Applied Surface Science 210 (2003) 206–221

Surface chemistry and microstructural analysis of

CexZr1
xO2
y model catalyst surfaces$
Alan E. Nelsona, Kirk H. Schulzb,*
a
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alta., Canada T6G 2G6
b
Dave C. Swalm School of Chemical Engineering, Mississippi State University, P.O. Box 9595, Mississippi State, MS 39762, USA
Received 30 May 2002; received in revised form 30 May 2002; accepted 27 January 2003

Abstract

Cerium-zirconium mixed metal oxides are widely used as promoters in automotive emissions control catalyst systems (three-
way catalysts). The addition of zirconium in the cubic lattice of ceria improves the redox properties and the thermal stability,
thereby increasing the catalyst efficiency and longevity. The surface composition and availability of surface oxygen of model
ceria-zirconia catalyst promoters was considered to develop a reference for future catalytic reactivity studies. The microstructure
was characterized with X-ray diffraction (XRD) to determine the effect of zirconium substitution on crystalline structure and
grain size. Additionally, the Ce/Zr surface atomic ratio and existence of Ce3þ defect sites were examined with X-ray
photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) for samples with different zirconium concentrations.
The surface composition of the model systems with respect to cerium and zirconium concentration is representative of the bulk,
indicating no appreciable surface species segregation during model catalyst preparation or exposure to ultrahigh vacuum
conditions and analysis techniques. Additionally, the concentration of Ce3þ defect sites was constant and independent of
composition. The quantity of surface oxygen was unaffected by electron bombardment or prolonged exposure to ultrahigh
vacuum conditions. Additionally, XRD analysis did not indicate the presence of additional crystalline phases beyond the cubic
structure for compositions from 100 to 25 at.% cerium, although additional phases may be present in undetectable quantities.
This analysis is an important initial step for determining surface reactions and pathways for the development of efficient and
sulfur-tolerant automotive emissions control catalysts.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Cerium; Zirconium; Oxide; Model; Catalyst; Emissions; Automotive

1. Introduction of oxygen near the catalyst surface [1,2]. Despite its

Cerium oxide (CeO2) is used in automotive emis-
sions control catalysts to regulate the partial pressure
$
A portion of this work was performed at Department of
Chemical Engineering, Michigan Technological University, 1400
Townsend Drive, Houghton, MI 49931, USA.
*
Corresponding author. Tel.: þ1-662-325-2480;
fax: þ1-662-325-2482.
E-mail address: schulz@che.msstate.edu (K.H. Schulz).
widespread use and application, pure cerium dioxide
has poor thermal stability and is known to sinter at
1123 K [3]. In order to increase its thermal stability
and ability to store and release oxygen during opera-
tion, zirconium is substituted into the cubic structure
of ceria. The addition of zirconium to the cubic
structure of ceria is reported [4–6] to increase the
oxygen storage capacity of the system while enhan-
cing the thermal stability under high temperatures [7],

0169-4332/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00157-0
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221
as compared to pure ceria. Indeed, a 10 at.% zirconium
substitution in cerium oxide markedly increases the
oxygen storage capacity compared to ceria-only sys-
tems [3]. Ceria-zirconia solid solutions are also reported
to have three to five times the oxygen storage capacity
(per gram of catalyst) than ceria-only systems [8].
Bulk reduction of pure ceria is reported to occur at
approximately 1173 K, while ceria-zirconia reduction
begins at lower temperatures near 853 K. Vliac et al.
[9] suggest the enhanced oxygen storage property of
the ceria-zirconia system is the result of enhanced
diffusion of bulk oxygen anions to the surface.
Additionally, Raman spectroscopy, X-ray diffraction
(XRD), and EXAFS analysis indicates zirconium has
a lower coordination number within the ceria lattice,
and consequently increases bulk oxygen mobility [9].
The near-neighbor zirconium oxygen atoms are not
observed in ceria-zirconia cubic matrices and their
absence is attributed to a high degree of structural
disorder. The oxygen atoms are positioned at a weak
bonding distance, resulting with increased oxygen
mobility. This is thought to be a mechanism for release
of the stress generated by the insertion of a smaller
zirconium ion into the lattice [9]. By moving the
oxygen ions to a non-bonding distance, mobile oxygen
anions are generated within the lattice.
In order to improve ceria-zirconia low-temperature
performance and resistance to deactivation (SO2), a
fundamental understanding of the structure and sur-
face chemistry is required. This paper presents infor-
mation on the characterization of cerium-zirconium
mixed metal oxide powders and model catalysts pre-
pared via co-precipitation routines. The surface seg-
regation of cerium and zirconium, as well as the
oxidation state of the metals, was investigated with
Auger electron spectroscopy (AES) and X-ray photo-
electron spectroscopy (XPS). This information will be
useful for comparing reaction and deactivation
mechanisms under oxidizing and reducing conditions
in subsequent investigations.
2. Experimental
2.1. Materials and synthesis
Several cerium-zirconium solid solution preparation
methods have been reported which produce medium
207
surface area mixed oxide powders suitable for auto-
motive catalyst emulation, including hydroxide, acetate,
and surfactant-assisted chloride precipitation [8,10]. In
this study, a complete range metastable cerium-zirco-
nium mixed metal oxide powders (CexZr1
xO2
y,
1  x  0) were prepared through a hydroxide
precipitation technique reported by Hori et al. [8].
Predetermined quantities of cerium(IV) ammonium
nitrate (Alfa Aesar, CAS #16774-21-3) and zirconium
oxynitrate (Alfa Aesar, CAS #13826-66-9) precursors
are completely dissolved in deionized water with mild
heat. Upon dissolution of the precursors, excess ammo-
nium hydroxide (100 vol.%) is added to precipitate
the cerium-zirconium mixed metal oxide powder.
The resultant precipitate is filtered in a vacuum funnel
and thoroughly washed with excess distilled water
(2 l/10 g precipitate). The ceria-zirconia powder is
allowed to dry in the hood overnight and is subse-
quently annealed at atmospheric conditions. Sample
annealing stabilizes the metal oxides and eliminates
carbonates and nitrate compounds remaining from the
preparation technique [7]. The annealed powders are
milled and stored in a dry environment. A sufficient
quantity of ceria-zirconia powder was initially pre-
pared and utilized through this research to eliminate
compositional inconsistencies that arise from multiple
preparations. The cerium-zirconium mixed oxides
were formed into model wafers using a standard
13 mm diameter FT-IR pellet die and hydraulic press.
The oxide powders (approximately 100 mg) are loaded
into the die and subjected to a pressure of 670 MPa for
a duration of 10 min. The prepared samples have a
thickness of approximately 100–150 mm, depending on
the initial quantity of oxide power used.
2.2. Equipment and analysis
Surface compositional analysis was performed with
AES and XPS. Auger electron spectroscopic analysis
was performed with a Physical Electronics 545
Scanning Auger Microprobe (SAM). The Auger spec-
trometer was operated with an electron gun filament
(tungsten) current of 2.0 nA and an incident electron
energy of 2.0 keV with a corresponding resolution of
0.6%. The spectrometer is operated at a background
pressure of approximately 2  10
10 Torr obtained
with a 220 l/s ion-pump and titanium sublimation
pump. Sample positioning was performed with a
208 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221
xyz-rotary ultrahigh vacuum sample manipulator and a
custom UHV terminal [11]. XPS was performed with
a Physical Electronics 1600 XPS Surface Analysis
System located in a dedicated stainless steel chamber
used exclusively for XPS surface characterization.
The analyzer is fitted with an Omni Focus III
small-area lens that produces 800 um diameter surface
analysis area. The XPS spectra were obtained by using
an incident achromatic Mg Ka X-ray source
(1253.6 eV) operated at 300 W with a corresponding
voltage of 15 kV. Survey spectra are an average of 10
scans over a range from 0 to 1100 eV with a pass
energy of 26.95 eV. The high-resolution XPS spectra
are a composite average of 15 scans with a pass
energy of 23.5 eV at an incident sample angle of
458. The background pressure during XPS analysis
was approximately 8  10
9 Torr. Additionally, the
microstructure of the ceria-zirconia model catalysts
was characterized with XRD and scanning electron
microscopy (SEM).
3. Results and discussion
3.1. Effects of catalyst annealing
Several methods of model catalyst preparation were
considered to produce a model catalyst suitable for
ultrahigh vacuum spectroscopic characterization,
while maintaining attributes similar to automotive
catalyst systems. Specifically, the effect of annealing
conditions on the final properties of the two-dimen-
sional model catalysts was investigated. The ceria-
zirconia samples require annealing to eliminate car-
bonates and nitrates remaining from the preparation
technique [8]. However, excessive annealing could
result in particle sintering and undesirable crystallite
migration [12]. Published research of ceria-zirconia
suggests particle sintering occurs at temperatures in
excess of 773 K at prolonged exposure times. As a
result, annealing conditions of 1 h at 773 K in atmo-
sphere were used throughout the experiments. Two
distinct preparation routines were investigated to dis-
cern the effects of annealing on the final two-dimen-
sional model catalyst properties. The first set of model
catalysts was prepared from the dry cerium-zirconium
mixed oxide powder followed by wafer formation
and subsequent sample annealing. The second set of
samples was prepared from annealed oxide powder,
which was formed into the model catalyst systems.
The SEM micrographs of each preparation method
are located in Fig. 1. The images clearly indicate the
samples prepared with annealed oxide powder directly
formed into the model catalysts have less surface
roughness and irregularity (Fig. 1b), compared to
samples prepared with dry mixed oxide powder fol-
lowed by wafer formation and subsequent annealing
(Fig. 1a). As a result of the SEM analysis, the pre-
paration method of annealing the oxide powders at
773 K for 1 h followed by subsequent milling and two-
dimensional wafer formation was adopted. Addition-
ally, the apparent bulk density of the model catalysts
was characterized with a modified Archimedes density
measurement method to ensure adequate density and
validate the model catalyst systems further (Table 1).
The measured density of CeO2 model systems is 95%
of theoretical compared to a ZrO2 density of 85% of
theoretical. The global average for all prepared and
analyzed samples is 89% of theoretical. Considering
alumina with a bulk density of 97% of theoretical is
sufficient for ultrahigh vacuum applications [13], the
densities of the model systems are adequate to limit
the extent of diffusional processes which arise in
desorption spectrocscopies.
3.2. Crystalline structure and grain size
The phase diagram for intermediate cerium-zirco-
nium oxides is the subject of debate due to reported
phases of metastable tetragonal crystallinity [14,15].
Indeed, several publications have indicated the
presence of three tetragonal phases, including t
(20–40 at.% cerium), t0 (40–65 at.% cerium), and t00
(65–80 at.% cerium) over the intermediate composi-
tional range [5,16–18]. However, the t00 phase exhibits
no tetragonality and the t0 phase is a metastable structure
formed through a diffusionless transition [18]. Hori
et al. [8] reported cerium-zirconium mixed metal oxides
in excess of 50 at.% cerium prepared via similar
co-precipitation routines and aged at 1273 K exist as
a cubic (fluorite) solid solution. They also report the
presence of a separate tetragonal phase (zirconium rich)
for compositions less than 49 at.% cerium.
The XRD patterns of the prepared cerium-zirco-
nium oxides are shown in Fig. 2 for comparison. The
reference pattern (PDF 34-0394) for a standard cubic
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221 209

Fig. 1. SEM micrographs of prepared CeO2 model catalyst surfaces. The micrographs represent two evaluated preparation methods, including
preparation with dry mixed oxide powder followed by wafer formation and subsequent calcination (a), and preparation with calcined oxide
powder directly formed into the model catalysts (b). The samples were imaged at 1000 magnification.

CeO2 sample, shown as vertical dotted lines, is super-
imposed on the XRD patterns. The pattern of the
100 at.% CeO2 sample matches with the reference
data, verifying the cubic crystalline structure (CaF2)
for the sample. As the amount of CeO2 in the mixed
oxide decreases, the positions of the peaks of spectra
shift farther away from those of pure CeO2 and the
peaks also broaden (FWHM) as a function of decreased
cerium loading. Duwez and Odell [14] and other
researchers have also reported similar results. Another
important observation from the XRD patterns is that a
cubic solid solution is still maintained up to 25 at.% of
cerium oxide (75 at.% zirconium oxide). There is no
indication from XRD analysis of a separate tetragonal
ZrO2 phase under any composition. In previous studies,
mixed oxides prepared via the same route could form a
solid cubic solution up to only 50 at.% cerium [8].
These results could be attributed to the zirconium oxide
precursor used in the preparation of the mixed oxides
and the preparation method itself, as the crystalline
structure of the final mixed oxide is highly sensitive to
these two factors. The pure zirconium oxide pattern is

Table 1
Bulk density and XRD

Bulk density X-ray diffraction (XRD)

Theoretical Archimedes Cubic lattice Scherrer grain

(g cm
3) (g cm
3)  0.08 parameter (Å)  0.005 size (Å)  0.05

Ce1.0Zr0.0O2
y 7.13 6.75 5.413 109.2

Ce0.9Zr0.1O2
y 7.00 6.36 5.390 70.62
Ce0.8Zr0.2O2
y 6.86 6.15 5.371 61.28
Ce0.7Zr0.3O2
y 6.71 5.89 5.353 50.89
Ce0.6Zr0.4O2
y 6.57 5.80 5.328 51.32
Ce0.5Zr0.5O2
y 6.42 5.68 5.301 46.82
Ce0.25Zr0.75O2
y 6.02 5.23 5.219 58.70
Ce0.0Zr1.0O2
y 5.60 4.83 Monoclinic 148.8
210 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Fig. 2. XRD patterns of cerium-zirconium oxides. The reference pattern (PDF 34-0394) for a standard CeO2 cubic structure is superimposed
on the XRD pattern as vertical lines. The data indicates a cubic solid solution from 100 to 25 at.% cerium and a monoclinic structure for pure
zirconia.

identified as the monoclinic ZrO2 spectra. This is in
agreement with the reported phase diagrams [14,15]
for a cerium-zirconium mixed oxide system at ambient
conditions. The shifted peak position as a function of
composition indicates a change in the cubic lattice
parameter of the system [8,19]. As a result, X-ray
powder diffraction characterization of the fresh oxide
powders indicates a cubic solid solution from 100 to
25 at.% cerium and a monoclinic structure for pure
zirconia. While our XRD analysis indicates a cubic
structure over the intermediate composition range
(25–100 at.% cerium), we acknowledge the limitations
of XRD and the possibility of intermediate tetragonal
phases at high zirconium concentrations.
The lattice parameters and grain sizes were calcu-
lated [19] from the diffraction patterns as a function of
sample composition (Table 1). The data indicates the
lattice parameter, a0, follows a downward trend with
increasing amount of zirconium incorporated into
the mixed oxides. This agrees well with Vegard’s
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221
law, which states that the lattice parameter of a solid
solution is directly proportional to the atomic percent
solute present [19]. Zirconium is reported to have an
atomic radius ratio (rcation/ranion) of 0.59 compared to
0.68 for cerium [20]. This implies that zirconium has a
smaller ionic radius and would result in a reduction
of the lattice parameter of the crystalline system as
Ce4þ ions are being substituted by Zr4þ ions. This
observation is consistent with the calculated cubic
lattice parameters. The lattice parameter of pure cer-
ium oxide, CeO2, is found to be 5.413 Å, a value which
is comparable to that reported in a previous study [14].
The data also indicates the grain size decreases gra-
dually with increasing amounts of zirconium.
3.3. AES analysis of surface composition
The chemical composition of the prepared model
catalysts was analyzed with AES to characterize sur-
face species segregation compared with the bulk
composition [21]. Initially, the effects of ultrahigh
vacuum conditions and electron beam bombardment
were examined to determine the potential impacts on
surface oxygen and surface reduction. A 100 at.%
cerium oxide sample was degassed under high vacuum
conditions for 1 h and subsequently transferred to the
ultrahigh vacuum chamber for Auger spectroscopic
characterization. Following the collection of an initial
Auger spectrum (1 h), the sample remained is position
for an additional 3 h, as to bombard the surface with
the incident electron source. The sample was again
analyzed at intervals of 28 and 96 h of ultrahigh
vacuum exposure. The specimen was not exposed
to additional electron bombardment except for sample
alignment and data collection. The collected Auger
spectra were normalized with respect to the cerium
MNN transition and the amplitude of the oxygen KLL
transition was determined (Table 2). Based on the
Table 2
Effect of ultrahigh vacuum on ceria surface oxygen
Time (h) Oxygen KLL (513 eV) transition amplitude
1 5570  50
4a 5500  50
28 5520  50
96 5530  50
a
Sample was bombarded with incident electron beam for 3 h.
211
quantification of the oxygen KLL transition ampli-
tude, it is evident that surface oxygen remains constant
for excess exposures to ultrahigh vacuum conditions.
Additionally, no appreciable reduction is surface
oxygen content occurs as a result of electron bombard-
ment. If any surface oxygen is removed as a result of
beam bombardment or ultrahigh vacuum exposure, it
occurs during initial degassing or sample positioning.
The zirconium MNN transition amplitudes for each
composition were numerically averaged (n ¼ 7) and
graphed as a function of bulk composition (Fig. 3).
Qualitative analysis of the zirconium peak amplitudes
indicates a linear correlation with respect to bulk
composition (R2 ¼ 0:9924). This regressed slope
value indicates that cerium is more sensitive to the
Auger electron process than zirconium for the com-
positions considered and analyzer used. This observa-
tion is in agreement with published sensitivity factors
for Auger spectroscopic analysis [22]. The Auger
analysis of the mixed oxides indicates the surface
composition is representative of the bulk regardless
of cerium-zirconium concentrations. In addition to
zirconium MNN peak intensity correlation, additional
numerical analysis was performed using the oxygen
KLL transition. Similar to the zirconium peak inten-
sity analysis, the amplitude of the oxygen KLL
(513 eV) transition was quantified and correlated to
bulk mixed oxide composition (Fig. 4). The oxygen
KLL peak intensity analysis indicates a non-linear
relationship with composition, decreasing with increas-
ing zirconium concentration. This decreasing trend
in surface oxygen concentration with increasing zirco-
nium substitution is suggested to result from surface
contamination, as opposed to surface oxidation state
and oxygen diffusion.
3.4. XPS analysis of surface composition
The catalyst systems were further analyzed with
XPS to verify surface composition and elemental
oxidation states. Due to observed charging effects
during XPS analysis, the binding energy scale was
calibrated using adventitious carbon (285.4 eV) [23].
This resulted in a binding energy correction of 6 to
10 eV for each spectrum. The spectral features were
fitted with Gaussian distributions and the peak posi-
tions and areas were determined (Table 3). The Ce 3d
Gaussian peak fits corresponding to Ce3þ and Ce4þ
212 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Fig. 3. Zirconium AES peak intensity analysis. The zirconium MNN transition amplitudes for each composition were numerically averaged
over seven data points. Linear regression analysis (zero constant) performed with the zirconium peak amplitude as a function of composition
produces a correlation with an R2 value of 0.9924.

states are based on published CeO2 XPS analysis by
Burroughs et al. [24] and Pfau and Schierbaum [25].
However, due to the complex electronic structure,
the absolute distinction between 3d94f2Vn
1 and
3d94f2Vn
2 final states for Ce3þ (v0, u0) and Ce4þ
(v, u) could not be resolved. As a result, the high-
resolution spectra for the Ce 3d3/2 and Ce 3d5/2 ioni-
zation features were numerically fitted with eight
Gaussian distributions representing the initial and final
states in Ce 3d core level X-ray photoelectron spectra
(Fig. 5). A composite spectrum of the Ce 3d3/2 and Ce
3d5/2 ionization features as a function of composition
is shown in Fig. 6.
The bands labeled v collectively represent the Ce
3d5/2 ionization, while bands labeled u represent the
Ce 3d3/2 ionization. The bands with unprimed labels
represent the primary Ce 3d5/2 and Ce 3d3/2 transi-
tions, while the primed labels represent ionization
satellite features. Specifically, the band (u0, u) located
at (901.0–901.4 eV) is the Ce 3d3/2 ionization and
the band (v0, v) located at (882.5–882.8 eV) is the Ce
3d5/2 ionization for Ce3þ and Ce4þ [24–26]. The bands
labeled v0 (885.5–885.8 eV), v00 (889.0–889.3 eV) and
v000 (898.3–898.6 eV) are satellites arising from the Ce
3d5/2 ionization, while bands u0 (904.0–904.3 eV), u00
(907.4–907.7 eV), u000 (916.7–916.9 eV) are satellites
arising from the Ce 3d3/2 ionization [24,25]. The Ce
3d3/2 and Ce 3d5/2 peak areas and amplitudes increased
as a function of increasing cerium concentration.
This is attributed to increasing cerium concentration,
as the amplitude and area of XPS photoemission
features are proportional to surface composition
[27]. The difference in Ce 3d3/2 and Ce 3d5/2 binding
energies is also in agreement with an expected value
of 18.6 eV [24]. Examination of the Ce 3d3/2 and
Ce 3d5/2 photoemission features indicates a slight
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221 213

Fig. 4. Oxygen AES peak intensity analysis. The amplitude of the oxygen KLL (513 eV) transition was averaged (n ¼ 7) for each
composition and correlated to bulk mixed oxide composition. The oxygen KLL peak intensity analysis indicates a non-linear relationship with
composition, decreasing with increasing zirconium concentration.

chemical shift to a higher binding energy (0.3–0.4 eV) surface electronic structure independent of oxidation
from 100 to 25 at.% cerium. Although a slight binding state.
energy shift is observed with changing composition, To verify the surface oxidation state as a function
the shift is suggested to arise from the changing of composition, the bands representative of Ce3þ and

Table 3
Summary of principle XPS binding energies

Photoemission binding energy (eV)

Ce 3d5/2 Ce 3d3/2 Zr 3d5/2 Zr 3d3/2 O 1s C 1s

Ce1.0Zr0.0O2
y 882.5 901.0 – – 529.6 285.4

Ce0.9Zr0.1O2
y 882.6 901.0 181.5 184.0 529.6 285.4
Ce0.8Zr0.2O2
y 882.7 901.2 182.4 184.9 529.8 285.4
Ce0.7Zr0.3O2
y 882.6 901.1 182.4 184.8 529.7 285.4
Ce0.6Zr0.4O2
y 882.7 901.3 182.4 184.8 529.9 285.4
Ce0.5Zr0.5O2
y 882.7 901.2 182.3 184.8 529.9 285.4
Ce0.25Zr0.75O2
y 882.8 901.4 182.4 184.8 530.0 285.4
Ce0.0Zr1.0O2
y – – 182.4 184.9 530.1 285.4
214 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Fig. 5. Ce 3d photoemission Gaussian peak fit for CeO2. The analyzed region of cerium illustrates the complex satellite structure arising from
a mixture of multielectron and multiplet interactions. The bands labeled v collectively represent the Ce 3d5/2 ionization, while bands labeled u
represent the Ce 3d3/2 ionization. Additionally, the bands with unprimed labels represent the primary Ce 3d5/2 and Ce 3d3/2 transitions, while
the primed labels represent ionization satellite features.

Ce4þ ions were further studied. The bands labeled u0
and v0 represent the 3d104f1 initial electronic state
corresponding to Ce3þ, while the peaks labeled u000
and v000 represent the 3d104f0 state of Ce4þ ions [25].
Analysis of the peak areas associated with the repre-
sentative Ce3þ (u0 , v0 ) and Ce4þ (u000 , v000 ) features
indicates a constant concentration of Ce3þ defect sites
on the surface independent of zirconium substitution.
Because the surface composition is representative of
the bulk, this suggests a constant cerium surface
oxidation state independent of composition. Addition-
ally, the intensities of the Ce3þ emissions (u0 , v0 ) are
relatively small compared to Ce4þ emissions (u000 , v000 ),
which are in relative proportion to highly oxidized
cerium oxide. Considering previously published ceria
XPS spectra [25], the intensities of the Ce4þ emissions
are consistent with surface oxygen stoichometry of
(y ¼ 0:0
0:08) for CexZr1
xO2
y.
The narrow scan spectra of the Zr 3d3/2 and Zr 3d5/2
features were deconvoluted with two Gaussian dis-
tributions representing the primary Zr 3d5/2 and Zr 3d3/
2 features. A composite spectrum of the Zr 3d3/2 and
Zr 3d3/2 ionization features as a function of composi-
tion is shown in Fig. 7. The ionization features are
distinct and uninfluenced by satellite features. The
Zr 3d5/2 ionization feature increases from 181.5 to
182.4 eV, while the Zr 3d3/2 ionization feature
increases from 184.0 to 184.9 eV as zirconium con-
centration increases. However, unlike the gradual
increase in binding energy observed with cerium
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221 215

Fig. 6. Ce 3d High resolution XPS analysis. The Ce 3d photoemission features are represented as a function of composition. The analysis
indicates a slight shift to higher cerium oxidation state as zirconium substitution increases, as evidenced by a chemical shift of the Ce 3d3/2 and
Ce 3d5/2 bands to a higher binding energy (0.3–0.4 eV) from 100 to 25 at.% cerium. Additionally, the Ce 3d3/2 and Ce 3d5/2 peak areas and
amplitudes linearly increase as a function of increasing cerium concentration.

ionization features, the zirconium binding energy
shifts markedly (0.9 eV) between 90 and 80 at.%
cerium, followed by a region of constant binding
energy independent of composition. In addition to
the noted photoemission features, additional bands
near 174 eV are suggested to correspond to satellite
features resulting from the use of an achromatic
X-ray source. The average delta between the Zr 3d3/2
and Zr 3d5/2 photoemission features is 2.4 eV and
independent of composition. This value is in excellent
agreement with the reported values of 2.43 [28] and
2.4 eV [23]. The constant binding energy separation
between the Zr 3d3/2 and Zr 3d5/2 features suggests a
constant zirconium oxidation state independent of
composition. Analysis of the Zr 3d5/2/Zr 3d3/2 peak
amplitudes and areas is consistent with expected
results. The peak amplitude ratio average is 1.47
(0.1):1, which is in good agreement with the 3:2
216 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Fig. 7. Zr 3d high resolution XPS analysis. The spectra for Zr 3d photoemission includes two distinct features corresponding to Zr 3d3/2 and
Zr 3d5/2 ionization bands. The analysis indicates an initial shift to a higher zirconium binding energy between 90 and 80 at.% cerium, followed
by a region of constant binding energy.

ratio expected on the basis of J multiplicities [24,27].
The peak areas and amplitudes increase as a function
of increasing zirconium (decreasing cerium) concen-
tration.
The high-resolution spectrum for the O 1s ioniza-
tion feature was numerically fitted with three Gaussian
features representing the primary O 1s ionization
feature and chemically shifted O 1s features from
chemisorbed surface species [23,28,29]. The analysis
of the O 1s photoemission feature results in the
deconvolution of three O 1s ionization binding ener-
gies, as supported by independent analysis of zirco-
nium oxide [23]. The O 1s Gaussian peak fit analysis
for pure ZrO2 is shown in Fig. 8, and the O 1s feature
as a function of composition is located in Fig. 9. The
primary band (529.6–530.1 eV) represents the O 1s
ionization for oxygen associated with the cerium-
zirconium complex [23,28,29], while the additional
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221 217

Fig. 8. O 1s photoemission Gaussian peak fit for ZrO2. The spectra for the O 1s ionization as a function of composition is numerically fitted
with three Gaussian features. The features include the primary O 1s feature corresponding to the metal oxide and two additional features
chemically shifted to higher binding energies suggesting the presence of surface contaminants.

bands (531.6–532.0 and 532.9–533.8 eV) are O 1s
features with slightly higher binding energy assign-
ments. The difference between the secondary O 1s
assigned features is compositional dependent, where
the binding energies are shifted to a lower binding
energy as a function of decreasing cerium (increasing
zirconium) concentration. In addition, the estimated
area of the O 1s primary feature is approximately
constant as a function of decreasing cerium concen-
tration, as is the total calculated area for the O 1s
feature.
The assignment of the O 1s bands beyond the
cerium-zirconium oxide is suggested through com-
parative analysis of similar studies [23,30]. The posi-
tion of the primary O 1s feature (ca. 529.8 eV) is
characteristic of metal oxides [29]. However, it is
impossible to distinguish between oxygen anions
associated with cerium and zirconium complexes
[29]. The frequently observed O 1s shoulder shifted
to higher binding energies is the result of chemisorbed
oxygen [29]. The binding energy for the O 1s ioniza-
tion arising from adsorbed water is 533.1 eV
[27,30,31]. This would suggest one secondary band
(533.3–532.5 eV) is the result of adsorbed surface
water or –OH species. Analysis of the remaining O
1s feature lends assignment to a carbon species. The O
1s shift from carbon bonding is highly variable and
strongly dependent on the chemical compound.
Indeed, the O 1s shift arising from carbon bonding
has been reported to occur between 534.9 and
542.6 eV [31] depending on carbon containing com-
pound. As a result, the final band (535.2–533.8 eV) is
suggested to arise from surface C–O species, as the
presence of surface carbon has previously been deter-
mined. The O 1s primary and secondary photoemis-
sion chemical shift as a function of composition can be
218 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Fig. 9. O 1s high resolution XPS spectra. The O 1s photoemission features are represented as a function of composition. The spectra suggest a
slight compositional shift in binding energy, and also indicate secondary O 1s bands suggested to arise from surface (–OH) and (–CO) species.

accounted for by the changing surface electronic
structure and the binding energies associated with
adsorbed surface water and C–O species, respectively.
Additional analysis of the O 1s feature also suggests
a low concentration of Ce3þ surface defect sites,
further supporting the conclusion of a highly oxidized
surface. The presence of Ce3þ surface defect sites
results in an additional O 1s band with a core level
shift of þ2.4 eV [25]. The absence of an O 1s band
2.4 eV higher than the binding energy for lattice
oxygen atoms (ca. 529.8 eV) indicates a relatively
low concentration of Ce3þ ions, suggesting a near-
stoichometric surface.
3.5. XPS peak area correlation
The peak areas for the dominant photoemission
features were calculated using an adjusted baseline
relative to the signal background. In this analysis, the
primary photoemission features included the Ce 3d3/2,
 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221 219

Table 4
XPS elemental surface concentrations

Atomic concentrations ( 0.5) Atomic ratios

Ce (at.%) Zr (at.%) O (at.%) C (at.%) Ce/Zr O/(CeþZr)

Ce1.0Zr0.0O2
y 19.4 0.0 49.1 31.5 – 2.5

Ce0.9Zr0.1O2
y 17.1 1.6 49.6 31.6 10.7 (9.0) 2.7
Ce0.8Zr0.2O2
y 14.2 3.1 46.5 36.1 4.6 (4.0) 2.7
Ce0.7Zr0.3O2
y 16.8 4.9 48.3 30.0 3.4 (2.3) 2.2
Ce0.6Zr0.4O2
y 12.8 8.3 50.2 28.6 1.5 (1.5) 2.4
Ce0.5Zr0.5O2
y 10.3 10.2 50.2 29.3 1.0 (1.0) 2.4
Ce0.25Zr0.75O2
y 8.0 15.0 51.3 25.6 0.5 (0.3) 2.2
Ce0.0Zr1.0O2
y 0.0 24.6 56.8 18.6 0.0 (0.0) 2.3

Zr 3d3/2, O 1s and C 1s bands. Surface atomic con-
centrations and atomic ratios calculated from these
core level transitions are located in Table 4. The
cerium to zirconium atomic ratio is in agreement
with the expected ratios calculated form the bulk
composition, as indicated by the values in parentheses.
Additional qualitative information regarding the sur-
face oxidation state was also extracted from the XPS
atomic concentration analysis. The ratio of the oxygen
concentration to the summation of the cerium and
zirconium concentrations was calculated and com-
pared to the expected ratio from the bulk composition.
The value ranged from 2.2 to 2.7, with a value of 2
indicating a fully oxidized surface and a correspond-
ing oxidation state of Ce4þ. Analysis clearly indicates
an excess quantity of surface oxygen with regards to
stoichometric cerium and zirconium concentrations. A
similar observation of excess surface oxygen was also
reported in an independent study of ceria-zirconia
systems [32] and is attributed to the high concentration
of surface oxygen as an adsorbed layer of oxidized
carbon species (CO, CO2) or water. This is further
supported in this analysis by the detection of surface
carbon species.
The area of the Zr 3d3/2 peak was also considered to
estimate the surface composition of the model catalyst
systems. The calculated Zr 3d3/2 peak areas were
linearly regressed as a function of zirconium concen-
tration to correlate zirconium photoemission peak
areas to bulk composition. The analysis produced
a linear relationship with bulk composition, as indi-
cated by an R2 value of 0.9852. The analysis provides
excellent correlation between XPS analysis of surface
compositions and the actual bulk composition.
3.6. Effect of electron bombardment on
surface composition
The effect of electron bombardment on ceria-
zirconia model catalysts was examined to determine
impact on surface oxygen and surface reduction. A
100 at.% cerium oxide sample was initially degassed
under high vacuum for 1 h and transferred to the
ultrahigh vacuum chamber for XPS characterization.
Following the collection of initial XPS data, the
sample was bombarded with an electron source for
2 h and subsequently analyzed with XPS. The sample
was bombarded for an additional 16 h before a final set
of XPS data was collected.
Two sets of XPS data were collected at different
spectrometer angles to discern between surface and
bulk species. The data included a 458 and 158 acquisi-
tion angle to determine elemental compositions to
depths of approximately 25–35 and 10–15 Å, respec-
tively. The 458 acquisition angle data is more repre-
sentative of the bulk composition, while the 158
acquisition angle is limited to surface compositions.
The data obtained at each spectrometer angle were
analyzed with peak fit routines and the surface atomic
concentrations were calculated (Table 5). Based on the
quantification of the oxygen and carbon photoemis-
sion features, it is evident that electron bombardment
is responsible for removing adsorbed surface carbon
contaminants. This is clearly evidenced by the reduc-
tion of surface carbon at a 458 analysis angle, and
enhanced at a 158 spectrometer angle. The decrease in
the carbon to oxygen and carbon to cerium ratios as
a function of electron beam exposure also supports
the observation of a reduction of adsorbed surface
220 A.E. Nelson, K.H. Schulz / Applied Surface Science 210 (2003) 206–221

Table 5
Effect of electron bombardment of surface species

Atomic concentrations ( 0.5) Atomic ratios

Ce (at.%) O (at.%) C (at.%) O/Ce C/O C/Ce

458 As prepared 19.1 50.5 30.4 2.6 0.60 1.59

2 (h) 17.8 58.0 24.2 2.1 0.42 1.34
16(h) 23.2 54.6 22.2 2.3 0.41 0.97
158 As prepared 10.9 50.1 39.0 4.6 0.78 3.58
2 (h) 22.5 55.4 22.2 2.5 0.40 0.99
16 (h) 32.1 54.6 13.4 1.7 0.25 0.42

carbon contaminants. The ratio of oxygen to cerium is
relatively constant as a function of electron beam
exposure at 458, while 158 angle analysis indicates
a decrease as a function of electron beam bombard-
ment. This might suggest a slight cerium reduction at
the gas phase boundary, although the 458 acquisition
indicates a relatively constant near surface oxygen to
cerium ratio. A constant cerium oxidation state as a
function of electron beam exposure is also supported
by the analysis of the Ce3d3/2 binding energy. As a
result, it is suggested the surface composition with
respect to cerium oxidation state is uninfluenced by
electron bombardment, while the removal of adsorbed
surface carbon species is evidenced.
4. Conclusions
The chemical composition and availability of sur-
face oxygen of ceria-zirconia model automotive emis-
sions control catalyst promoters were considered to
develop a reference for future catalytic reactivity ana-
lysis. The XPS and AES analysis of ceria-zirconia
model catalysts clearly indicate (1) no significant sur-
face species segregation occurs, confirming the surface
composition is representative of the bulk; (2) the
concentration of Ce3þ surface defect sites is constant
and independent of composition, suggesting incorpora-
tion of zirconium into the ceria lattice does not inher-
ently create additional defect sites; (3) the surface
chemistry of the oxides is unaffected by prolonged
exposure to ultrahigh vacuum or electron bombard-
ment; (4) the model catalyst surface stoichometry is
consistent with (y ¼ 0:0
0:08) for CexZr1
xO2
y.
Additionally, XRD analysis did not indicate the pre-
sence of additional crystalline phases beyond the cubic
structure for compositions from 100 to 25 at.% cerium,
although the existence of an additional phase is pos-
sible. This analysis is an important initial step for
determining surface reactions and pathways for the
development of efficient and sulfur-tolerant automo-
tive emissions control catalysts.
Acknowledgements
The authors gratefully acknowledge the assistance
of Melissa K. Graves in the Department of Chemical
Engineering at Mississippi State University for XPS
analysis. The authors would also like to acknowledge
financial support from the Ford Motor Company.
Additionally, A.E. Nelson would like to acknowledge
additional support from the Interdisciplinary Center for
Advanced Propulsion (ICAP) at Michigan Technolo-
gical University through the Department of Energy
(DOE) Graduate Automotive Education Technology
(GATE) program.
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