J. Phys. Chem.

C 2009, 113, 9239–9250 9239

A Density-Functional Theory Study of the Water-Gas Shift Mechanism on Pt/Ceria(111)

Richard T. Kinch, Carlos R. Cabrera, and Yasuyuki Ishikawa*

Department of Chemistry and the Chemical Physics Program, UniVersity of Puerto Rico,
P.O. Box 23346, San Juan, Puerto Rico 00931-3346
ReceiVed: NoVember 13, 2008; ReVised Manuscript ReceiVed: March 26, 2009
嘷
w This paper contains enhanced objects available on the Internet at http://pubs.acs.org/JPCC.

Density-functional theory has been used to model the interactions between ceria(111) and CO adsorbed on
platinum in order to provide insights into the mechanism behind the water-gas shift reaction on this material.
Morphological studies on ceria show the presence of various defect sites, both cerium and oxygen vacancies,
which are believed to be the reason for the catalytic activity of the substrate. Of these defect sites, the reported
calculations clearly show the preference for platinum to bind in cerium vacancies, as opposed to a defect-free
surface or an oxygen deficiency site. Currently there are two main pathways proposed for this mechanism: a
direct redox pathway and a formate-intermediate pathway. In both scenarios the initial step is the same: the
oxygen storage capacity of ceria provides the oxygen necessary to oxidize CO into CO2; water then adsorbs
and is dissociated in these oxygen vacancies helping reform the ceria surface. The key difference between
the two mechanisms is either the desorption of CO2 and the formation of H2 when a second water molecule
adsorbs at a site where water had been previously dissociated (catalyzed by platinum), or the formation of a
formate species from the interaction of the adsorbed CO2 with adjacent water molecules. Energy pathways
are mapped for both processes, demonstrating the preference toward the initial direct redox pathway. However,
the resulting formation of adsorbed hydroxide species in the oxygen vacancies adjacent to the platinum hinders
this pathway. A bifunctional mechanism is then presented as a means to remove these species and thereby
form formate. The activation of these adsorbed hydroxides is also studied.

1. Introduction molecular hydrogen, are also of particular interest by presenting

Alternate sources of energy are becoming a necessity as
nonrenewable fossil fuels like petroleum are being depleted.
One such area that is generating great interest is the hydrogen
fuel cell. Hydrogen is the most efficient fuel available for use
in proton exchange membrane fuel cells (PEMFC); however, it
has many drawbacks derived from two key physical properties:
(1) it is a gas at room temperature and (2) it is highly explosive,
especially when transported under high pressure. To avoid these
limitations and simultaneously take advantage of an already
well-established petroleum-based infrastructure, a fuel that has
similar properties to petroleum can be used: simple, liquid
hydrocarbons, such as methanol and ethanol, have received
increased interest over the past years as fuel cell technology
advances for these reasons.
Direct methanol fuel cells (DMFC) are intensively studied
because methanol can be readily introduced as an alternative
fuel without significantly altering the transportation, storage,
and delivery requirements that are in use for petroleum.
Methanol, however, has its own problems when used in fuel
cells. CO poisoning of the platinum catalyst and methanol
crossover through the proton exchange membrane are just a few
of the problems to overcome in order to successfully implement
DMFCs as a viable alternative energy source.1-3 Even if these
limitations are overcome, molecular hydrogen still possesses a
much higher energy density. Because of this, reformer units,
which convert a hydrocarbon fuel through various stages into
* To whom correspondence should be addressed. Phone: +1 787 764
0000. Fax: +1 787 756 7717. E-mail: yishikawa@uprrp.edu.
10.1021/jp810021e CCC: $40.75  2009 American Chemical Society
Published on Web 05/04/2009
a viable means to store and transport a liquid source of molecular
hydrogen.4
CnHm + nH2O f nCO + ((m/2) + n)H2 (1.1)
H2O + CO f CO2 + H2 (1.2)
Catalytic steam reforming of methanol (SRM) devices
operates at a temperature range of 250-300 °C and at
atmospheric pressure.5,6 These devices can then be attached to
a hydrogen fuel cell to generate electricity, thereby providing
all the advantages of a fuel such as methanol without the
drawbacks that would be present by using it directly in a fuel
cell. These operating conditions are also very promising for
portable technology.
One of the main steps in the conversion of a hydrocarbon
fuel to molecular hydrogen is the water-gas shift reaction
(WGSR) (eq 1.2). It is a crucial part of the reformation process
because its purpose is to oxidize the CO resulting from the
dehydrogenation of the hydrocarbons or alcohols, and in the
process produce additional H2. Platinum, in particular, has
proven to be a reliable, although expensive catalyst for this
process. Recently, there has been increasing interest in develop-
ing new, more cost-effective systems to be used as catalysts
for low-temperature WGSR.4 One group of these new catalysts
is based on cerium oxide (ceria). Among other materials, ceria
has been used extensively as a three-way catalyst in automobiles;
the ability for ceria to readily donate oxygen from its lattice,
referred to as oxygen storage capacity, is believed to account
for its efficiency.7 The same ability this catalyst has to efficiently
oxidize CO into CO2 is now being harnessed for use in reformer
cells to generate H2. This unique property has prompted several
9240 J. Phys. Chem. C, Vol. 113, No. 21, 2009
research groups to develop ceria-based catalysts by doping or
depositing a variety of catalytically active metals (Cu, Pt, Au,
Pd).8-12 The focus of this new research is to attempt to reduce
the operating temperature of the process with the goal of
implementing onboard reformer units for fuel cells to power
machinery such as automobiles.
The details on how the WGS process occurs on Pt/ceria
catalysts are the subject of a number of speculations and debates.
There are two main pathways that have been proposed to help
explain how molecular hydrogen is formed in the WGS reaction.
One pathway is a direct redox process involving the mobile
surface oxygen atoms of the ceria substrate,13 and the other
involves the formation of a formate intermediate mechanism.10,14
The formate-intermediate pathway has been studied by Rod-
riguez et al.15 to explain the WGS mechanism on catalytic metal
surfaces, and the presence of formic acid has been identified
through several studies.16,17 However, the thermal stability of
these intermediates, and therefore their involvement in the
reaction, is debatable at the high operating temperatures that
can be achieved.18
Gorte et al. proposed the redox process with the following
reaction pathway:
CO + σ f COads
H2O + σ f Oads + H2
COads + Oads f CO2 + 2σ
where essentially ceria is oxidized by water and reduced by
CO. The second pathway, posited by Shido and Iwasawa, is
summarized as follows:
CO + σ f COads
H2O + 2σ f Had + OHads
OHads + COads f HCOOads + σ
HCOOads + σ f CO2,ads + Hads
2Hads f H2 + 2σ
In this notation, σ is assigned to an arbitrary adsorption
site, whether it be on the ceria surface, the metal catalyst, or
both.
Several groups have developed Pt/ceria catalysts for the
WGS reaction.8-13,15,19-21 Bera et al. synthesized one such
catalyst through a combustion synthesis reacion, which
yielded finely dispersed platinum over the ceria surface.8
Another technique used to create these catalysts involved
solution deposition of the metal followed by a high-
temperature reduction of the material.11 Of particular interest
is the work of Flytzani-Stephanopoulos et al., who developed
a highly active catalyst with a minimal amout of platinum
loading.9 A deposition-precipitation technique19 was used
to deposit platinum on dispersed ceria nanoparticles, and the
excess metal was removed via cyanide leaching, which
removed over 90% of the deposited platinum. Most impor-
tantly, the catalytic activity of these materials before and after
cyanide leaching was virtually unaffected. Characterization
of these catalysts by scanning transmission electron micros-
copy (STEM), energy-dispersive X-ray spectroscopy (EDX),
and X-ray photoelectron spectroscopy (XPS) identified these
remaining platinum particles to be atomic or finely dispersed
and ionic.9
The focus of this study is a theoretical examination of the
WGS mechanism on Pt/ceria. Using density-functional theory
(DFT)22,23 and direct first-principles molecular dynamics,24-26
we probe the nature of active reaction environments, and
compare the energetics of the different steps in both the direct
Kinch et al.
redox pathway and the formate-intermediate pathway described
earlier. The direct molecular dynamics calculations were
performed to confirm different steps in each of these mecha-
nisms. The goal of this study is to map the WSG mechanism
on Pt/ceria and gain atomic-level understanding of the catalytic
processes and solid-gas interactions involved in the WGSR.
2. Computational Details and Methodology
The calculations presented herein were obtained by using
DFT,22,23 expanding the Kohn-Sham orbitals with a double
numerical basis set (dnp) as defined in the DMol3 code from
Accelrys, Inc.27,28 Exchange and correlation interactions were
described with the Perdew-Burke-Ernzerhof (PBE) func-
tional.29 The reaction pathways were mapped to locate their
transition states (TS) and respective activation energies
utilizing the nudged elastic band (NEB) technique30 by
iteratively fixing the distance by a fraction of an angstrom
between two atoms of interest and performing a partial
optimization. A full optimization was performed both before
the constraint was applied and after the TS were located to
ensure that the energy of both the initial and final structures
was at a minimum. For all geometry optimizations, the core
electron energies were described with a density-functional
semicore pseudopotential (dspp); for all energy calculations
all core electrons were included and a scalar correction for
relativistic effects on heavier atoms was applied.31 In all
cases, all the atoms surrounding the surface vacancies along
with any platinum, water, or CO molecules present (and any
other structures they formed during this process) were
allowed to relax during the optimization. Because of the
nature of the ionic cluster that is studied, it was necessary to
apply a thermal smearing to the low-lying states for the
system. The occupation of all states that were 0.05 eV above
the ground state was averaged by using the thermal smearing
code to allow for energy convergence.32
Direct first-principles molecular dynamics24-26 is a quasi-
classical molecular dynamics (MD) method in which the
potential surface is generated “on the fly” as each trajectory
develops rather than being fit to an analytical form. The
energies and gradients were calculated with use of the DMol3
code. The Verlet algorithm33 was employed to integrate the
classical equations of motion with time steps of 0.5 fs. The
zero-point vibrational energy (ZPE) for CO was calculated
separately, and the turning point bond distance was intro-
duced. No ZPE was given to the ceria cluster or platinum.
The initial temperature T of the system was calculated from
the total kinetic energy, which was scaled to 300 K:
∑ i Miυi2/2 ) (3N - 6)kT/2 (2.1)
where N is the number of nuclei in the system, and Mi and υi
are the mass of the ith nucleus and its velocity, respectively.
All the atoms were allowed to move freely during the MD
simulation.
3. Metal Oxide Cluster Modeling
The high-vacuum scanning tunneling microscopy (STM)
study performed by Esch et al. on ceria(111)34 clearly shows
the presence of numerous oxygen vacancy sites, whose number
and structure are temperature dependent. There are also some
defect sites that were unable to be characterized, which could
be cerium deficiency sites on the surface.
Flytzani-Stephanopoulos et al. reported that the use of ceria
nanoparticles of around 3 nm has been shown to increase the
The Water-Gas Shift Mechanism on Pt/Ceria(111) J. Phys. Chem. C, Vol. 113, No. 21, 2009 9241

Figure 1. Top and angular view of the cluster model for a cerium vacancy defect site (a) and an oxygen vacancy site (b). Red spheres and lines
are oxygen atoms, and white spheres and lines are cerium atoms. Orange spheres are the active oxygens that surround the cerium vacancy. The top
layers of the clusters have been represented with a ball and stick model to highlight the surface structure.

catalytic activity of systems for the WGS reaction.35 The (111)

surface was chosen because various studies have shown that
for polycrystalline samples and nanosized ceria particles, this
is the most prevalent and most stable face.36,37 Characterization
of the catalysts prepared by Bera and Flytzani-Stephanopoulos8,9,19
indicates the presence of finely dispersed or atomic platinum
on the ceria surface (or also within the lattice, as is the case
with Bera et al. and their procedure to dope ceria with platinum).
The XPS characterization of the catalyst developed by Flytzani-
Stephanopoulos et al. clearly elucidated the ionic nature of the
platinum on the ceria surface. In addition, scanning transmission
electron microscopy/EDX measurements showed no metal
particles remaining. The catalytic activity of this catalyst
remained unaffected even after over 90% of the metal was
removed from the surface. High-resolution transmission electron
microscopy studies also confirmed the removal of all metallic
platinum.9
Considering these two studies8,9,19 and the previous work
on Pt/ceria catalysts,10-12 a simple model can be constructed
to elucidate the WGS mechanism on this surface. Ceria was
modeled in a small cluster of 36 oxygen and 24 cerium atoms,
with the top layer of the surface comprised of oxygen as
shown in Figure 1, parts a and b. Since ceria is nonconduct-
ing, a small cluster can be used to model the behavior of the
surface of a larger nanoparticle. This system was used to Figure 2. Top and angular view of the cluster model for a linear
oxygen vacancy site. Red spheres and lines are oxygen atoms, and white
model platinum deposition in single oxygen or cerium spheres and lines are cerium atoms. The top layers of the clusters have
vacancy sites. In the case of a linear oxygen vacancy, as been represented with a ball and stick model to highlight the surface
seen in the STM images by Esch et al.,34 a slightly larger structure.
cluster was used consisting of 68 oxygen and 34 cerium
atoms, as seen in Figure 2. Platinum was placed in each
vacancy type and its final position was optimized. model with the sum of the energies of the cluster with the
The binding energies of cerium and oxygen were calculated defect and the removed atom as seen in the following
by comparing the energy of the optimized defect-free cluster equation:
9242 J. Phys. Chem. C, Vol. 113, No. 21, 2009
B.E. ) (Evac/CeO2 + Eatom) - Eatom / CeO2 (3.1)
in which Eatom/CeO2 is the total energy for the geometrically
optimized system of the defect-free ceria cluster, Evac/CeO2 is the
total energy of the system removing the selected atom (oxygen
or cerium) thus forming the defect site (the atoms that comprised
the defect site were allowed to relax during the optimization),
and Eatom is the total energy of a single removed atom.
The results show that the binding energy for cerium is nearly
three times greater than that for oxygen (∼122 kcal/mol and
∼48 kcal/mol, respectively). These values are much smaller that
the results obtained by Minervini et al.38 for the formation of
oxygen and cerium vacancies of 3.2 eV (74 kcal/mol) and 11.11
eV (256 kcal/mol), respectively, which were obtained from
periodic calculations of bulk ceria. This discrepancy is due to
the surface atoms not being fully coordinated (as in the case of
a bulk study). On the (111) surface, for example, each oxygen
atom is coordinated to three cerium atoms, half the number for
bulk ceria (which accounts for the binding energy of the surface
atoms being approximately half the reported value of the
periodic calculations).
These defect sites were also chosen based on these previous
experimental works. The cerium vacancy site was studied
primarily to account for the combustion synthesis procedure
Bera et al. developed to produce platinum-doped ceria,8 as well
as to help account for the results from the work performed by
Flytzani-Stephanopoulos et al.9,19 Both these studies present an
XPS analysis for the platinum region and both show that the
majority of the platinum present in the catalyst is in either Pt(II)
or Pt(IV) charged states. Flytzani-Stephanopoulos et al. em-
phasize that these oxidized metal species are the active sites
for the WGSR.35 The following DFT calculations will show
that this is attributed to the platinum replacing cerium atoms
within the lattice or on the surface. Oxygen vacancy sites are
the most abundant defect sites on the ceria surface; however, it
is unlikely that platinum would remain within an oxygen
vacancy site. Furthermore, if a platinum ion were to replace a
surface oxygen atom, it would then acquire a formally negative
charge. The other possibility is for the platinum atom to simply
be chemisorbed to the ceria surface, interacting with the surface
oxygen. However, considering the sodium cyanide leaching
technique used by Flytzani-Stephanopoulos et al. to remove the
excess platinum from the surface, any platinum adsorbed on
the surface would preferentially complex with the cyanide ions
and hence be removed.
4. Results and Discussion
4.1. Platinum Adsorption Site. To identify the active site
for the WGSR, it was necessary to determine where platinum
Figure 3. Top view (a) and angular view (b) of the optimized structure for platinum adsorbed above an oxygen vacancy. Red spheres and lines
are oxygen atoms, white spheres and lines are cerium atoms, and the blue sphere is a platinum atom.
Kinch et al.
was most stable on the ceria surface. High vacuum surface
studies performed by Esch et al. clearly show that the most
abundant defect sites on the ceria surface are oxygen vacancies.34
However, this alone does not necessarily mean that these are
the defect sites where platinum becomes embedded. There are
two different scenarios available for platinum to adsorb on the
surface: (1) oxygen vacancy sites, whether they are single or
grouped together in different arrays, or (2) cerium vacancy sites,
which could be present on the surface or where platinum atoms
could replace ceria within the lattice and on the surface.
To this extent, two small ceria clusters were constructed: one
containing a cerium vacancy in the center, and another with an
oxygen vacancy in the center, as detailed previously. Platinum
was placed within each of the vacancies and its position was
optimized. Platinum remains within the cerium vacancy after
optimization; however, a different picture emerges for its
interaction with the oxygen vacancy site. The adjacent cerium
atoms repel the platinum atom, and instead of binding within
the cavity at or near the location of the removed oxygen atom,
it repositions itself about 2 Å above the surface.
The binding energy of the platinum atom was calculated
by using the same method for calculating the cerium and
oxygen binding energies in the ceria lattice (eq 3.1). In this
case, Eatom/CeO2 is the total energy for the geometrically
optimized system with platinum embedded in the particular
defect site, Evac/CeO2 is the total energy of the system removing
the platinum and maintaining the defect site (the atoms that
comprised the defect site were allowed to relax during the
optimization), and Eatom is the total energy of a single
platinum atom. A negative value would indicate that the
platinum is not bound.
The binding energy for platinum in a cerium vacancy (as
would be the case for doped Pt/ceria) was 54.22 kcal/mol, while
the binding energy of platinum within (or more precisely
adsorbed above) an oxygen vacancy was only 13.55 kcal/mol.
In a linear oxygen vacancy, the behavior of platinum remains
unchanged. The optimized structure for this weakly adsorbed
platinum over an oxygen vacancy is presented in Figure 3.
Comparing these binding energies, the platinum adsorbed in
the oxygen vacancy can be attributed to the weakly bound
platinum on the catalyst prepared by Flytzani-Stephanopoulos
et al. that can be removed via cyanide leaching.9 The fact that
these catalysts retain the same catalytic activity before and after
cyanide leaching further justifies that the remaining platinum
in that catalystsin essence the active platinum sitessrests within
a cerium defect site. Figure 4 presents the geometrically
optimized Pt/ceria cluster, clearly illustrating that platinum is
embedded within the cerium deficiency site, with the surround-
The Water-Gas Shift Mechanism on Pt/Ceria(111) J. Phys. Chem. C, Vol. 113, No. 21, 2009 9243

Figure 4. Optimized structure for platinum within cerium vacancy: top view (a) and angular view (b). Red spheres and lines are oxygen atoms,
white spheres and lines are cerium atoms, the blue sphere is a platinum atom, and the orange spheres are the active oxygen surrounding the cerium
vacancy site.

TABLE 1: Mulliken Population Analysis for Selected Atoms

during Different Stages of the Water-gas Shift Reaction predominant charge states in the catalyst synthesized by
Flytazni-Stephanopoulos et al. are Pt(II) and Pt(IV), as seen
charge from the X-ray photoelectron spectra of the platinum region.9
formation of H 2O The reason for platinum to be present in this oxidized state is
initial Pt/ Pt-CO2 dissociation because it is replacing the formally charged Ce(IV) ion within
atom ceria system complex on Pt the lattice. However, in agreement with other studies in the
subsurface oxygen -0.762 -0.777 -0.744 area,40,41 ex situ XPS may not necessarily reflect the true charged
subsurface oxygen -0.763 -0.735 -0.783 states during reaction conditions (which can be shown with
subsurface oxygen -0.763 -0.733 -0.744 significantly different charges of the platinum atom during
active surface oxygen -0.624 -0.625 -0.628
different steps of the mechanism). Despite this discrepancy, there
active surface oxygen -0.623 -0.625 -0.627
active surface oxygen -0.624 -0.551a -b is little dispute as to whether the platinum atoms that participate
platinum 0.999 0.582 0.571 in the reaction are ionic or metallic. The charge analysis clearly
oxygen (OHads) -0.617 indicates that the platinum atom is in a reduced charge state
hydrogen (OHads) 0.231 due to the charge transfer from the surrounding oxygen atoms.
hydrogen (ads:Pt) 0.163 4.2. CO Adsorption and CO2 Formation. The first step of
carbon (CO) 0.458 the WGS mechanism is the adsorption of CO and the formation
oxygen (CO) -0.249
of CO2. Energetics studies show that CO binds strongly to the
surface cerium 1.287 1.255
platinum atom in the cerium deficiency site, and spontaneously
a
This oxygen has been removed from the oxygen vacancy after forms a very stable Pt-CO2 complexs36.62 kcal/mol lower
interacting with CO to form CO2. b This oxygen atom is missing in energy than the reactant asymptote for the processsby
because of the removal of CO2 from the system. extracting one of the oxygen atoms adjacent to the platinum. It
is interesting to note that the adsorbed CO2 is nonlinear, which
ing surface oxygen atoms (these atoms have been colored orange is attributed to the interaction of the extracted oxygen atom with
to highlight their positions) expanding around it. The Ce-O the ceria surface. The equilibrium distance of Pt-C for this
distance for these active oxygen ranges from 2.56 to 2.59 Å, structure is 2.13 Å, and the O-C-O angle formed by the
slightly larger than the corresponding distance in the crystal Pt-CO2 complex is 126.2°. To obtain the energy necessary for
(2.34 Å). As will be shown later, these reactive oxygen atoms removal of CO2 from the surface, the distance between the
are a vital part of the catalytic activity of this system. platinum atom and the carbon of the CO2 molecule was
Mulliken population analysis39 was performed on the system, iteratively stretched by 0.1 Å, and the system was geometrically
and the results show that the adsorbed platinum atom in the reoptimized. After each geometry optimization, the energy of
cerium vacancy site is ionic in nature. Table 1 shows the each system was evaluated by using all-electron DFT, removing
Mulliken charge for various cerium and oxygen atoms as well the pseudopotential that was applied during the geometric
as the adsorbed platinum (examples of these are indicated in optimization. Figure 5a presents the energy diagram for the
Figure 4). Although Mulliken population analysis does not adsorption of CO, and formation and evolution of CO2 in the
provide a highly accurate description of the charge separation absence of water. The dissociation of the Pt-C bond requires
of the atoms in the system, it does provide a semiquantitative 11.71 kcal/mol. It is interesting to note that although the CO
view of how charge is distributed. When the Mulliken charge extracts an oxygen atom from the surface, it remains weakly
for the various subsurface oxygen atoms is compared during physisorbed in the oxygen vacancy of ceria surface. This weak
different steps of the mechanism, no significant change is physisorption is only 5.71 kcal/mol, and can be overcome
observed. It can be clearly seen that the active oxygens all have thermally. The net process is highly exothermicsthe difference
a consistently lower Mulliken charge than the other oxygen in between the reactant and product asymptotes for this step of
the ceria lattice. Another key feature is the change in Mulliken the mechanism is 19.19 kcal/mol.
charge of the platinum atom as different species are adsorbed In the presence of water, this process is hindered, but the net
to it. These results coincide with the characterizations performed result is still exothermic. Water adsorbs to the ceria surface and
by Bera and Flytzani-Stephanopoulos, who both clearly state can hydrogen bond to the CO2 adsorbed on the platinum atom,
that the platinum present in their catalysts is ionic.8,9 The increasing the energy required for the CO2 to escape the surface.
9244 J. Phys. Chem. C, Vol. 113, No. 21, 2009
Figure 5. Energy diagrams for the CO2 formation-evolution pathway (a) in the presence of one H2O molecule and (b) in the absence of H2O.
Figure 5b shows the energy pathway for the formation and
evolution of CO2 in the presence of one adsorbed water
molecule. This trend persists for increasing amounts of adsorbed
water.
Direct MD calculations were performed on the cluster to
confirm the formation of the Pt-CO2 complex. Figure 6 presents
snapshots of these MD simulations of CO approaching the Pt/
ceria surface. A movie clip of the MD snapshots presented in
Figure 6 is also available online. The initial temperature for
this calculation was 300 K, and the CO molecule was given an
initial kinetic energy of 0.005 eV (0.12 kcal/mol). The ZPE for
CO was calculated separately, and the turning point bond
distance was introduced. The results from the direct molecular
dynamics calculation confirm the spontaneous nature of the
formation of CO2. The MD simulation shows that as CO
impinges on the surface, it binds to one of the active oxygen
forming CO2 molecules at the 12.5 fs time step, and then binds
to the platinum atom, confirming the formation of the previously
described Pt-CO2 complex. The CO2 molecule then begins to
vibrate, and slowly breaks away from the platinum atom,
becoming more linear in the process. At 94 fs, the CO2 takes
on a linear geometry and the captured oxygen from the ceria
surface is no longer bound to the surface. The initial spontaneous
formation of the Pt-CO2 complex is highly exothermic,
releasing 36.88 kcal/mol. Even with the deformation of the ceria
cluster from the high exothermicity of the complexation, this
release of energy is imparted to the kinetic energy of the product,
Kinch et al.
providing the driving force for CO2 to break away from the
platinum atom, even though the minimum energy pathway for
this process (Figure 5) shows that it is a very stable complex.
4.3. Water Dissociation on the Ceria Surface. The active
oxygen atoms on the ceria surface are depleted with each
subsequent oxidation of CO, leaving several oxygen vacancy
sites surrounding the platinum atom. These vacancies are the
most favored sites for water adsorption. Figure 7 compares the
energy for water adsorbed on different sites on the catalyst
surface and the difference in energy between each of them.
These results demonstrate that water is most stable when
adsorbed in an oxygen vacancy site. Once water is adsorbed in
the cavity (with the oxygen located slightly above where the
surface oxygen used to be), platinum catalyzes its dissociation.
This dissociation is a crucial step not only because it helps
regenerate the catalyst surface, but also because this process is
a source of atomic hydrogen for the later steps of the mechanism.
Water binds in the oxygen vacancy site with an exothermicity
of 9.68 kcal/mol. The dissociation of the water molecule by
stretching the bond between the hydrogen atom facing the
adsorbed platinum and the oxygen atom of the water molecule
requires 7.98 kcal/mol. The net result is only slightly exothermic
(2.96 kcal/mol). Atomic hydrogen is then bound to the platinum
atom, while the hydroxide settles in the oxygen vacancy. Figure
8a shows the energy pathway for the activation of water in one
of the oxygen vacancies surrounding the platinum atom.
The Water-Gas Shift Mechanism on Pt/Ceria(111)
Figure 6. Snapshots from the direct molecular dynamics calculation
of CO impinging on the Pt-ceria surface. (An MD animation consisting
of 148 frames run at a temperature of 300 K for the CO adsorption
and CO2 formation, each frame corresponding to 0.5 fs, is provided as
a Web Enhanced Object.)
Additional water that is dissociated by platinum requires less
energy as seen in Figures 8b and 9.
Calculations done by Rodriguez et al. on oxide clusters on
bulk metal surfaces show that H2O is dissociated on the oxide,
and this is the highest energy barrier (14 kcal/mol) to overcome
in this process.15,21 Theoretical calculations performed by Liu
et al.42 and Gokhale et al.43 on metal surfaces (Cu and Au)
consistently show that the dissociation of water is the highest
energy barrier to overcome. Liu et al. report energy barriers for
bulk metals ranging from 27.21 kcal/mol (1.18 eV) to 35.28
kcal/mol (1.53 eV), depending on the metal studied and face
exposed. Metal nanoparticles still show high-energy barriers,
but are lowered by up to 5.5 kcal/mol (0.24 eV) due to the
higher activity of the lower coordinated surface atoms. Ad-
ditionally, after comparing the results for the metal nanoparticles
on metal ZnO2 and ceria, Liu et al. conclude that ceria must be
directly involved in the WSGR.42 Gokhale et al.43 report an
Figure 7. Adsorption energies for water on different sites on the ceria surface.
J. Phys. Chem. C, Vol. 113, No. 21, 2009 9245
activation energy barrier of 40.59 kcal/mol (1.76 eV) for this
process. When these results are compared to the activation
energy for the dissociation of water on Pt/ceria (7.89 kcal/mol),
the vital role of ceria in this catalyst becomes apparent.
4.4. Formation of H2. The final step of the WGS reaction
is the formation and evolution of molecular hydrogen. As
previously stated, there are two schemes that stand out: (1) a
formate intermediate mechanism proposed by Shido and
Iwasawa10,14 and (2) a direct redox process driven by the oxygen
storage capacity of ceria.13,20 In the subsequent sections we
discuss the routes for the generation of molecular hydrogen for
each of these posited mechanisms.
4.4.1. Direct Formation of H2. Considering an active site
where all active oxygen atoms surrounding the platinum atom
are removed either by CO2 formation and its subsequent removal
or by temperature reduction of the ceria surface, it can be shown
that one water molecule can settle in these vacancies and be
dissociated by platinum, leaving up to three adsorbed hydrogen
atoms on the metal. Figure 8 presents the energy pathways for
the dissociation of additional H2O in these oxygen vacancies.
The resulting hydroxide adsorbates on the ceria surface are
highly reactive; other molecules that impinge on the platinum
atom can disturb these radicals and facilitate the reformation
of water, which still remains stable in the oxygen vacancy. In
addition, water can hydrogen bond to these adsorbates and
weaken their binding energy within the vacancy.
Even when platinum is saturated by three adsorbed hydrogen
atoms, spontaneous H2 generation between the adsorbed atoms
is not observed. Even as the distance between two adsorbed H
atoms is decreased no evolution is evident; the energy of the
system increases rapidly at an almost exponential rate and even
after exceeding the equilibrium bond distance of molecular
hydrogen. Cheng et al. performed a DFT study of H2 dissocia-
tion on Pt6 clusters, and observed that these clusters can be
saturated with hydrogen at a Pt/H ratio of up to 1:4.44
Since it is not apparent that H2 forms from two adsorbed
hydrogen atoms on platinum, an alternate approach was
implemented by introducing an additional water molecule to
observe its interaction with the adsorbed hydrogen. The
optimized structure of Pt-ceria after introducing a fourth water
molecule is shown in Figure 10. As can be seen in the image,
the surface hydroxides can be removed from the oxygen vacancy
by ambient watersforming a H2O-OH complexsalthough they
remain weakly bound in the oxygen vacancy. This complex has
been identified and found to be stable in the gas phase by
9246 J. Phys. Chem. C, Vol. 113, No. 21, 2009 Kinch et al.

Figure 8. (a) Platinum-catalyzed water dissociation in adjacent oxygen vacancy. (b) Platinum-catalyzed second water dissociation in adjacent
oxygen vacancy.

Figure 9. Platinum-catalyzed third water dissociation in final adjacent oxygen vacancy.

Schofield et al.45 Although the formation of this complex is
possible, the energy required for this complex to escape the
surface is 18 kcal/mol. The migration of this complex across
the ceria surface requires 8.10 kcal/mol, but it is possible that
the hydroxide species can easily reoccupy the oxygen vacancy
site. It is also possible for hydroxide species adsorbed on the
ceria surface within oxygen vacancies to migrate along linear
oxygen vacancies. This process requires only 4.9 kcal/mol. With
the removal of the hydroxide, whether by complexation or
migration across vacancies, another water molecule could then
bind in the oxygen vacancy next to the platinumswhich now
has one to three adsorbed hydrogen atomssand react to gene-
rate H2. Once the distance between the water molecule and the
adsorbed hydrogen on platinum reaches approximately the
equilibrium bond distance of molecular hydrogen (0.7 Å),
the formation of H2 is clearly observed. The energy diagram
for the formation of H2 from a hydrogen-saturated platinum is
displayed in Figure 11a; the behavior of this process when there
is a single adsorbed hydrogen on the platinum atom is slightly
different energetically and can be observed in Figure 11b.
4.4.2. Regeneration of the Oxygen Vacancy. The initial and
spontaneous formation of CO2 is highly dependent on the
presence of adjacent reactive oxygen atoms from the ceria
surface. Once these oxygen atoms are depleted, in order for
The Water-Gas Shift Mechanism on Pt/Ceria(111)
Figure 10. Geometrically optimized structure of Pt-ceria with three
dissociated water molecules after the introduction of an additional water
molecule.
the reaction to continue, it is necessary to generate CO2 from
other surface adsorbates. After the initial generation of H2,
hydroxide species remain in the oxygen vacancy site. It is
possible for these hydroxides to react with adsorbed CO on
the platinum atom to form some intermediate species which
could either directly generate CO2, similar to the bifunctional
mechanism that presides over platinum/ruthenium (Pt/Ru)
catalysts for methanol oxidation46-48 or a formate or formic
acid intermiediate.
4.4.3. Generation of a Formate Species. The pathway
proposed by Shido and Iwasawa14 posits that adsorbed CO
reacts with an adjacent adsorbed OH species to generate a
formate intermediate, which then decomposes into CO2,
leaving an adsorbed hydrogen atom. One approach that could
generate formate or formic acid is the reaction of an adsorbed
CO2 with an adjacent water molecule also adsorbed on the
ceria surface. For this scenario, two water molecules were
placed in adjacent oxygen vacancies, one having a hydrogen
atom facing the carbon of the CO2, and another placed in a
Figure 11. Energy diagrams for the formation of H2 from (a) an adsorbed hydrogen atom on H-saturated platinum with an adjacent water molecule
and (b) a single adsorbed hydrogen on platinum with an adjacent water molecule.
J. Phys. Chem. C, Vol. 113, No. 21, 2009 9247
vacancy facing the oxygen of the CO2, and their positions
were optimized. The results of this optimization can be seen
in the initial state of the energy diagram in Figure 12. The
water placed in the vacancy facing the carbon remains
adsorbed in this site, yet the water that was placed in the
vacancy facing the oxygen escapes the defect site and
hydrogen bonds to the CO2. To test the formation of formate,
or any other intermediate, the O-H distance of the adsorbed
water facing the carbon atom was stretched and the activation
energy for this dissociation was mapped. Figure 12 shows
the energy diagram for this process, which does not present
the formation of formate or any other intermediate, but rather
simply presents a path similar to the platinum-catalyzed
dissociation discussed in the previous section, with an
activation energy of 5.69 kcal/mol. It appears that the
presence of the adsorbed CO2 does not affect this dissociation.
To generate formate, it is necessary to involve the interaction
of these two adsorbed species on the platinum atom. To test
the viability of this reaction, only the interatomic distance
between the carbon and the adsorbed hydrogen were constrained.
As the C-H distance shortened, the bond length of the Pt-CO2
complex increased accordingly, until when the C-H distance
approached 1.24 Å. The CO2 desorbed, and subsequently formed
a formate species, which was not bound to the surface. Figure
13 illustrates the energetics for the formation of this formate
species.
The water molecule that formed a hydrogen bond with the
adsorbed CO2 was then applied the same constraints. This
dissociation, which requires 8.76 kcal/mol, results in a
hydroxide species adsorbed in the oxygen vacancy and the
formation of an adsorbed HOCO on platinum. However, this
structure was not stable and reverted back to the initial
structure with the slightest perturbation. From these results
9248 J. Phys. Chem. C, Vol. 113, No. 21, 2009 Kinch et al.

Figure 12. Energy diagram for the dissociation of water in the presence of Pt-CO2 complex.

Figure 13. Energy diagram for the formation of formate from H and CO2 adsobed on platinum.

there appears to be only one viable path for the direct

formation of formate: the interaction of an adsorbed CO2 with
an adjacent water molecule. The resulting formate could then
react with an adjacent water (or even the adsorbed hydroxides
on the surface) to generate H2 and CO2.
As previously stated, it is possible that adsorbed CO can
interact with adsorbed surface hydroxide species to form
either formate or HOCO similar to the bifunctional mecha-
nism proposed by Watanabe et al. to explain the activity of
Pt/Ru catalysts.46-48 To test this route, CO was adsorbed to
the platinum center with no active oxygen surrounding it (as
would be the case of a surface that has been quickly depleted
of these oxygens due to the facile oxidation of CO). This
was done due to the preference of CO to spontaneously form
CO2 as detailed earlier. The distance between the carbon atom
Figure 14. Energy diagram for the formation of HOCO from COads:Pt
of the adsorbed CO and the oxygen atom of the adsorbed and OHads:ceria.
hydroxide was decreased at intervals of a fraction of an
angstrom and the activation energy for the process was
mapped. This simulation resulted in the formation of a stable Flyztani-Stephanopoulos for the “slow formate” process.49
HOCO species adsorbed on the platinum center. Figure 14 From other DRIFTS studies on Pt/CeO2 Meunier, et al. have
presents the energy diagram for this process along with the also proposed that the formate pathway can only account for
structure of the adsorbed HOCO. The energy barrier for the roughly 5% of all CO2 produced.50 The presence of a carboxyl
formation of this species is 9.21 kcal/mol, which is on par species (HOCO) has been shown in this mechanism, but it
with most of the other steps of the mechanism. Simulations does not interact directly with adjacent water to form H2.
performed in the gas phase for the isomerization of HOCO However, with the formation of HOCO via a path similar
into formate present an energy barrier of over 30 kcal/mol. to a bifunctional mechanism, it is possible that platinum could
When the HOCO species is adsorbed on the platinum, the capture the hydrogen, thereby forming CO2,ads and Hads. From
isomerization takes a different route, requiring 20 kcal/mol. the previous calculations, it is clear that CO2 can readily
These results coincide with experimental interpretations of escape the surface, leaving simply Hads. This process then
DRIFTS spectra of Au/Ce(La)O2 catalysts prepared by generates a cyclic path where water can once again approach
The Water-Gas Shift Mechanism on Pt/Ceria(111)
Figure 15. Complete energy diagram for the WSGR considering the redox mechanism.
Figure 16. Complete energy diagram for the WSGR after the depletion of all active oxygen surrounding the platinum atom.
an oxygen vacancy and produce H2. Afterward, CO binds to
the platinum and the formation of another HOCO species
takes place.
4.5. Overview of the Mechanism. Combining the indi-
vidual steps that have been identified for the WGSR on this
catalytic surface, it is evident that the process is highly
exothermic, even with some energy barriers of up to 12 kcal/
mol. Figure 15 presents the complete pathway for the WGSR
on this catalyst following a direct redox process starting with
the spontaneous formation of CO2 (oxidation of CO by lattice
oxygen). After the evolution of CO2, H2O adsorbs in the
newly formed oxygen vacancy (VO), and is catalytically
dissociated by the adjacent platinum (as observed in Figure
8). This process can continue iteratively until all active
oxygen atoms surrounding the platinum atom have been
depleted (Figure 15). Once water has been dissociated, it is
possible to generate molecular hydrogen by removing the
adsorbed surface hydroxide, which can migrate across a linear
oxygen vacancy (4.9 kcal/mol). Another water can then
J. Phys. Chem. C, Vol. 113, No. 21, 2009 9249
adsorb in the newly available oxygen vacancy adjacent to
the platinum and react with the adsorbed hydrogen on the
platinum atom to generate H2; the energetics for this step is
similar to what is illustrated in Figure 11. Alternatively, CO
can sequentially remove all the active oxygen atoms before
any water is able to dissociate (Figure 16) due to the fast
kinetics for this process, as seen in the MD simulations. Once
all active oxygen atoms are depleted via the formation of
CO2, a water molecule can then dissociate in one of the
vacancies and the resulting hydroxide on the surface must
migrate (which requires only 4.9 kcal/mol) to free an oxygen
vacancy for a second water to adsorb and subsequently form
H2. It is important to note that additional CO molecules may
continue to adsorb on the platinum center, which in turn can
react with the hydroxide adsorbed in the oxygen vacancy
and generate a HOCO species. This HOCO species can
isomerize to generate a formate species, which can then be
catalyzed by the platinum atom, resulting in an adsorbed
hydrogen on the platinum and CO2 escaping the surface. The
9250 J. Phys. Chem. C, Vol. 113, No. 21, 2009
process can then continue with the adsorption of a water
molecule that will be catalyzed, react with the adsorbed
hydrogen, and form H2, leaving an adsorbed hydroxide
species in an oxygen vacancy.
5. Conclusions
Density-functional theory calculations were used to model
Pt/ceria(111) catalysts and present a clear mechanistic pathway
of the WGSR on this material. Key active sites for this
mechanism, both cerium and oxygen deficiency sites, have been
successfully identified. The metal catalyst is strongly bound
within the cerium deficiency sitesas would be the case for
doping the materialsalthough surface studies on pure ceria(111)
in high vacuum do not present these defect sites as the most
abundant on the catalyst surface. The initial step in the pathway
is the spontaneous generation of a Pt-CO2 complex. Oxygen
vacancies, whether produced by the formation and evolution
of CO2 or by the reduction of the ceria surface at high
temperature, provide a site for platinum-catalyzed H2O dis-
sociation, which generates the atomic hydrogen crucial for the
generation of H2. The formation of HOCO gives way to the
regeneration of adsorbed hydrogen atoms, which can then react
with ambient water generating additional H2. The process for
the generation of formate, which has been experimentally
observed, has also been identified. The energetics clearly shows
that the process is exothermic; all the steps in the mechanism
have energy barriers in the range of 8 to 12 kcal/mol, and are
heavily dependent on the presence and reactivity of the oxygen
vacancies of ceria surface.
Acknowledgment. The authors gratefully acknowledge fi-
nancial support from the NASA-UPR Center for Nanoscale
Materials under NASA URC Grant No. NCC3-1034.
Supporting Information Available: Figure illustrating the
Pt-CO2 complex structure; figure illustrating the TS of the
platinum-catalyzed dissociation of water; figure illustrating the
TS of the platinum-catalyzed dissociation of a second water;
figure illustrating the TS of the platinum-catalyzed dissociation
of a final water; figure illustrating the TS for the formation of
H2; figure illustrating the TS for the dissociation of HCOO;
figure illustrating the transition state for the formation of HOCO;
figure illustrating the TS for the migration of hydroxide across
a linear oxygen vacancy; structural data files for the Pt/ceria
cluster model, Pt-CO2 complex, dissociated water on Pt/ceria,
and the transition states for each step of the mechanism
presented in the previous figures; and a full Mulliken charge
analysis for the three models presented in Table 1 with the
reference to their structural data files. This material is available
free of charge via the Internet at http://pubs.acs.org.
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