Article

pubs.acs.org/JPCC

A DFT Study of CO Oxidation at the Pd−CeO2(110) Interface

Weiyu Song,†,‡ Yaqiong Su,‡ and Emiel J. M. Hensen*,‡
†
State Key Laboratory of Heavy Oil, College of Science, China University of Petroleum-Beijing, Beijing 102249, P. R. China
‡
Inorganic Materials Chemistry, Eindhoven University of Technology, P.O.Box 513, 5600 MB Eindhoven, The Netherlands
*
S Supporting Information

ABSTRACT: Ceria-supported Pd is one of the main components in

modern three-way catalysts in automotive applications to facilite CO
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oxidation. The exact form in which Pd displays its high activity remains
not well understood. We present a DFT+U study of CO oxidation for
single Pd atoms located on or in the ceria surface as well as a Pdn
nanorod model on the CeO2(110) surface. The oxidation of Pd to the
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2+ state by ceria weakens the Pd−CO bond for the single Pd models
and, in this way, facilitates CO2 formation. After CO oxidation by O of
the ceria surface, Pd relocates to a position below the surface for the
Pd-doped model; in this state, CO adsorption is not possible anymore.
With Pd on the surface, O2 will adsorb and dissociate leading to PdO,
which can be easily reduced to Pd. The reactivity of the Pd nanorod is
low because of the strong bonds of the metallic Pd phase with CO and
the O atom derived from O2 dissociation. These findings show that highly dispersed Pd is the most likely candidate for CO
oxidation in the Pd−CeO2 system.

1. INTRODUCTION enhance the performance again due to the reduction to metallic

Palladium supported on ceria is one of the main components of
the three-way catalyst used to clean the exhaust gas of gasoline
engines.1 Because of strong metal−support interactions, Pd
atoms tends to be present on the ceria support in highly
dispersed forms. The nature of the catalytically active Pd
phaseas ions in the ceria, isolated atoms, and clusters or
larger particlesis strongly influenced by aging at high
temperature under reducing and/or oxidizing conditions. It
has not been unequivocally resolved yet how the rate of CO
oxidation depends on the active phase form and which phase is
the most active.
Kumatowaska et al.2 reported that as-prepared nanocrystal-
line Ce0.89Pd0.11O2−y demonstrates moderate activity in CO
oxidation. Reduction at 400 °C in H2 strongly improved the
catalytic activity, suggesting that Pd atoms in positions where
they substitute Ce cations are less active than Pd on the ceria
surface. Fernandez-Garcia et al. studied room-temperature CO
oxidation of Pd/CeO2 prepared by wet impregnation and
concluded that ceria promotes the formation of metallic Pd
clusters as the active centers for CO oxidation.3 Hinokuma et
al. found that Pd/CeO2 displayed increased room-temperature
CO oxidation activity after thermal aging at 900 °C in air due to
increased metal−support interactions and phase transforma-
tions from Pd oxide into metallic Pd particles.4 In a recent
contribution of the same group,5 an arc-plasma process to
deposit Pd nanoparticles on CeO2 was found to lead to more
active catalysts than conventional preparation methods.
Thermal aging at 600 °C in air lowered the catalytic activity,
which was attributed to the oxidation of metallic Pd to Pd
oxide. Aging at 900 °C in 10% H2O/air was observed to
Pd.
Other studies provide evidence for the opposite conclusion.
Gulyaev et al.6 employed the same arc-plasma method as
Hinokuma et al. to synthesize Pd/CeO2 with high activity at
room temperature and argued that the activity must derive from
a PdCeOx solid solution and highly dispersed PdOx nano-
particles at the ceria surface. Room temperature CO oxidation
over Pd/CeO2 was also reported by Boronin et al.,7 who found
that subnanometer Pd particles have increased interaction with
the ceria surface. Recently, Colussi et al. used DFT calculations
to propose a Pd−O−Ce surface structure.8 XPS combined with
X-ray absorption spectroscopy studies of the oxidation state
and local atomic structure of Pd species led Zhou et al. to
propose that Pd ions interacted with the ceria support, and the
resulting PdOx species are the most active component for CO
oxidation.9 Using a combustion-based method, Bera et al.
synthesized ceria-supported Pd catalyst for CO oxidation and
observed higher activity compared with alumina-supported
Pd.10 The observed enhanced catalytic activity of Pd/CeO2 was
attributed to the ionic forms of highly dispersed Pd on CeO2
leading to strong metal−ceria interactions, likely in the form of
a solid solution.
Despite the importance of these experimental efforts,
relatively few theoretical studies have been carried out aimed
at elucidating the active state of Pd in Pd/CeO2 catalysts for
CO oxidation. Ab initio thermodynamic calculations were
Received: September 23, 2015
Revised: October 30, 2015
Published: November 16, 2015

© 2015 American Chemical Society 27505 DOI: 10.1021/acs.jpcc.5b09293

J. Phys. Chem. C 2015, 119, 27505−27511
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Figure 1. Structure of Pd−CeO2(110) models (color scheme: red = O; white = Ce4+; cyan = Ce3+; green = Pd).
Figure 2. Reaction mechanism of CO oxidation on the Pd1/CeO2(110) model. The electron density difference plot for CO adsorption on Pd1/
CeO2(110) (color scheme: gray = C) is inserted next to the structure (state ii). The blue and yellow colors indicate respectively a decrease and an
increase in the electron density.
employed by Mayernick et al. to determine the stability of Pd
atoms doped into the ceria lattice as compared with isolated Pd
atoms and small Pd clusters as a function of the temperature
and oxygen partial pressure.11 The activity of the various Pd-
CeO2 models toward methane activation has also been
investigated by the same group.12,13 In comparison, more
work has been done on the topic of CO oxidation for the Au−
CeO2 combination. Song et al. investigated the active state of
gold in Au/CeO2 for CO oxidation14,15 and the water-gas shift
reaction,16 comparing Au models and different reaction
pathways. Here, we use the same approach to compare the
performance of a single Pd atom adsorbed on the ceria surface,
a single Pd atom incorporated in the ceria lattice, and a Pd
nanorod adsorbed on ceria as catalysts for the CO oxidation
reaction. The latter nanorod surface structure allows modeling
Pd nanoparticles by DFT calculations.17 Experimental as well
theoretical investigations14,15,18,19 suggest that CeO2(110) is a
reactive surface termination of ceria, likely involved in catalytic
reactions. The vacancy formation energy for the (110) surface
is lower than for the (111) surface. Ceria nanorods that
according to many authors expose predominantly (110) surface
show increased performance in CO oxidation.20 The dominant
surface termination of ceria nanorods is, however, under
debate; Agarwal et al. have recently shown that ceria nanorods
may be terminated by CeO 2 (111) surfaces. 21 In our
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calculations, we adopt the CeO2(110) surface model as a
point of reference for future calculations.
2. COMPUTATIONAL DETAILS
Density functional theory (DFT) with the PBE (Perdew−
Burke−Ernzerhof) functional22 as implemented in the Vienna
Ab Initio Simulation Package (VASP)23−25 was employed. A
Hubbard U term was added to the PBE functional (DFT+U)
employing the rotationally invariant formalism by Dudarev et
al.,26 in which only the difference (Ueff = U − J) between the
Coulomb U and exchange J parameters enters. Spin-polarized
calculations were performed. The projector augmented wave
method (PAW)27−29 was used to describe the interaction
between the ions and the electrons with the frozen-core
approximation. The Ce (4f, 5s, 5p, 5d, 6s), O (2s, 2p), and Pd
(4p, 4d, 5s) electrons were treated as valence states using a
plane-wave basis set with a kinetic energy cut off of 400 eV. For
Ce, a value of Ueff = 4.5 eV was used, which was calculated self-
consistently by Fabris et al.30 using the linear response
approach of Cococcioni and de Gironcoli.31 This value is
within the 3.0−5.5 eV range reported to provide localization of
the electrons in the Ce 5f orbital left upon oxygen removal
from CeO2.32 For all the surface calculations, the model was a
periodic slab with a (3 × 3) surface unit cell, and for the
Brillouin zone integration, a Monkhorst−Pack 1 × 1 × 1 mesh
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was used. The CeO2 (110) slab model is four layers thick, and a
vacuum gap was set to be 15 Å. The bulk equilibrium lattice
constant (5.49 Å) previously calculated by PBE+U (Ueff = 4.5
eV) was used.33 A nanorod of 32 Pd atoms was placed on the
(3 × 3) surface unit cell of CeO2(110) to serve as a model for
supported Pd clusters and nanoparticles. The Pd adatom and
the two top atomic layers of the ceria slab were allowed to relax,
while the two bottom layers were kept fixed to their bulk
position. Atoms were relaxed until forces were smaller than
0.05 eV Å−1. The location and energy of transition states were
calculated with the climbing-image nudged elastic band
method.34
3. RESULTS AND DISCUSSION
Pd1/CeO2(110). We identified three adsorption sites for a
single Pd atom on the CeO2(110) surface (Figure 1). The first
two involve Pd coordinating in a bridging fashion between two
surface O atoms. In the symmetric mode (Figure 1a), the
distance of the Pd atom to each of these O atoms is 2.02 Å; the
adsorption energy of the Pd atom is −2.02 eV. A very similar
adsorption site has been identified before,11 with a slightly
lower adsorption energy of −1.78 eV and longer Pd−O
distances. The difference most likely arises from the smaller
supercell used in the calculations of Mayernick et al., leading to
increased lateral repulsive interactions. The adsorption of the
Pd atom results in the reduction of one of the Ce atoms in the
surface to the +3 oxidation state. We also identified another less
symmetric adsorption mode in which Pd bridges between two
O atoms in the way shown in Figure 1b. It is the result of the
migration of one of the O atoms in the symmetric structure to a
bridge site between Ce and Pd atoms with Ce−O and Pd−O
bond distances 2.20 and 1.92 Å, respectively. This nonsym-
metrical adsorption site is more stable by 0.54 eV as compared
with the symmetric adsorption model in Figure 1a. The most
stable adsorption site for a single Pd atom on the CeO2(110)
surface is the 4-fold hollow site with Pd connected to four
surface O (Figure 1c). The adsorption energy is −2.99 eV. The
bond distance between the Pd atom and the four surface O
atoms is close to 2.09 Å. In this adsorption mode, two surface
ceria atoms are reduced to 3+, implying a formal oxidation state
of +2 for Pd. The replacement of a Ce atom for a Pd atom in
the surface is also considered (Figure 1d). In the next section,
we will discuss the mechanism of CO oxidation for the Pd atom
in the 4-fold site of CeO2(110) denoted by Pd1(4f)/
CeO2(110) and the Ce surface substitution model denoted
by Pd1Ce1−xO2(110).
CO Oxidation on Pd1(4f)/CeO2(110). As a first step in the
catalytic cycle, CO adsorbs on Pd with an adsorption energy of
146 kJ/mol (state ii, Figure 2). The bond distance of C to Pd is
1.84 Å. The C−O bond distance is slightly elongated to 1.17 Å
as compared with the C−O distance of 1.14 Å in gas-phase CO.
It points to electron back-donation from the Pd d orbitals to
the antibonding orbitals of CO. Electron back-donation is also
evident when the electron density differences following
adsorption of CO on Pd1(4f)/CeO2(110) are visualized
(Figure 2). As a result of the electron redistribution, Ce3+
present before CO adsorption is oxidized to Ce4+. The
adsorption of CO also leads to the migration of the Pd atom
to the bridge site between two O atoms. In contrast to strong
CO adsorption (−146 kJ/mol), O2 binds only weakly on Pd1/
CeO2(110) with an adsorption energy of −16 kJ/mol.
Consistently, the bond length of O2 is only slighty elongated
to 1.25 Å (gas phase 1.23 Å). The result points out that Pd1/
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CeO2 will bind CO preferentially. The CO2 product is formed
by tilting of the adsorbed CO molecule to the surface (state iii,
Figure 2). The activation barrier for this process is 82 kJ/mol,
and the reaction energy is −51 kJ/mol. Two Ce4+ ions in the
surface are reduced to Ce3+. Desorption of CO2 into the gas
phase costs 79 kJ/mol, and it generates a surface oxygen
vacancy (state iv, Figure 2). The vacancy can be filled by
adsorption of molecular oxygen (state v, Figure 2). Adsorption
of O2 is strongly exothermic (ΔE = −223 kJ/mol). The O−O
bond length is elongated to 1.46 Å (cf. gas-phase O−O bond
length = 1.23 Å). The next CO molecule can absorb to the Pd
atom with an adsorption energy of 106 kJ/mol (state vi, Figure
2), slightly lower than the adsorption on the bare Pd1(4f)/
CeO2(110) surface. Consistent with this, the bond distance
between Pd and C is 1.88 Å, slightly longer than for CO bound
to Pd1(4f)/CeO2(110) (1.84 Å, Figure 2). All of these data
indicate that electron back-donation from the Pd d orbitals to
the antibonding orbital of CO molecule is weaker because the
Pd has been further oxidized by the adsorption of O2. The
barrier for O2 dissociation is 51 kJ/mol. In the transition state,
the O−O bond is elongated to 1.81 Å; the associated reaction
energy is downhill by 137 kJ/mol. One of the O atoms fills the
oxygen vacancy site, accompanied by reoxidation of two
Ce3+atoms back to Ce4+. The other O atom coordinates to Pd
together with CO and forms CO2 with a relatively low barrier
of 31 kJ/mol (ΔE = −87 kJ/mol) (state viii, Figure 3).
Desorption of the second CO2 molecule costs 39 kJ/mol and is
followed by the migration of the Pd atom back to the 4-fold
site, completing the reaction cycle (state i, Figure 2).
Figure 3. Reaction mechanism of CO oxidation on the
Pd1Ce1−xO2(110) model.
CO Oxidation on Pd1Ce1−xO2(110). After doping the
CeO2(110) surface with Pd, the top layer is composed of Pd,
Ce, and O atoms (state i, Figure 3). The Pd atom is
coordinated to four surface O (Pd−O bond distance: 2.18 Å)
and two subsurface O atoms at a slightly larger distance of 2.24
Å. CO adsorbs on the Pd atom with an adsorption energy of 96
kJ/mol (state ii, Figure 4). The Pd−C bond distance is 1.85 Å.
The relatively weak adsorption of CO on the Pd atom is clear
from the C−O bond distance of 1.15 Å, which is almost the
same value as for gas-phase CO. CO oxidation proceeds by
tilting the adsorbed CO molecule to the closest surface O atom
(state iii, Figure 3). The reaction energy for this process is very
strongly exothermic (ΔE = −408 kJ/mol), which is due to the
weak binding of the reacting O atom that bridges between the
Pd and Ce surface atoms. This result is in keeping with
literature findings.11 CO2 desorption is very facile with a
desorption energy of only 22 kJ/mol. Because of the removal of
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Figure 4. Projected density of states (DOS) analysis for d-orbital of Pd
on varies Pd−CeO2 model (reference energy is the Fermi level marked
by the vertical dashed line).
a surface O atom and desorption of the CO2 product, Pd will
migrate deeper into the surface by 0.73 Å; it is then coordinated
to two surface O atoms (bond distance: 2.00 Å) and two
subsurface O atoms (bond distance: 2.03 Å) (state iv, Figure 3).
For this stable state, we found that neither CO nor O2 can
adsorb, which means that the catalyst is deactivated.
Thus, for the Pd1Ce1−xO2(110) system CO adsorption is
possible on the stoichiometric surface (state i, Figure 3). After
removal of the first O atom adjacent to the Pd atom, Pd moves
to a subsurface position and CO adsorption is not possible
anymore. It is worthwhile to compare this case with a Pd-doped
CeO2(111) surface. Then, the top layer of the surface contains
only O atoms; the Pd and Ce atoms are located in the second
layer, and no stable CO adsorption state can be identified. We
note that for a similar model weak CO adsorption has been
reported using the PW91 functional.35 It is well-known that the
Figure 5. Reaction mechanism of CO oxidation on the Pdn/CeO2(110) model.
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PW91 functional overestimates binding energies as compared
with the PBE functional36 that was used in the present study.
The use of more accurate functionals is thus needed to
understand the weak CO adsorption on these Pd-doped ceria
surfaces. It is clear, however, that CO adsorption will be
strongly preferred on the other systems discussed in this work.
These findings suggest that geometrical factors influence the
adsorption of on the Pd atoms located on or in the surface. To
illustrate that these differences are not due to the electronic
state of Pd, Figure 4 depicts the projected density of states
(PDOS) of the Pd 4d-orbitals for a Pd atom in different
configurations on CeO2(111) and CeO2(110) surfaces.
Integration of the PDOS allows estimating the oxidation state
of the Pd atom. The oxidation state of Pd doped in
stoichiometric (111)- and (110)-terminated surfaces is about
+2.35 e. On the former surface CO adsorption on Pd is not
possible, while CO strongly adsorbs on Pd on the latter surface.
When Pd is located below the top layer in Ce1−xO2−y, the
oxidation state is only slightly lower (+2.1 e). CO adsorption is
not possible on this Pd atom. When the Pd atom is located in
the CeO2(110) surface, the oxidation state is almost the same
(+2.07 e), but in this case CO adsorption is relatively strong.
From these findings, we infer that the geometry around the Pd
atom determines whether CO adsorption can take place: when
the Pd atom is below the surface, the O atoms repel the CO
molecule so that binding to the Pd atom is not possible.
CO Oxidation on Pdn/CeO2(110). We also studied CO
oxidation on a Pd nanorod placed on the CeO2(110) surface,
which serves as a model for Pd clusters and nanoparticles. The
reaction energy diagram and the key intermediate structures are
shown in Figure 5. CO adsorbs on a 3-fold hollow site of the
Pd nanorod with an adsorption energy of 222 kJ/mol (state ii,
Figure 5). The C−O bond distance of 1.20 Å is substantially
longer than the gas-phase C−O bond distance. Comparing the
three above models, we note that increased metallic character
(Pd n /CeO 2 (110) > Pd 1 Ce 1 − x O 2 (110) > Pd 1 (4f)/
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Ce1−xO2(110)) results in stronger Pd−CO bonds and weaker
C−O bonds due to electron back-donation from Pd into CO
antibinding orbitals. The energy barrier for reaction of the
adsorbed CO with a surface O atom is 122 kJ/mol, and the
reaction energy is exothermic by 20 kJ/mol. We compare these
values to the same reaction on a Aun/CeO2(110) model, for
which the reaction barrier is negligible and the exothermic
energy 146 kJ/mol.15 The difference relates to the much
stronger Pd−CO bond.
Formation of CO2 results in the reduction of two Ce4+ ions
to Ce3+ (state iii, Figure 5). Desorption of CO2 costs 50 kJ/mol
and results in an oxygen vacancy at the interface between the
Pdn rod and the ceria surface (state iv, Figure 5). Molecular
oxygen will adsorb at this site with (ΔE = 108 kJ/mol) (state v,
Figure 5). O2 dissociates with a barrier of 55 kJ/mol, resulting
in healing the surface vacancy and migration of the other O
atom to the Pd nanorod (state vi, Figure 5). In this way, the
reduced Ce3+ ions are reoxidized back to Ce4+. The reaction
cycle is then completed by reaction of CO adsorbed in a 3-fold
hollow site with this O atom (state viii, Figure 5). The barrier
for this latter reaction of 133 kJ/mol is very close to the barrier
for CO oxidation on the Pd(111) surface.37 Contrasting these
findings with data for Au n /CeO 2 (110) 15 and Au n /
CeO2(111),38 one appreciates that the lower binding energy
of O on gold surfaces leads to negligible barrier for CO2
formation. This implies that the synergy of ceria with Au
nanoparticles in CO oxidation will be greater than with Pd
nanoparticles. For Pd nanoparticles supported on ceria, CO
oxidation by an O atom adsorbed on the metallic phase is the
most difficult step, and this step is as difficult as for an extended
Pd surface.
An alternative mechanism would involve O2 adsorption to Pd
followed by dissociation or direct reaction with coadsorbed CO
as has been explored for Aun/CeO2(111).38 We investigated O2
adsorption on the Pd cluster and found an adsorption energy of
114 kJ/mol, much lower than that of CO adsorption on Pdn/
CeO2(110) (222 kJ/mol). In addition to the lower adsorption
energy, two other factors will contribute to unfavorable
adsorption of O2 vs CO. First, the adsorption of O2 needs
two metal sites, whereas CO requires only one binding site.
Second, O2 adsorption involves spin flip of O2 from the triplet
gas phase state to the singlet state,39 which will significantly
lower the sticking coefficient for adsorption. All of these factors
contribute to predominant CO coverage under typical CO
oxidation conditions. This is reasonable as typically these
catalysts suffer from self-poisoning by CO.40 This discussion
brings to the fore the important role of the Pd−ceria interface
for O2 adsorption and activation.
Discussion. We investigated here three models for Pd in
interaction with the CeO2(110) surface for CO oxidation.
When a single Pd atom is considered either on or in the surface,
the Pd atom will be oxidized. This decreases the CO bond
energy as compared with metallic Pd. The lower binding energy
of CO with the single Pd atom benefits the formation of CO2.
The single Pd atoms in these two models are also very close to
the O atoms of the ceria surface, further facilitating CO2
formation. In contrast, when Pd is present in the form of a
metallic nanorod, the binding energy of CO and the reaction
barrier for CO2 are much higher. This holds for the reaction of
adsorbed CO with an O atom of the ceria surface as well as an
O adatom on the Pd nanorod surface. Another contributing
factor is the much stronger adsorption of the O atom from O2
dissociation on the nanorod metallic surface (158 kJ/mol vs
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gas-phase O2) than on the single Pd atom on the surface (77
kJ/mol). In the case of Pd doping into the ceria surface, we
show that the geometry of the surface strongly influences CO
adsorption. Only when Pd is in the first surface layer can CO
adsorption take place; when Pd is in the second layer as occurs
after one O vacancy is generated or when Pd is doped into the
CeO2(111) surface, repulsion by the surface O atoms inhibits
CO adsorption. The same holds for O2 molecule which is weak
with an adsorption energy of 8 kJ/mol. With the formation of
one oxygen vacancy generated by CO, the Pd will migrate in
the subsurface layer and coordinate with four oxygen atoms.
The oxidized Pd atom shows much decreased ability to adsorb
O2. Also, the repulsive interactions between the large ceria
surface O anions and an impinging O2 molecule decrease its
possibility to bind to the surface. The combination of these two
factors explains weak O2 adsorption. These considerations have
also been discussed for oxygen adsorption in the Au−
CeO2(111) system.41 We conclude that the oxygen vacancy
site is a necessary but not a sufficient condition for O2
adsorption.
From the present findings, we infer that highly, preferably
atomically, dispersed Pd on ceria is more active in CO
oxidation than Pd atoms doped in the ceria or metallic Pd
nanoparticles. Experimental studies have pointed out that CO
can be oxidized effectively by Pd-doped ceria;6−9 we counter
however that such works cannot exclude the presence of Pd
adatoms on the surface. In this respect, it is worthwhile to
mention the theoretical study of Kim et al.42 that shows CO
adsorbed on a metallic adatom cluster can easily react with O
atoms that neighbor to the metal atoms doped in the ceria
surface. Our results also show that Pd clusters and nano-
particles do not benefit from the ceria surface despite the
involvement of its surface O atoms: removal of the O adatom
on the metallic Pd particle by CO has almost the same barrier
as CO oxidation on Pd(111).
4. CONCLUSIONS
The DFT+U approach was employed to study the interface of
Pd with the CeO2(110) surface for CO oxidation. Three
models were compared involving doping of the surface with a
single Pd atom, placing a single Pd atom on the surface and a
nanorod model placed on the surface. CO adsorption is
possible on all three models. Because Pd is oxidized in the
single atom models to a 2+ oxidation state, CO adsorbs weaker
than on the metallic Pdn nanorod model. The lower CO
adsorption strength explains the lower activation energy for the
formation of CO2. When CO2 is removed, the single Pd atom
that was doped into the ceria surface migrates to subsurface
positions, which deactivates the catalyst because further CO or
O2 adsorption is not possible. This is a geometric rather than an
electronic effect. For the Pd atom on the surface, O2 adsorption
and dissociation heals the oxygen vacancy in the surface and
leads to PdO on the surface which is easily reduced to Pd with
CO. The strong binding energy of CO on the metallic nanorod
surface and the lower activation of the O atom of the ceria as
compared with the single Pd models explain the higher barrier
for CO2 formation. The most difficult step is the removal of the
O atom from the surface after O2 dissociation at the interface.
The barrier is close to the one computed for CO oxidation on
the Pd(111) surface. These findings indicate that high
dispersion, possibly atomic dispersion of Pd over the ceria
support yields to intrinsically more active catalysts than metallic
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Pd particles. Doping of Pd in the surface cannot contribute to
the catalytic activity as the catalytic cycle cannot be closed.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b09293.
Additional information (total energy of each state in
Figures 2, 3 and 5; optimized structure file of selected
structure) presented in Figure S1 (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail e.j.m.hensen@tue.nl; Tel +31-40-247 5178 (E.J.M.H.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge financial support for this research from China
University of Petroleum-Beijing (no. 2462015YJRC005) and
the National Natural Science Foundation of China (no.
21503273). E.J.M.H. acknowledges financial support from
The Netherlands Organization for Scientific Research through
a VICI grant. Supercomputing facilities were funded by The
Netherlands Organization for Scientific Research.
■
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27511 DOI: 10.1021/acs.jpcc.5b09293

J. Phys. Chem. C 2015, 119, 27505−27511