of Ceria The resultant increased availability of reactive sites
allows the reduction of NOx (largely NO) by CO. Other­
To be beneficial, ceria must be dispersed through the wise, the excess absorbed oxygen inhibits NOx reduction
washcoat support of the precious metal [3,4]. Normally by preventing NO dissociation and rapidly consuming the
the ceria and alumina are applied together in a slurry reductant CO through oxidation. Several researchers
during coating. The ceria therefore is mixed intimately have reported on ceria's beneficial effect on NO reduc­
with theγ-alumina and ends up in the micropores and tion, including kinetic studies of the NO-CO reaction [9]
macropores of the alumina. There are also sol-gel as well as comparisons of NO dissociation on catalysts
processes [5] which may offer some advantages in with and without ceria [10].
dispersing the ceria in the alumina. In addition, there are The storage/release mechanism significantly in­
impregnation methods for preparing ceria on alumina in creases the overall CO and NOx conversions. It is most
a two-step process. Different preparation methods can effective when the A/F perturbations are small enough
lead to larger or smaller beneficial effects of ceria in that they do not exceed the oxygen storage capacity of
aged catalysts depending on the benefits that come from the catalyst. Extended rich excursions can deplete the
highly dispersed or crystalline ceria [6,7], but this subject ceria of oxygen, resulting in decreases in the CO conver­
will not be the focus of this paper. Initially when pre­ sion. Extended lean excursions saturate the ceria with
pared by either method, the ceria particles are highly oxygen, so that the ceria can no longer remove oxygen
dispersed and have a large surface area/volume ratio. from the exhaust. At this point, the NOx reduction is
This enables the ceria to interact with the highly dis­ inhibited by oxygen saturation of the surfaces of the
persed metal in the catalyst and to store and release a ceria and the metal.
large amount of oxygen through changes in ceria's This simple view of the role of ceria in cycled A/F
oxidation state [2-4]. ratio exhaust could not fully explain the magnitude of CO
conversion enhancement observed in cycled laboratory
Ceria and the Oxygen Storage/Release Phenomenon feedstreams. This led to studies which showed that
ceria was also promoting the water-gas shift reaction
Under the typical feedback control systems found on [4,11,12]:
today's vehicles, the A/F ratio of the exhaust cycles
between lean and rich conditions. The frequency of the
oscillation varies between 0.5 to 3 Hz, depending on the
exhaust manifold design and the location of the oxygen However, this reaction which is important largely on the
sensor. Under these oscillating exhaust conditions the rich side, can be inhibited in the presence of SO2 [11].
oxidation state of the ceria is described as changing from There are other cases where ceria has beneficial
the Ce4+ state in CeO2 to the Ce3+ state in Ce2O3 as the effects on the steady state (i.e., not cycled) activity of
ceria releases oxygen or, vice versa, as it is stored [4]: various reactions [6,13]. For example, Oh and Eickel [6]
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931034 3
have reported that the effect on CO oxidation activity also play some role as a stabilizer of the micropore
enhancement is a strong function of the feedstream structure (i.e., the high surface area) of the -alumina
stoichiometry; the activity promotion was most pro- support [14]. This stability depends greatly on the way in
nounced under rich conditions and diminished under which the catalyst is made and treated during its manu-
strongly oxidizing conditions. facture. Lanthana and barium are more recognized as
Hydrocarbon (HC) conversion efficiency is less stabilizers of the alumina support than is ceria [14,18].
dependent on oxygen storage/release than CO conver-
sion efficiency. This may be due in part to the fact that RESULTS AND DISCUSSION
hydrocarbon conversion can occur at rich A/F ratios
through reactions other than oxidation by O2, such as Catalyst Performance versus Ceria Content
steam-reforming, which can occur under oxygen defi-
cient conditions: Since ceria has so many benefits, a valid question is
whether the entire support could be made of ceria.
However, there is considerable data in real exhaust that
suggests that there is an optimal concentration or range
Steam reforming is analogous to the water-gas shift of concentrations of ceria. Ceria loadings on either side
reaction which assists in CO removal, also under rich of this optimal range result in decreased emission
conditions. performance after aging.
The ceria particles that are best able to store and To examine this contention in a controlled way, 2.8 L
release oxygen on the time scale of typical A/F oscilla- monolith catalysts were prepared with the same noble
tions (0.5 - 3 Hz) are largely those that are in intimate metal loading (0.14 Pt/0.014 Rh), but with different ceria
contact with precious metal sites [8,14]. At these sites concentrations ranging from 0 to 50% of the washcoat by
during the storage of oxygen (lean conditions), the weight. The samples were aged on a rapid aging
oxygen molecules dissociated by the precious metal schedule [19] which simulates 4000 miles of vehicle
produce oxygen atoms which react directly with neigh- aging. The catalysts were then tested on an A/F ratio
boring Ce2O3 particles to form CeO2 (Eq. 1), although sweep test [20] in which the HC, CO, and NOx conver-
presumably direct oxidation of ceria also occurs at some sions are determined as the mean A/F ratio is swept
rate. During the release of oxygen (rich conditions), CO, from 0.5 lean to 0.5 rich. The inlet temperature and flow
HC, or hydrogen absorbed on neighboring noble metal are held at 482°C and 23 g/s, respectively. The catalysts
sites are oxidized with oxygen atoms from CeO2 in the were then aged on a second rapid aging schedule with
vicinity of the precious metal particles, thereby reducing higher temperatures [20], intended to simulate high
the CeO2 to Ce2O3. Overall, these benefits of ceria mileage conditions (e.g., 100,000 miles of driving). The
appear to maximize at a content intermediate between catalysts were then tested on the same A/F ratio sweep
15 and 30 in some experiments [15], but we will test.
return to this subject later. Figure 1 shows the HC, CO, and NOx conversions at
stoichiometry as a function of the ceria loading for the
Effect of Ceria on Catalyst Durability two conditions of aging. We find that, for this washcoat
formulation, the performance after the simulated high
One of the main beneficial effects of ceria on catalyst mileage aging is optimized at the near 30 ceria level
durability is derived from its ability to promote/stabilize for all three monitored gases and that ceria concentra-
precious metal dispersion [4]. The higher a catalyst's tions on either side of this optimal level result in de-
dispersion, the more of its metal atoms are found on the creased performance. An optimal ceria loading for HC
surface of catalytic particles and the catalyst is more conversion has also been reported elsewhere [21]. It is
active. A 100 dispersion means all of the precious clear that simply using increasing amounts of ceria is not
metal atoms are accessible to the reacting gases. For the solution to reaching the highest catalyst perfor-
instance, there is evidence [16] that ceria on alumina mance.
may help stabilize Rh more as isolated atoms (ions) or An interesting observation from Figure 1 is that the
as two-dimensional islands, instead of three-dimensional CO and NOx conversions are particularly enhanced by
balls, better maintaining its dispersion. the presence of ceria, while the improvement in HC
However, upon aging in cycled A/F ratio conversion in aged catalysts with this loading is much
feedstreams, at least by temperatures near or above less pronounced. Compared with the alumina (i.e., no
800°C, both precious metal and the ceria form larger ceria) catalyst, the catalyst with the optimized level of
particles and the interaction between the metal and 30% ceria has an approximately 40 higher absolute
ceria, which is only a metastable condition of the cata- CO conversion level and a 20 higher NOx conversion.
lyst, largely disappears. This brings to an end much of In contrast, the difference in HC conversion between the
the significant oxygen storage/release and much of the two ceria contents is about 5 in this study. Presumably
benefit ceria brings directly to catalyst activity. As noble the HC conversion remains high without the ceria due to
metal and ceria particle sizes grow, the beneficial metal- other reactions involving hydrocarbons, such as steam
ceria interaction decreases significantly [17]. reforming. Another factor in the hydrocarbon efficiency's
Finally, up to temperatures near 1000°C ceria may general insensitivity to ceria content may be the lower
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931034
OBD-II Catalyst Performance Monitoring

To meet OBD-II regulations for monitoring catalyst

performance, the dual oxygen sensor approach has
been proposed [22,23] as a means of detecting catalyst
"failure," where the threshold of failure for 1994-5 OBD-II
applications occurs "... when total HC conversion
efficiency falls below 60 percent... based on a steady
state test... [24]." However, since this method utilizing
oxygen sensors before and after the catalyst is designed
to measure the oxygen storage capacity of the catalyst
[25] and not hydrocarbon conversion efficiency, it is
important to examine the possible relationship between
these quantities. Even though there are beneficial
effects of the oxygen storage/release aspects of ceria,
catalysts made with no ceria and operated with the
exhaust A/F ratio held close to stoichiometry, can also
react CO, NO, and hydrocarbons very well. Exhaust
catalysts without high cerium content were used effec-
tively in cars before the mid-1980's. Similarly, modern
automotive catalysts, which contain high surface area
ceria, can still be very active even after losing much of
their oxygen storage capacity.
The presence of high steady state hydrocarbon
conversion activity without oxygen storage capacity is
well shown in a study by Hepburn and Gandhi [26]. In
their study of 17 catalysts, aged varying amounts from
4,000 to 100,000 miles and in the lab, they found that the
oxygen storage capacity (OSC) of the catalysts drops
sharply during the early stages of aging, while the steady
state hydrocarbon conversion efficiency of a catalyst falls
near the 60 value only after severe aging (see Fig. 2).
Several catalysts which have OSC's only 10 of those
of nearly fresh catalysts still have hydrocarbon conver-
sion efficiencies near 90 . The highly non-linear
behavior seen in Fig. 2 is reminiscent of and directly
related to the non-linear relationship, often referred to as

mobility of hydrocarbons or hydrocarbon fragments,

relative to CO, to find reactive sites on the catalyst
surface. Taken all together this data indicates that the
oxygen storage capacity of ceria primarily benefits the
CO and NOx conversions, and that oxygen storage
capacity is not the most appropriate parameter to
monitor for diagnosing the HC performance of the
converter.
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931034 5

a "hockey stick" curve, between steady state HC effi-

ciency and indices of catalyst performance using data
from front and rear oxygen sensors [26-28].
The result from Fig. 2 that catalysts with low OSC's
can have high steady state HC efficiency occurs be-
cause the noble metal particles which catalyze the
reactions are still present on the support surface and
sufficiently active at stoichiometry, even after being aged
at high temperatures. The differences between the
nearly fresh catalysts, such as H in Fig. 2, and the
catalysts with low oxygen storage capacity and high
conversion efficiency, such as Q and P in Fig. 2, are
shown schematically in Fig. 3. Fig. 3a shows both ceria
and precious metal particles with a high surface area,
while Fig. 3b is representative of a catalyst that still has
sufficiently high precious metal surface area, but has lost
much of its ceria surface area and its interaction with the
metal. These pictures are consistent with information on
ceria and metal particle sizes in aged automotive
exhaust catalysts [29] and they rationalize the evidence
that the oxygen/storage capability of the catalyst, and all
of the beneficial effects that come with it, can disappear
at an earlier time than the aging sufficient to cause a
significant loss of catalytic activity.

A Case Study Using Multiple Oxygen Sensors for

Catalyst Monitoring

An example of loss of oxygen storage without

significant loss of catalytic activity in a context important engine, so that it will warm up quickly and reduce cycle 1
to OBD-II diagnostics can be seen in Figures 4 and 5. emissions to help meet LEV standards. The first oxygen
Signals from three oxygen sensors are seen in Fig. 4 sensor signal at the bottom of Fig. 4 is the signal from
during a steady state cruise by a six-cylinder vehicle the pre-catalyst control oxygen sensor. In the middle is
using two converters aged to mimic 3,000 miles of the signal from a sensor behind a warm-up converter,
driving. One is in a normal underfloor location, while the but in front of an underfloor converter. On top is the
other, called a warm-up converter, is closer to the signal from an oxygen sensor behind the underfloor
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6 931034
converter, after the entire exhaust treatment system. as an oxygen storage agent under cycled A/F ratio
The overall FTP catalyst efficiency of the system and the conditions can be lost, while the catalyst system is still
efficiencies of the individual converters are shown. The performing very well.
HC efficiencies of the overall system and the warm-up
converter are very high (96.7 and 90.8 , respectively) SUMMARY
as compared with the underfloor converter (63.9 ).
Fig. 5 shows the sensor signals from the same vehicle We have discussed the beneficial effects of ceria on
after the catalysts have been aged in a way that is catalyst activity, their disappearance upon aging of the
representative of 50,000 miles driven. The HC efficien- catalyst, and the effect the loss of oxygen storage/
cies of the overall system and the warm-up catalyst are release can have on measurements of catalyst activity
still quite good (95.7 and 86.6 , respectively) and the using oxygen sensors. The key comments are that:
underfloor converter efficiency has increased to 71.5 .
One interesting aspect of this data is the efficiency 1. Properly prepared ceria promotes oxygen storage/
increase by the aged underfloor converter (relative to 3 K release of the catalyst which improves the catalyst
miles) for at least two monitored gases. This probably activity under cycled A/F ratio conditions. Ceria also
occurs for a combination of reasons. As the efficiency of enhances the activity of the catalyst for other
the warm-up converter falls, it leaves more unreacted reactions, such as the water-gas shift reaction under
gases (e.g., CO) to be catalyzed in the underfloor rich conditions.
converter. If, for example, NO conversion were initially
limited by the availability of CO in the underfloor con- 2. Ceria also appears to help catalyst durability some-
verter, then NO conversion would go up after aging. what by enhancing precious metal dispersion. It
More reaction in the underfloor location means that may also play some role as a stabilizer of the
converter will have a greater exotherm and will be support.
somewhat warmer and more active. Also, as the warm-
up converter's oxygen storage decreases, cycled A/F 3. There is an optimal ceria content in an alumina
oscillations will pass through to the underfloor converter washcoat for best catalyst performance. In this study
and enhance its conversion efficiency. This compensa- we find a ceria content near 30 maximizes aged
tion effect between the warm-up and underfloor convert- catalyst performance.
ers tends to keep the overall emissions performance of
the system high, even as the warm-up converter ages. 4. The oxygen storage capacity of the catalyst can
Comparison of Figs. 4 and 5 shows another aspect of decrease after high temperature exposure, due to
the data more relevant to the choice of an OBD-II the decreased surface area of the ceria and precious
catalyst monitor. We find the signals of only one of the metal particles and their decreased interaction with
oxygen sensors, the one behind the warm-up converter, each other.
changes dramatically after catalyst aging. The control
oxygen sensor, of course, does not change between 5. Catalysts which have suffered loss of oxygen
tests. It simply shows the variation in voltage of the storage capacity as a result of high temperature
oxygen sensor as the A/F ratio varies between rich (high exposure can still provide high conversion efficien-
voltage) to lean (low voltage). These oscillations are not cies on powertrains which have well controlled air/
seen in the post-catalyst system oxygen sensor. Be- fuel ratios.
cause the still excellent oxygen storage/release capacity
of the underfloor catalyst converts oxygen to products, 6. We have shown an important case, involving warm-
the A/F ratio oscillations damp out. Algorithms that would up converters, where there is little correlation
compare signals from the post-catalyst system sensor or between the oxygen storage/release capacity of a
the post-warm-up converter sensor in Fig. 4 to that from catalyst system and its emissions performance (e.g.,
the control sensor, by using, for example, an area HC conversion). Therefore, methods that use
difference approach [22,23], can show both 3 K aged oxygen storage to determine catalyst activity,
converters meet OBD-II standards. However, in Fig. 5 particularly for warm-up catalysts, will not provide the
the signal from the sensor after the 50 K aged warm-up level of accuracy required for reliable on-board
converter shows oscillations that are closely matched to monitoring of catalyst performance.
those of the control sensor. There is little sign that there
is still oxygen storage/release capacity in the warm-up
ACKNOWLEDGMENTS
converter to damp this signal. The same algorithms
would indicate failure of this warm-up converter using the
The authors would like to thank several colleagues at
dual oxygen sensor diagnostic technique. However, the
GM Research: Se Oh for many thoughtful discussions
warm-up converter's HC efficiency has dropped only 4
and Don Beck, Dave Belton, and Dave Monroe for their
from the value at 3,000 miles and the system is still
very helpful comments. We also thank Bill LaBarge of
performing very well. Figure 3b may approximately
ACR for preparing the catalysts with the various ceria
describe this catalyst. This example with a warm-up
catalyst demonstrates how the beneficial effect of ceria loadings and we acknowledge the support and encour-
agement of John Oldani and Rod Rhodes at GM Power-
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931034 7
train. In addition, we thank Larry Murrell of Lehigh 22. W. B. Clemmens, M. A. Sabourin, and T. Rao,
University and John Nunan and Heinz Robota of Allied- "Detection of Catalyst Performance Loss Using On-
Signal Research and Technology for discussions of their Board Diagnostics." SAE Paper #900062, 1990.
published work. 23. J. W. Koupal, M. A. Sabourin, and W. B. Clemmens,
Correspondence concerning the subject matter of "Detection of Catalyst Failure On-Vehicle Using the
this paper should be directed to Galen B. Fisher, Physi- Dual Oxygen Sensor Method." SAE Paper #910561,
cal Chemistry Department, General Motors Research, 1991.
Warren, Ml 48090-9055. 24. California Air Resources Board Mailout #92-56,
Section 1968.1 (b) (1.2.4), Title 13, California Code
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