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Perspective
pubs.acs.org/acscatalysis
Increasing Oxide Reducibility: The Role of Metal/Oxide Interfaces in
the Formation of Oxygen Vacancies
Antonio Ruiz Puigdollers, Philomena Schlexer, Sergio Tosoni, and Gianfranco Pacchioni*
Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, via R. Cozzi, 55 I-20125 Milano, Italy
S Supporting Information
*
ABSTRACT: Reducibility is an essential characteristic of oxide catalysts in oxidation
reactions following the Mars−van Krevelen mechanism. A typical descriptor of the
reducibility of an oxide is the cost of formation of an oxygen vacancy, which measures
the tendency of the oxide to lose oxygen or to donate it to an adsorbed species with
consequent change in the surface composition, from MnOm to MnOm−x. The oxide
reducibility, however, can be modified in various ways: for instance, by doping and/or
nanostructuring. In this review we consider an additional aspect, related to the
formation of a metal/oxide interface. This can be realized when small metal
nanoparticles are deposited on the surface of an oxide support or when a
nanostructured oxide, either a nanoparticle or a thin film, is grown on a metal. In the past decade, both theory and experiment
indicate a particularly high reactivity of the oxygen atoms at the boundary region between a metal and an oxide. Oxygen atoms
can be removed from interface sites at much lower cost than in other regions of the surface. This can alter completely the
reactivity of a solid catalyst. In this respect, reducibility of the bulk material may differ completely from that of the metal/oxide
surface. The atomistic study of CO oxidation and water-gas shift reactions are used as examples to provide compelling evidence
that the oxidation occurs at specific interface sites, the actual active sites in the complex catalyst. Combining oxide
nanostructuring with metal/oxide interfaces opens promising perspectives to turn hardly reducible oxides into reactive materials
in oxidation reactions based on the Mars−van Krevelen mechanism.
KEYWORDS: oxide, reducibility, oxygen vacancy, density functional theory, CO oxidation, water-gas shift reaction
the material. Oxides such as SiO2, MgO, Al2O3, and many other
main-group oxides belong to this class. Usually these materials
are characterized by a very large band gap (typically >3 eV)
separating the valence band (VB) from the conduction band
(CB). The excess electrons left on the material when oxygen is
removed in the form of O2 or H2O are trapped in specific sites
(e.g., an oxygen vacancy) and give rise to new defect states in
the band gap.2 This process is energetically very costly, and
therefore these as-prepared materials are highly stoichiometric,
stable, and chemically inert.3 The group of reducible oxides, in
contrast, is characterized by the capability to exchange oxygen
in a relatively easy way. This is because the lowest empty states
available on the material (CB) consist of cation d orbitals which
lie at not overly high energy with respect to the VB. These
oxides usually have semiconductor character, with band gaps <3
eV. The removal of oxygen results in excess electrons that are
redistributed on the cation empty levels, thus changing their
oxidation state from Mn+ to M(n−1)+. Transition-metal oxides
such as TiO2, WO3, NiO, Fe2O3, CeO2, etc., just to mention a
few, belong to this category.4
The difference between nonreducible and reducible oxides is
of fundamental importance for the chemical reactivity of these
materials. A substantial fraction of industrial catalysis is dealing
1. INTRODUCTION: OXIDES IN HETEROGENEOUS
CATALYSIS
Metal oxides are widely used in catalysis, as they represent
essential components of an active heterogeneous catalyst.
Searching the Web of Science for “oxides AND catalysis OR
catalyst” provides about 300000 papers. Due to the huge variety
of compositions and electronic and geometrical structures,
metal oxides offer a very broad spectrum of properties and
behaviors that can result in specific functionalities and chemical
activities. Oxides can be used as “inert” supports of finely
dispersed active metal nanoparticles or directly as catalysts. In
this latter case, the oxide surface must be able to exchange
chemical species with the liquid- or gas-phase surroundings or
to adsorb chemical species and promote dissociation and
regeneration of chemical bonds. The great flexibility of oxide
surfaces stems from the presence on the surface of both Lewis
and Brønsted acid and basic sites, sometimes acting in a
cooperative way.1
Oxides can be divided into two main classes, depending on
their chemical behavior: nonreducible and reducible oxides.
Nonreducible oxides consist of materials that do not easily lose
oxygen, due to the intrinsic resistance of the corresponding
metal cations to change oxidation state. Since oxygen is
formally in a −2 oxidation state, the excess electrons that are
left on the material by removal of a neutral O atom cannot be
accommodated in the cation empty states which lie too high in
energy, contributing to the formation of the conduction band of
© XXXX American Chemical Society
Received: June 12, 2017
Revised: August 15, 2017
Published: August 18, 2017
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1.1. Oxide Reducibility: Effect of Doping. Doping oxides
by heteroatoms and the effect on oxide reducibility have been
studied recently both experimentally and theoretically with the
hope of producing better catalytic materials, in particular for
oxidation reactions.12−14 The chemical, electrical, and optical
properties of an oxide largely depend on the presence and the
concentration of intrinsic or extrinsic defects. Defect engineering is the science that aims at manipulating the nature and the
concentration of defects in a solid, as well as tuning its
properties in a desired manner. For instance, defects can turn a
colorless insulator into a black material with metallic
conductivity or improve the photoactivity of an oxide
semiconductor, making it able to absorb solar light.15 In a
similar way, one can modify the chemistry of an oxide surface
by introducing heteroatoms in the structure.14 One example is
the substitution of a metal cation in an oxide of formula MxOy
with another dopant, D. This results in a direct modification of
the electronic structure of the oxide, with important
consequences on its properties. If the doping heteroatom D
has the same valence of the metal cation M that is replaced,
then the modifications are restricted to size effects or, at most,
to a shift of the frontier orbitals with consequent changes in the
strength of the M−O and D−O bonds. Much more complex is
the situation occurring when the dopant D has a different
valence in comparison to the replaced cation. In this case, the
simple substitution of the cation M results in a charge
imbalance that needs to be compensated by the creation of
other defects in the structure. The number of possibilities is
extremely large, since in principle all atoms of the periodic table
can be used to replace a metal cation in an oxide. The
possibility to explore theoretically with first-principles simulations the effect of doping is thus of great help for the design of
new catalytic materials. This problem has been extensively
investigated and reviewed by Metiu and co-workers in a series
of DFT calculations where several dopants have been
introduced in an oxide matrix.16 Both non-transition-metal
and transition-metal atoms have been tested.16 The general
assumption is that any oxide modification that facilitates the
removal of surface oxygen will facilitate the MvK mechanism in
oxidation reactions. Since oxygen is electrophilic, one can
expect to lower the cost to remove it from the surface by
making the surface more electron deficient. This can be done,
at least in principle, by replacing some of the cations of the host
oxide with cation dopants D having a lower valence. Indeed,
several theoretical studies indicate that the cost to create a VO
center near a low-valence dopant is lower than that on the
undoped surface. It has also been observed that the presence of
a low-valent dopant affects oxygen atoms several sites away
from the dopants, with a relatively long-range effect. However,
the easiest oxygen atom to remove remains that in direct
contact with the dopant D. These conclusions appear to be
rather general, as they have been obtained for several oxides,
such as TiO2, CeO2, ZnO, La2O3, CaO, and NiO.16
The theoretical conclusions are supported by some
experimental evidence that, indeed, doping improves the
catalytic performances, by improving the conversion, the
selectivity, or the surface area of the catalyst.
Oxide anions can also be replaced with direct effects on the
properties of the material and in particular on its reducibility. A
classic example is that of doping TiO2 with nitrogen. Doping
semiconductor oxides with nonmetal atoms has attracted huge
interest in the last 15 years, in the attempt to improve the solar
light absorption and to increase the generation of electron−
with oxidation reactions or oxidative dehydrogenation
processes. In most cases the active catalyst is an oxide, and
the reaction follows a mechanism originally described by Mars
and van Krevelen5 and thus is named after the two authors
(MvK). The key of the MvK mechanism is that the oxide
surface is not just a spectator of the reaction but rather is
directly involved via its most reactive oxygen atoms. An organic
substance can react with these specific sites at the oxide surface
(e.g., oxygen atoms located at low-coordinated sites). A weakly
bound surface O atom is added to the reactant forming the
oxygenated compound, leaving behind an oxygen vacancy on
the surface, hereafter referred to as VO. This results in a MOn−x
compound, with a stoichiometry which is no longer that of the
starting MOn oxide since oxygen has been lost in the process. In
order to be catalytic, the reaction must occur under oxygen
pressure so that molecular oxygen can interact with the surface,
dissociate, and eventually refill the vacancy created in the
oxidative process. In this way, the original stoichiometry and
composition of the catalyst are restored, closing the catalytic
cycle. Using isotopically labeled oxygen, it is possible to prove
that the oxygen atom incorporated in the organic reactant does
not come from the gas phase but rather is directly extracted
from the solid surface.6
Clearly, in this kind of process a very good descriptor of the
reaction is the cost of removing an oxygen atom from the clean
surface of the catalyst. This in fact determines both the kinetics
and the thermodynamics of the overall reaction. This simple
example already shows that the generation of oxygen vacancies
on the surface of an oxide is a very important aspect of its
chemistry. The problem is that the identification and
characterization of oxygen vacancies on oxide surfaces are far
from trivial. In fact, one is dealing with the identification of a
missing atom. For this reason, some years ago some of us
discussed the role of oxygen vacancies on oxide surfaces as “the
invisible agent on oxide surfaces”.7 In recent years several
techniques have been developed to better identify and
characterize these centers. Among others, scanning tunneling
microscopy (STM) and atomic force microscopy (AFM) have
progressively grown in importance for the atomistic characterization of these defects.1,3,8,9 In particular, enormous progress
has been made in the use of AFM which, at variance with STM,
can be employed also on nonconducting supports. Since many
oxides are insulating, in particular the nonreducible ones, this
has opened the perspective to better characterize these centers
on all forms of oxides, reducible and nonreducible. A
combination of AFM and STM measurements can provide
information on the localization and charge state of defects in
oxides.10,11
A better knowledge of the nature and characteristics of anion
vacancies on oxide surfaces is important because it allows the
design of materials with tailored properties, in particular to
prepare oxides that can be more or less reactive and that can
(or cannot) exchange oxygen with adsorbed chemical species.
This has prompted several researchers to explore methods or
procedures to improve the reducibility of a metal oxide. In
general, there are three main conceptual approaches to this
target: (i) doping the material with heteroatoms, (ii) producing
the oxide in form of nanocrystallites or thin films, and (iii)
depositing metal nanoparticles on the surface of an oxide. All of
these procedures are relatively novel, but probably, the
importance of the last method, i.e. the formation of metal/
oxide interfaces, has been fully realized only very recently. This
is also the topic of this perspective article.
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hole pairs.17−20 The N dopant can either replace an O atom in
the lattice or take an interstitial position. In both cases, it
introduces new defect states in the gap, just above the top of
the valence band, thus lowering the energy required to excite an
electron into the CB. An important secondary effect observed
in N-doped titania is that the presence of partially filled N 2p
states deep in the gap favors the formation of oxygen vacancies
and hence the reducibility of the oxide.19,20 The partially filled
low-lying acceptor N 2p orbitals are able to trap the electrons
released when an O atom is removed from the surface. The
excess electrons, instead of being accommodated in the highlying Ti empty 3d states (Ti4+(3d0) + e− → Ti3+(3d1)), close to
the bottom of the CB, fill the low-lying singly occupied N 2p
orbitals, with a large gain in stability. As a consequence, the cost
to create a vacancy in bulk TiO2 drops from 4.63 to 0.27 eV.21
This effect is general and has been observed for many other
oxides, including materials with high band gap and low
reducibility such as ZrO222 and MgO.23 Thus, the presence
of heteroatoms can have unexpected but profound consequences on the stability of the oxide and on its capability
to release oxygen.
While conceptually very attractive, the idea to selectively
dope an oxide material is difficult to realize in practice. The
incorporation of heteroatoms, in fact, requires a specific
chemical synthesis designed for this purpose, and the product
has to be carefully characterized at an atomistic level to make
sure that the preparation results in a doped material. This is far
from simple. With a chemical synthesis, it is hard to know a
priori the kind and concentration of dopants in the structure.
This depends on the external conditions of temperature,
pressure, purity of reactants, annealing, etc. Second, there is a
large number of possible mechanisms for charge compensation,
which opens a wide spectrum of combination of defects. For all
these reasons, while doping with heteroatoms can significantly
help the catalyst reducibility, our present understanding and
control of the doping process for the rational design of new
efficient and practical catalysts are still rudimentary.
1.2. Oxide Reducibility: Effect of Nanostructuring.
Another way to improve oxide reducibility is to control the
morphology and dimensionality of oxide particles. Oxygen ions
at low-coordinated sites of an oxide surface can behave very
differently from the corresponding bulk counterparts. One of
the first oxides considered in this context was MgO.24 MgO is
an ionic oxide with a rock salt structure, a wide band gap, and
very low chemical activity when it is prepared in single-crystal
form. The (001) surface of MgO is notoriously inert and defect
free. CO adsorption on a single crystal of MgO can only be
realized at very low temperatures; in fact, the CO molecule is
weakly bound by van der Waals forces to the surface and easily
desorbs as the temperature exceeds 57 K.25,26 Slightly higher
desorption energies are measured for CO bound to Mg cations
at steps and edges of the surface. Virtually no chemistry occurs
on a single-crystal MgO surface. In contrast, if MgO
nanocrystals are exposed to CO at 60 K, this results in a rich
and complex chemistry, as shown, for instance, by a multitude
of features due to the formation of carbonates and other [O−
CO]n2− species appearing in the infrared spectrum.27−29 This is
due to the much higher reactivity of the low-coordinated O
sites at steps and corners, a result that has been fully
rationalized in terms of the different Madelung potential at
these sites in comparison to the regular MgO (001) surface.30
In a similar way, generation of oxygen vacancies has a very
different energy cost at the surface, where the cost is
prohibitively high, and along steps and corners, where it
decreases significantly.24 Thus, oxide nanostructuring, which
increases the ratio of surface versus bulk atoms, and in
particular of the number of low-coordinated ions on the
surface, can result in deeply modified properties of oxide
materials.
The problem has been recently investigated for the case of
ZrO2. ZrO2 is a highly ionic insulating oxide with a band gap of
∼6 eV;31,32 it is considered a nonreducible oxide like MgO.33
The removal of a O4c ion from bulk has a energy cost of 6.16
eV. This is computed at DFT level with respect to 1/2O2, the
standard reference for O vacancy formation energies. This
reduces to 5.97 eV when a O3c atom is removed from the (101)
surface, a very small change (notice that the values of the VO
formation energy in ZrO2 reported in this review may change
by ±0.1 eV due to the different sizes of the adopted supercells).
Instead, when ZrO2 is nanoscaled down to nanoparticles of 1−
2 nm size, the formation energy of an O vacancy is significantly
lower. For instance, removing a corner O2c atom from the
Zr16O32, Zr40O80, and Zr80O160 nanoparticles has energy costs
of 3.94, 3.70, and 2.26 eV, respectively; 4−5 eV is required to
remove O3c atoms at facets of the nanoparticles.34,35 The O2c
and O3c sites in the nanoparticles become important catalytic
centers in reactions involving oxygen transfer. The possibility of
modifying the reducibility of zirconia may have important
implications in catalysis. For example, prereduced solid catalysts
based on ZrO2 nanoparticles display a better activity in the
transformation of biomass into fuels.36,37 In addition, reduced
ZrO 2−x is shown to be photocatalytically active in H 2
production under solar light while stoichiometric ZrO2 is
inactive.38
A similar response has been found for CeO2. Differently from
zirconia, CeO2 is a reducible oxide, whose catalytic activity is
closely related to the change from +4 to +3 in the oxidation
state of the cerium cations and its capacity to release oxygen
according to the reaction 2CeO2 → Ce2O3 + 1/2O2.39 The
energy required to create a O4c vacancy in bulk CeO2 is 4.73
eV;40 this reduces to 2.25 eV on the (111) surface (O3c).41,42
However, when Ce21O42, Ce40O80, and Ce80O160 nanoparticles
are considered, the formation energies of a corner O2c vacancy
decrease to 1.67, 0.80, and 1.20 eV, respectively.43 The
enhanced reducibility at the nanoscale is observed also when
a metal cluster is deposited on a CeO2 nanoparticle. It has been
demonstrated, both by experiment and by DFT calculations,
that O spillover occurs spontaneously at room temperature
from the supporting CeO2 nanoparticle to a deposited Pt
cluster, while on the extended CeO2 surface this process is
highly endothermic (this topic will be reconsidered below, at
the end of this Perspective).41,42 Thus, CeO2 nanoparticles can
dramatically improve the catalytic activity in comparison to
bulk ceria.
Therefore, as for ZrO2, also for CeO2 the redox behavior
changes dramatically at the nanoscale, where formation of VO
centers becomes easier. A deep understanding of these
phenomena is essential for the use of these oxides in catalysis.44
The phenomenon can be rationalized in two ways. First,
nanoparticles contain a large fraction of undercoordinated
cations such as corners and edges, whose empty d or f states are
stabilized with respect to the bottom of the CB. Thus, empty
Mnd defective electronic states are introduced in the band gap
that lower the energy cost to accommodate the extra charge
associated with an O vacancy.34,35 Consequently, the electron
density of the reduced system tends to be localized in low6495
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ref
title
2016
60
Formation and removal of active oxygen species for the noncatalytic CO oxidation
on Au/TiO2 catalysts
2016
61
How temperature affects the mechanism of CO oxidation on Au/TiO2: a combined
EPR and TAP reactor study of the reactive removal of TiO2 surface lattice oxygen
in Au/TiO2 by CO
2016
62
Mild activation of CeO2-supported gold nanoclusters and insight into the catalytic
behavior in CO oxidation
2016
63
Direct evidence for the participation of oxygen vacancies in the oxidation of CO
over ceria- supported gold catalysts by using operando Raman spectroscopy
2016
64
Catalytic oxidation of carbon monoxide over of gold-supported iron oxide catalyst
2015
65
An atomic-scale view of CO and H2 oxidation on a Pt/Fe3O4 model catalyst
2015
66
High activity of Au/γ-Fe2O3 for CO oxidation: effect of support crystal phase in
catalyst design
2014
67
On the origin of the selectivity in the preferential CO oxidation on Au/TiO2−
Nature of the active oxygen species for H2 oxidation
2013
68
Origin of the high activity of Au/FeOx for low-temperature CO oxidation: Direct
evidence for a redox mechanism
2013
69
Generation of oxygen vacancies at a Au/TiO2 perimeter interface during CO
oxidation detected by in situ electrical conductance measurement
2011
70
Active oxygen on a Au/TiO2 catalyst: Formation, stability, and CO oxidation activity
2011
41
Support nanostructure boosts oxygen transfer to catalytically active platinum
nanoparticles
2010
71
Support effects in the Au-catalyzed CO oxidation−Correlation between activity,
oxygen storage capacity, and support reducibility
exptl methods useda and short description
TAP, TPD
distinction between noncatalytic “irreversible” oxygen species and catalytically active “reversible” oxygen species for the CO
oxidation reaction over Au/TiO2, the latter being titania lattice oxygen
EPR, TAP
removal of TiO2 surface lattice oxygen from a Au/TiO2 catalyst and Ti3+ formation upon exposure to CO
TAP
redox cycle in which CO could reduce the surface of CeO2 to produce oxygen vacancies
active oxygen species present on the surface of the pretreated catalyst react with CO pulses to generate CO2
operando Raman, IR
direct spectroscopic evidence for the participation of oxygen vacancies in the oxidation of CO over ceria-supported gold
FTIR, TEM, XRD
the reducibility of the support is greatly enhanced and shifted to lower temperatures; this shift is due to strong interaction
between the support and Au nanoparticles
STM
CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface
CO-TPR, sequential pulse reaction, in situ Raman spectroscopy
Au/γ-Fe2O3 shows higher activity for CO oxidation than Au/α-Fe2O3
systematic study shows that this higher-redox-property-based higher activity could be extended to γ-Fe2O3-supported Ptgroup metals and to other reactions that follow Mars−Van Krevelen mechanism
TAP
absolute amount of active oxygen for H2 oxidation is identical to that in CO oxidation, and is positioned at the Au/TiO2
interface perimeter.
FTIR, Raman spectroscopy, microcalorimetry, DFT
unambiguous evidence that the surface lattice oxygen of the FeOx support participates directly in the low-temperature CO
oxidation
verification via DFT: oxygen vacancy formation at Pt8−10/FeOx perimeter
in situ ECM
detection of Ti3+ formation under reaction conditions for CO oxidation with O2 over Au/TiO2 catalyst
TAP
correlation between oxygen storage capacity and CO oxidation activity
results allow clear identification of the nature of the active oxygen species and their location on the catalyst surface
RPES and DFT
electron transfer from the Pt nanoparticle to the support and oxygen transfer from ceria to the Pt nanoparticle.
oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt.
TAP
four different metal oxide supported Au catalysts with similar Au loading and Au particle sizes (Au/Al2O3, Au/TiO2, Au/
ZnO, Au/ZrO2) are compared
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year
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Table 1. Overview of Direct Experimental Evidence That the Presence of a Metal Facilitates the Formation of Oxygen Vacancies on an Oxide Surface
year
ref
title
exptl methods useda and short description
oxygen storage capacity and activity for CO oxidation differ significantly for these catalysts and are correlated with each other
and with the reducibility of the respective support material, pointing to a distinct support effect and a direct participation of
the support in the reaction
ACS Catalysis
Table 1. continued
STM, AES, TDS, LEED, DFT
oxygen enrichment of FeO/Pt(111) to FeOx/Pt(111) (with x → 2) and subsequent CO oxidation via the Mars−van
Krevelen mechanism
6497
2010
72
The interplay between structure and CO oxidation catalysis on metal−supported
ultrathin oxide films
2009
73
Reactive oxygen on a Au/TiO2 supported catalyst
2009
74
Kinetic and mechanistic studies of the water-gas shift reaction on Pt/TiO2 catalyst
2007
75
Activation of a Au/CeO2 catalyst for the CO oxidation reaction by surface oxygen
removal/oxygen vacancy formation
2004
76
Nanocrystalline CeO2 increases the activity of Au for CO oxidation by 2 orders of
magnitude
2004
77
Strain-induced formation of arrays of catalytically active sites at the metal-oxide
interface
STM, DFT
annealing under vacuum leads to the formation of a CeO2−x phase, as indicated by the transformation of Ce4+ into Ce3+
species
metal−oxide interface creates preferential sites for the reduction of the ceria
2004
78
CO spillover and oxidation on Pt/TiO2
TPD
observation of CO2 production upon exposure of the Pt/TiO2 catalyst to CO, even without supply of O2 in the gas mixture
TAP
both the oxygen storage capacity and the activity for CO oxidation scale linearly with the Au/TiO2 perimeter length
SSITKA, DRIFTS
redox mechanism demonstrated as the prevailing mechanism on a Pt/TiO2 catalyst, where labile oxygen and oxygen
vacancies of TiO2 near the metal−support interface can participate in the reaction path of the water-gas shift reaction
TAP
first experimental verification of a CO oxidation rate enhancement by oxygen surface vacancies on a realistic oxide-supported
Au catalyst
TEM, IR, XPS, GC
formation of Ce3+ under exposure of the catalyst to CO at 60 °C
a
Acronyms: AES = Auger electron spectroscopy, CO-TPR = temperature-programmed reduction with CO, DFT = density functional theory, DRIFTS = diffuse reflectance infrared Fourier transform
spectroscopy, ECM = electrical conductance measurement, EPR = electron paramagnetic resonance, (FT)IR = (Fourier transform) infrared spectroscopy, GC = gas chromatography, LEED = low-energy
electron diffraction, RPES = resonant photoelectron spectroscopy, SSITKA = steady-state isotopic transient kinetic analysis, STM = scanning tunneling microscopy, TAP = temporal analysis of products,
TDS = thermal desorption spectroscopy, TPD = temperature-programmed desorption, XPS = X-ray photoelectron spectroscopy, XRD = X-ray diffraction.
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coordinated Zr3+ and Ce3+ centers that, trapping a single
electron, become magnetic and can be detected by electron
paramagnetic resonance (EPR).34,35,40,33,45,46 The second
aspect is the increased structural flexibility. Nanoparticles and
in general nanostructures are more flexible than extended
surfaces or the bulk material.47 Atomic relaxation around the
created O vacancy occurs at much lower cost, thus contributing
to stabilize the defect.34,35,45 In short, both the size and
morphology of oxide supports are very important in
determining the catalytic processes.
1.3. Oxide Reducibility: Effect of Metal/Oxide Interface. The interface between an oxide surface and a metal is of
crucial importance in several modern technologies. Metal/oxide
interfaces find application in microelectronic devices to create
Schottky contacts and metal/oxide resistive random access
memories, in electrochemistry for contact electrodes, in
corrosion protection as oxide films to form a protective barrier
against the oxidation of the underlying metal, in catalysis for
supported metal nanoparticles, etc. Despite the technological
importance of metal/oxide interfaces, our knowledge of the
interface between a metal and an oxide is still very
unsatisfactory. The reason is that the interface is difficult to
access experimentally with the typical techniques available in
surface science and is also difficult to describe theoretically, as it
involves two materials with completely different properties: a
conductive metal on one side and an insulator or semiconductor phase on the other. DFT has problems in treating on
an equal footing these two classes of materials: methods that
work very well for one category (e.g., standard GGA functionals
for metals) usually perform poorly for the second component
(the insulating phase); vice versa, self-interaction corrected
functionals work well for semiconductors and insulators but
may fail when it comes to describing a metallic phase.48
Despite these problems, it is becoming increasingly clear that
the contact region between an oxide and a metal is chemically
very active. One aspect of key importance is the occurrence of a
direct charge transfer between the metal and the oxide.49
Metals with low work function deposited on oxides with high
electron affinity can induce the reduction of the oxide by direct
electron transfer. The oxide surface becomes electron rich and
thus changes its chemical properties. Of course, oxygen
exchange can be affected by this phenomenon as well, although
this has not been studied in detail until very recently.
The interface between a metal and an oxide is strongly
affected by the presence of oxygen vacancies. So far, most of the
attention has been dedicated to the fact that vacancies, when
present, play an important role in stabilizing deposited metal
nanoparticles and eventually in tuning their chemical
activity.50−56 Theory has shown that metal atoms and clusters
bind much more strongly to these defect sites. New
experiments have been designed to nucleate clusters under
controlled conditions or even to deposit via soft-landing
techniques mass-selected clusters generated in the gas phase.57
These experiments offer a unique opportunity to study the
cluster reactivity as a function of the particle size and of the
deposition site,56,58,59 opening new perspectives for the
understanding of the basic principles of catalysis by small
metal particles. For very small cluster sizes, in the nanometer
size regime, the strong interaction with a surface defect may
lead to a modification of the chemical activity of the
particle.50,51,56 The literature about the role of surface oxygen
vacancies in promoting nucleation and growth of deposited
metal atoms and clusters is very abundant and covers several
oxides and virtually every metal.
What has attracted much less attention, however, is the fact
that by depositing a metal cluster on an oxide surface one may
also favor the formation of oxygen vacancies. The idea is that
the metal/oxide interface, in particular the periphery between a
metal nanoparticle and the oxide support, are regions where the
oxide reactivity is significantly enhanced and where oxygen can
be easily removed. This is also the main topic of this review. By
considering a number of examples, from both theory and
experiment, we will demonstrate that the reducibility of an
oxide can be deeply modified by creating contacts between
metals and oxide surfaces. Table 1 reports a noncomprehensive
overview of direct experimental evidence that the presence of a
metal facilitates the formation of oxygen vacancies on oxide
surfaces.60−78 This will be further commented upon in the next
sections.
2. METAL/OXIDE INTERFACE AND OXIDE
REDUCIBILITY
2.1. Theory of Metal Clusters on Oxide Surfaces: VO
Formation Energies. Likely, the first indication that oxygen
vacancies can form at lower cost when a metal is in contact with
an oxide surface came from theory. About 20 years ago it
became possible, thanks to continuous advances in computer
power and to the development of accurate functionals for DFT
calculations, to study systems of increasing complexity,
including cases of small metal clusters supported on oxide
surfaces or even of extended metal/oxide interfaces. As we
mentioned above, it was immediately realized that, in the
presence of surface oxygen vacancies, the adhesion energy of
the metal increases, and consequently the tendency of the
supported particles to diffuse and aggregate decreases.
However, it was only about 15 years ago that it was reported
explicitly that the role of the metal could also be that to reduce
the cost to create an oxygen vacancy, thus favoring the
reduction of the oxide. A DFT study of the Pd/MgO interface
reported that the formation energy of VO at the Pd/MgO
interface, 8.4 eV, is about 1 eV smaller than that on the regular
surface, where it is 9.5 eV (these values are referenced to a gasphase O atom).79,80 The difference is modest but relevant, and
the effect was attributed to the stabilizing effect of the metal
when the vacancy is formed.
The topic was then reconsidered shortly after by Honkala
and Hakkinen, who found on studying Au clusters deposited on
the MgO(001) surface that the formation of an interfacial VO
defect center is thermodynamically more favorable than the
formation of a surface vacancy.81 These studies, however, were
dealing with a nonreducible oxide, MgO, and were not directly
supported by experimental evidence. Furthermore, even a
reduction of about 1 eV out of formation energy close to 10 eV
is not going to significantly change the landscape of the MgO
surface chemistry. Thus, it is not surprising that these findings
did not attract particular attention.
Things changed shortly thereafter, when it started to emerge
that the role of supported metal nanoparticles could be
significant in the context of the reducibility of semiconductor
oxides. The effect of metal clusters on the reducibility of TiO2
was explicitly discussed in a DFT study by Cheettu and
Heyden.82 They used both cluster and slab models with
standard (PBE) and hybrid (PBE0) functionals to investigate
the influence of Au and Pd dimers and trimers on the cost to
remove an O atom from the TiO2(110) rutile surface. The
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Figure 1. (a) Oxygen storage capacity of the Au/TiO2 catalysts in multipulse experiments at 80 °C after different calcination pretreatments (400,
500, 600, and 700 °C). (b) Relative conversion of CO at 80 °C of the same catalysts during simultaneous CO/Ar and O2/Ar pulses. Reprinted with
permission from ref 73. Copyright 2009 Elsevier Ltd.
Figure 2. Loss of oxygen referenced to the oxygen content after oxidative pretreatment (C400), after reduction by CO/Ar pulses (CO(1)), after
reoxidation by O2 /Ar pulses (O2(1)), and after second sequences of CO (CO(2)) and O2 (O2(2)) pulses at different temperatures: 80 °C (○); 160
°C (◇); 240 °C (△); 400 °C (□). Reprinted with permission from ref 90. Copyright 2014 American Chemical Society.
calculations showed a substantial effect. The formation energy
of a VO center on rutile was found to be 3.75 eV (PBE) or 4.37
eV (PBE0); these values are slightly reduced in the presence of
Au clusters and strongly reduced by the presence of Pt clusters.
In particular, a Pt dimer lowers the formation energy of the
vacancy to 2.12 eV (PBE) or 2.10 eV (PBE0), i.e. by about
1.6−2.3 eV, depending on the method adopted.
Further evidence came from some key experiments that
showed unambiguously the role of lattice oxygen in oxidation
reactions catalyzed by supported metal particles. We are
referring in particular to the case of CO oxidation over gold
particles supported on TiO2.
2.2. CO Oxidation on Au/TiO2. Probably, CO oxidation
over supported gold nanoparticles is one of the most studied
reactions in catalysis. Searching for “CO oxidation” in the ISI
WoS gives 14000 papers, which are reduced to about 1000 if
the search is restricted to “CO oxidation AND Au/TiO2”.
Despite the large number of studies, the mechanism of CO
oxidation on Au/TiO2 is still a matter of debate. Several
mechanisms have been proposed, but clearly different reaction
paths are followed at different temperatures. In the so-called
low-temperature regime, it is assumed that both CO and O2
molecules from the gas phase adsorb on the metal particle, with
O2 bound at the interface between gold and the oxide
support.83−87 The bond of the O2 molecule is weakened by the
interaction with the solid surface. CO can react and bind an O
atom of the activated O2 molecule to form CO2 and an
adsorbed O adatom, overcoming a low barrier. A second CO
molecule binds to the Au catalyst and reacts with the O adatom
to form CO2. There are several pieces of evidence that this is
the mechanism, and it has been shown that an excess of
negative charge on the Au cluster, due for instance to the
presence of an oxygen vacancy, can result in the formation of
the more reactive superoxo O2− species, which is paramagnetic
and has a characteristic EPR signal.83 This mechanism is of
Langmuir−Hinshelwood (LH) type and requires that both CO
and O2 can stick to the surface, diffuse, and react while bound
to the catalyst. However, O2 binds only weakly to Au: it desorbs
from Au surfaces for T > 170 K.88 Thus, this mechanism cannot
work at room or higher temperatures since there is no adsorbed
oxygen under these conditions.
This prompted some groups to propose a different
mechanism, of MvK type, where the active species is the
titania lattice oxygen. On the basis of kinetic measurements and
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another experiment, Widmann et al.61 detected the formation
of Ti3+ species under exposure of a Au/TiO2 catalyst to CO in a
combined EPR and TAP reactor study. They showed that CO
oxidation via the Au-assisted MvK mechanism takes readily
place at 120 °C and is still possible at −20 °C, although with a
slower kinetics. The formation of oxygen vacancies via
abstraction by CO is then completely inhibited at −90 °C.
Thus, at low temperatures, an LH type mechanism is proposed
to be the dominant reaction pathway.
The feasibility of the MvK mechanism for CO oxidation over
Au/TiO2 has been studied and also confirmed computationally.
Li et al.91 performed Born−Oppenheimer molecular dynamics
(BOMD) simulations of the CO oxidation reaction over Au16
and Au18 clusters supported on the titania rutile (110) surface.
They found that CO adsorbed at the Au16/TiO2 perimeter
prefers the removal of a titania lattice oxygen instead of an O2
molecule adsorbed at a close-by dual perimeter site, as shown in
Figure 3.
temporal analysis of products (TAP) reactor measurements,
Kotobuki et al.73 demonstrated that both the oxygen storage
capacity (OSC) of Au/TiO2 catalysts and the catalytic activity
for CO oxidation scale linearly with the Au/TiO2 perimeter
length. OSC is the amount of O2 that can be stored on the
catalyst surface. The Au/TiO2 catalysts were prepared with
equal Au loading but different Au mean diameters, obtained by
different calcination pretreatments at 400, 500, 600, and 700 °C
(denoted as C400, C500, C600, and C700, respectively). The
treatments resulted in Au particle mean diameters of 3.5 ± 0.9,
4.8 ± 1.0, 6.7 ± 1.5, and 11.6 ± 3.1 nm. Exposing the catalysts
to CO pulses at 80 °C results in CO2 formation, although no
O2 was supplied in the gas mixture, indicating an effective
reduction of the catalyst. Upon exposure of the reduced catalyst
to O2 pulses (still at 80 °C), a part of the oxygen remained on
the catalyst, indicating its reoxidation. The reduction and the
reoxidation are completely reversible, except for the first
exposure to CO.
The OSCs of the different catalyst samples are shown in
Figure 1a. A linear dependence of the OSC on the Au/TiO2
perimeter length can be observed. Figure 1b shows the relative
CO conversion under steady-state conditions of the catalysts
under simultaneous exposure to CO and O2. Again, a roughly
linear dependence of the relative CO conversion and the Au/
TiO2 perimeter length can be observed. These findings clearly
indicate that the Au/TiO2 perimeter sites are the active sites
under the reaction conditions applied. However, no further
specification of the exact nature of the oxygen species stored at
the Au/TiO2 perimeter can be deduced from these experiments.73
Widmann et al.89 compared the OSCs and catalytic activities
of Au nanoparticles supported on different oxides under
identical conditions and found that they differ significantly for
different catalyst types. Both the OSC and the catalytic activity
correlate with the oxide reducibility, indicating a direct
participation of the support in the reaction. Widmann et al.70
also established the nature of the active oxygen species on the
basis of multipulse measurements performed in a TAP reactor
at temperatures between 80 and 400 °C. Upon sequential
exposure to CO and O2 pulses, they observed the reversible
removal and replenishment of oxygen species of the catalyst,
whereby the amount of oxygen removed from the catalyst
increased with increasing temperature, as shown in Figure 2.
The temperature dependence of the amount of oxygen
removed from the catalyst indicates that the catalyst reduction
is an activated process (Figure 2). The high stability of the
active oxygen species speaks against molecularly adsorbed
oxygen. Furthermore, the fact that the oxygen removed
increases with the temperature, but not the total amount of
active oxygen after reoxidation, is a clear indicator that the
active oxygen is lattice oxygen from the supporting TiO2. This
implies that CO abstracts a TiO2 lattice oxygen at the Au/TiO2
perimeter with creation of an oxygen vacancy, which is then
refilled in the subsequent exposure to O2. This reaction
pathway corresponds to a Au-assisted MvK mechanism.90 Note
that no reaction occurs without the Au nanoparticles.
Further evidence for the formation of oxygen vacancies were
provided by Maeda et al.,69 who performed in situ electrical
conductance measurements showing a sharp increase of the
electrical conductance of the Au/TiO2 catalyst upon exposure
to the CO/O2 reactant mixture. The method is highly sensitive
toward detection of oxygen vacancies in TiO2, as these centers
are responsible for the generation of conducting electrons. In
Figure 3. Reaction pathway for CO oxidation at Au16/TiO2 interface,
following the Au-assisted MvK mechanism. Ead (eV) represents
adsorption energy and ETS (eV) represents the reaction barrier for the
generation and refilling of the oxygen vacancy. Negative and positive
values indicate exothermic and endothermic processes, respectively.
Reprinted with permission from ref 91. Copyright 2014 American
Chemical Society.
The activation barrier for the oxygen removal from the titania
lattice was as small as 0.19 eV in this case (Figure 3). The
replenishment of the oxygen vacancy by O2 exhibited a barrier
of 0.35 eV. On the other hand, the alternative LH mechanism
including the formation of a OCOO species exhibited an
activation barrier of 0.62 eV. For the Au18 cluster, the reaction
barriers for both reaction mechanisms were quite low as well
(below 0.5 eV). In this case, however, the LH mechanism
exhibited lower barriers than the MvK mechanism. Here, the
LH mechanism was also the observed reaction pathway in the
BOMD simulations. This difference between Au16 and the Au18
clusters was attributed to the larger fluxionality of Au16.92
Furthermore, a relation between the O2 binding strength at the
Au/TiO2 interface and the energy required to remove a lattice
oxygen from the support has been proposed: the stronger the
O2 molecules bind to the dual perimeter sites, the easier is to
extract the lattice oxygen.
In a DFT+U study employing a Au rod supported on the
titania rutile (110) surface, Duan et al.93 obtained a similar
picture considering the cost to create an oxygen vacancy upon
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Figure 4. (a) Standard Gibbs free energy change for the formation of an oxygen vacancy ΔG°(VO) for different systems and VO positions. (b) ΔG°
for the formation of different intermediates on the model systems. OInt and OPeri show ΔG° for CO2 formation on Au10/TiO2 using interface and
perimeter oxygen atoms, respectively. OPeri-Au3/TiO2 and clean TiO2 show CO oxidation using OPeri of Au3/TiO2 and lattice oxygen of clean TiO2
surface, respectively. O2 adsorption and the second cycle of MvK represent the adsorption of O2 on the perimeter vacancy and CO oxidation by
atomic oxygen on the Au10/TiO2 catalyst, respectively. Reprinted with permission from (a) ref 94, copyright 2015 Royal Society of Chemistry, and
(b) ref 95, copyright 2016 Elsevier Ltd.
Although the findings of the various computational studies
differ in their details, there are some recurring motifs, such as
the role of the Au particles in stabilizing the oxygen vacancies
by electron capture and an intimate interaction of a Au atom
with the vacancy. The latter aspect is clearly related to the
particle fluxionality, since rigid clusters are less capable of
establishing a close interaction with the vacancy. Molecular and
atomic oxygen at dual Au/TiO2 perimeter sites enhance the
electron affinity of the supported Au clusters and therefore
increase their ability to stabilize oxygen vacancies by capturing
excess charge. The adsorption energies reported for molecular
O2 adsorption at the cluster/surface perimeter are strongly
dependent on the oxidation state of the ions in this region.
Under highly oxidizing conditions, O2 molecules adsorb only
weakly at the Au/TiO2 perimeter and should therefore desorb
at high temperatures. Most important, the computational
studies demonstrate the feasibility of CO oxidation with the
titania lattice oxygen thanks to relatively small activation
barriers. Thus, the experimental findings that the Au-assisted
MvK mechanism is the dominating reaction pathway under dry
reaction conditions and at “elevated” temperatures (T > 80 °C)
is clearly supported by theoretical studies.
2.3. CO Oxidation: Not Only Au on TiO2. In this section,
we discuss other cases of CO oxidation reactions with direct
involvement of lattice oxygen at the metal/oxide interface,
beyond Au/TiO2 . Diebold, Parkinson, and co-workers
performed an STM study65 of a catalyst consisting of Pt on
Fe3O4 in CO and H2 oxidation. Pt nanoclusters of size from
one to six metal atoms were obtained from deposition of Pt
atoms on a Fe3O4(001) surface. Exposure of the sample to CO,
O2, and H2 at room temperature did not produce any
observable change in the STM images of the supported species.
However, CO exposure at 550 K resulted in large holes
covering about 3.7% of the surface and associated with at least
one Pt cluster (Figure 5).
None of the morphological changes observed occurs in the
absence of the Pt clusters, and DFT+U calculations provided
evidence that the O atoms near the Pt/oxide interface are easier
to remove. When the Pt/Fe3O4 model catalyst is exposed to O2
formation of atomically adsorbed oxygen at the Au/TiO2
interface. They found a barrier of only 0.24 eV for CO
oxidation via the LH mechanism, whereas the removal of lattice
oxygen by CO was found to exhibit a barrier of 0.55 eV. The
role of oxygen adatoms at the Au/TiO2 interface is thereby to
act as an electron acceptor, retrieving the excess electrons
associated with the formation of an oxygen vacancy.
In two sequential DFT+U studies, Saqlain et al.94,95
investigated the thermal activation of lattice oxygen on the
TiO2 anatase (001) surface with and without Au clusters. They
observed a clear decrease in the oxygen vacancy formation free
energy, ΔG°(VO), at Au10/TiO2 perimeter sites with respect to
the Au-free titania surface (Figure 4a). They also established
that, at these Au10/TiO2 sites, ΔG°(VO) becomes negative for
T > 230 °C, the temperature at which the formation of oxygen
vacancies becomes exergonic (Figure 4a). Then, they
investigated CO oxidation with a titania lattice oxygen via the
MvK mechanism. In agreement with the trend observed for the
oxygen vacancy formation energies (Figure 4a), CO oxidation
with a lattice oxygen at the Au10/TiO2 perimeter sites is
favorable even at very low temperatures (Figure 4b). The
activation barrier for the removal of lattice oxygen is 0.55 eV,
according to this study. The barriers involved in the reoxidation
process were below 0.4 eV. The observed difference between
the Au3 and the Au10 clusters in stabilizing the oxygen vacancies
has been explained by the fact that Au10 can capture more
electron density from the vacancy.
In a study based on ab initio molecular dynamics simulations
(AIMD) and microkinetic modeling, Wang et al.96 proposed a
single gold atom MvK and hybrid single atom/nanoparticle
mechanisms at the interface between a Au20 cluster and the
titania rutile (110) surface. In this mechanism, a stable Oad−
Au+ species forms and adsorbs CO, resulting in an Oad−Au−
CO species in proximity to the Au particle. Under highly
oxidizing conditions, the Au20/TiO2 perimeter can be oxidized
via formation of oxygen adatoms at dual perimeter sites. This
facilitates the abstraction of a vicinal lattice oxygen by CO (of
the Oad−Au−CO species).
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substantial lowering to 2.13 eV near the cluster, while the cost
for the bare surface is of 3.04 eV (computed with respect to 1/
2O2).99
Quite interestingly, the CO oxidation reaction can also occur
via a MvK mechanism on a nonreducible oxide such as ZrO2,
provided that gold nanoparticles are deposited on it.100 Using a
DFT approach, it has been found that Au/ZrO2 can catalyze
the reaction in three subsequent steps. First, CO reacts with a
lattice oxygen at the Au/ZrO2 interface, forming CO2 with an
energy barrier of 0.79 eV and a reaction energy of −0.83 eV
(Figure 6). Then, in a second step an O2 molecule dissociates at
the interface with an energy barrier of 0.33 eV, and the vacancy
is refilled with a similar barrier (ΔETS = 0.43 eV). Finally, in the
last step a second CO molecule reacts with the O adatom
forming CO2 with a barrier of 0.81 eV and an energy gain of
−0.69 eV. The key aspect is that the formation energy of a
surface O vacancy decreases from 5.79 eV without gold to 2.43
eV in the presence of gold.
Before the conclustion of this section, it is useful to mention
that the generation of O vacancies at the metal/oxide interface
can also lead to other reactions. In a careful theoretical/
experimental study on Au/CeO0.62Zr0.38O2 catalyst in CO
oxidation, it has been shown that the presence of CO2 in the
gas phase retards the CO oxidation process. This is due to the
fact that CO2 interacts with the O vacancies at the cluster/
surface boundary, forming stable carbonates and thus hindering
the replenishment of the vacancy by molecular oxygen.101 This
is a nice underreaction demonstration of the metal-assisted
MvK mechanism for CO oxidation.
2.4. Water-Gas Shift Reaction. Another process affected
by the easier formation of oxygen vacancies near the interface
with supported metal particles is the water-gas shift (WGS)
reaction:
Figure 5. (a) STM images acquired following exposure of the Pt/
Fe3O4(001) model catalyst to 1 × 10−7 mbar of CO at 550 K.
Approximately 50% of the Pt clusters sit at the edge of or inside
monolayer holes in the Fe3O4(001) terrace. (b) Illustration showing
how CO extracts lattice O atoms from the cluster perimeter and how
CO2 desorbs from the surface. Undercoordinated Fe atoms diffuse into
the Fe3O4 bulk. Reprinted with permission from ref 65. Copyright
2015 John Wiley and Sons.
at 550 K, the Pt clusters catalyze the growth of a new
stoichiometric Fe3O4(001) surface. The work65 provides clear
evidence that the reduction and reoxidation of the Fe3O4
support are catalyzed by the Pt clusters.
The role of the metal/oxide interface in promoting CO
oxidation has also been confirmed by recently reported DFT
calculations on Au/CeO2. Kim and Henkelman considered the
reaction on Au12 nanoclusters supported on the regular and
stepped CeO 2(111) surface, finding an MvK type of
mechanism mediated by lattice oxygen;97 the same role for
the CeO2 lattice oxygen was found experimentally by Li et al. at
the boundaries of thiolate-capped Au144 clusters.98 Hoh et al.
studied the effect of Au nanoparticles supported on a
Fe2O3(001) surface on the VO formation energy, showing a
CO + H 2O → CO2 + H 2
The reaction has ΔH°298 K = −41.1 kJ/mol but is kinetically
hindered. The general assumption is that there is a direct
involvement of the oxide support in the reaction, and in
particular two mechanisms have been proposed: (a) a redox
mechanism,102,103 where CO adsorbed on the metal phase is
oxidized to CO2 by labile oxygen of the support and then the
support is reoxidized by water, with formation of H2, and (b)
an associative mechanism,104 which proceeds via the interaction
Figure 6. (top) Reaction energy profile and (bottom) side and top views of the structures of the CO oxidation reaction with a surface Olatt. The Olatt
abstracted is indicated by a green filled circle and the O vacancy by a dotted circle. Zr is represented by blue atoms, O by red atoms, Au by golden
atoms, and C by brown atoms. Reprinted with permission from ref 100. Copyright 2017 John Wiley and Sons.
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However, Pt clusters of various size deposited on the rutile
TiO2(110) surface decrease the VO formation energy. The
effect is larger for the smaller Pt clusters, in agreement with
previous literature results from the same group.82 For the larger
Pt clusters (e.g., Pt8), this converges to a decrease in the VO
formation energy by about 0.7−0.9 eV. On the basis of the
DFT results, a thermodynamic analysis has been performed as a
function of the oxygen partial pressure and temperature.
Entropy effects have also been considered so that the results are
based on Gibbs free energies, showing that the presence of Pt
clusters promotes the reducibility of the titania surface and the
formation of oxygen vacancies at the Pt/TiO2 interface and that
the process becomes thermodynamically favorable under
reducing conditions (Figure 8).106 This is consistent with (a)
EPR measurements which indicate that Ti3+ ions are formed
when Pt/TiO2 is reduced at 250 °C109 and (b) temperatureprogrammed desorption experiments showing that Pt/TiO2
exposed to CO is reduced at low temperatures.110
The critical role of oxygen vacancies at the interface between
a Pt8 cluster and TiO2 in the WGS reaction has been further
demonstrated in a microkinetic model determined from firstprinciples calculations by the same group.107 Different routes
have been considered for the WGS reaction at Pt/TiO2 (Figure
9). The computed rates suggest that the CO-promoted redox
pathway dominates in the lower temperature range of 473−623
K, while the classical redox pathway becomes dominant for
higher temperatures (>623 K). According to this study, the
oxygen vacancies formed during the reaction should not be too
stable and should also be able to activate H2O in order to
complete the reaction with release of molecular hydrogen.
of adsorbed CO with the hydroxyl groups of the oxide surface
leading to a formate intermediate, which then decomposes to
CO2 and H2.
In a kinetic and mechanistic study of the reaction over a Pt/
TiO2 catalyst, Kalamaras et al. found,105 on the basis of various
transient 18O-isotopic exchange experiments, that the WGS
reaction on the Pt/TiO2 catalyst occurs via a redox mechanism,
where CO adsorbs on Pt, diffuses toward the metal−support
interface, and then reacts with labile oxygen of the titania
support at the metal−support interface to form CO2 (Figure 7).
Figure 7. Proposed elementary reaction steps of the WGS reaction
over 0.5 wt % Pt/TiO2 catalyst after 16O/18O exchange followed by a
C16O/H216O WGS reaction (T = 200 °C). Reprinted with permission
from ref 105. Copyright 2006 Elsevier Ltd.
The reaction has been studied in great detail in an extensive
ab initio thermodynamic study by Ammal and Heyden106,107
and recently extended to Pt/CeO2 catalysts.108 It has been
observed that the computed energy to remove an oxygen atom
from the surface of TiO2, between 3 and 5 eV depending on the
method used, is too high in comparison to the small apparent
activation barrier (0.3−0.5 eV) of the catalyzed WGS reaction.
Figure 8. (a) Gibbs free energy (ΔG) for the formation of an oxygen vacancy on the TiO2 surface (TiO2 → TiO2−x + 1/2O2) versus oxygen
chemical potential, Δμ(O). (b, c) Gibbs free energy (ΔG) for the formation of an oxygen vacancy on the TiO2 surface under reducing conditions
(TiO2 + CO/H2 → TiO2−x + CO2/H2O) versus the difference in chemical potentials Δμ(CO2) − Δμ(CO) and Δμ(H2O) − Δμ(H2), respectively.
Reprinted with permission from ref 106. Copyright 2011 American Chemical Society.
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Figure 9. Proposed reaction pathways for the WGS at the TPB that involve surface oxygen atoms: (a) classical redox pathway and (b) associative
pathway with redox regeneration. Reprinted with permission from ref 107. Copyright 2013 Elsevier Ltd.
Figure 10. Top views of (a) Ru10/MgO, (b) Ru10/BaO, (c) Ru10/SiO2, (d) Ru10/ZrO2, (e) Ru10/TiO2, and (f) Aurod/TiO2. The metal−metal bonds
of the Ru10 cluster are shown in green (a−e), and those of the Aurod are shown in yellow (f). VOn labels refer to the sites where oxygen vacancies are
created. The images represent the actual size of the adopted surpercell.
footing VO formation energies as a function of a few
parameters: oxide, supported metal, VO distance from the
metal nanoparticle, etc. In this respect, it is not the absolute
value of Ef(VO) that matters but rather its changes. We have
considered nonreducible oxides such as MgO, BaO, and SiO2, a
scarcely reducible oxide such as ZrO2, and a reducible oxide,
TiO2. In all cases, the deposition of a Ru10 cluster has been
considered. The choice of Ru is due to the fact that this metal
has been used to improve the performances of oxide catalysts in
biomass conversion,114,115 a reaction recently studied in detail
by our group.116,117 The effect of the metal and of the particle
size has been addressed for the TiO2 anatase (101) surface
comparing a Ru10 cluster with a Au periodic nanorod.
The most stable surface of each oxide is adopted, namely
(100) in the case of MgO and BaO, while for zirconia and
titania we studied the (101) surfaces of the tetragonal and
anatase polymorphs, respectively. In the case of silica, we focus
on the reconstructed α-quartz (001) surface.118 In all cases, we
recur to the PBE(+U)+D2′ approach to describe the electronic
structures, where the two main drawbacks of GGA functionals
(the underestimation of the oxide band gap due to the selfinteraction error and the underestimation of long-range
dispersive forces) are corrected respectively by adding a
Hubbard U parameter to the d orbitals of the transition
metals119,120 and ad hoc semiempirical C6 coefficients.121 A
complete description of the computational scheme is reported
in the Supporting Information. A top view of the surfaces and
considered VO sites is shown in Figure 10.
For all systems, the effect of the supported metal cluster on
the VO formation energy is studied as a function of the distance
Similar experiments have been performed on ceria-supported
metals. Au/CeO2111,112 and Cu/CeO2111,113 catalysts were
reduced under exposure to the WGS (CO + H2O) reaction
mixture, while clean CeO2 remained stoichiometric. The CO
molecule is adsorbed on the metal particle and then is desorbed
as CO2 by either detaching a lattice O or by forming carbonateor formate-like surface species that in turn decompose into
CO2. The O vacancy left on the surface once the CO2 is formed
is stabilized by the metal particle, and it is reoxidized by
dissociating the incoming H2O molecules and releasing H2,
which is the rate-limiting step in the WGS reaction. Thus, the
presence of the metal particles is the key to catalyzing the WGS
process.
3. VACANCY FORMATION ENERGIES AT
METAL/OXIDE INTERFACE
From the above discussion it emerges that the formation energy
of an oxygen vacancy is an excellent descriptor of the reactivity
of an oxide surface in oxidation reactions. However, the energy
costs to create a vacancy can be very different in the bulk or on
the surface of an oxide and can change significantly at the
metal/oxide interface. This raises some questions. How
important is the decrease in the VO formation energy at the
periphery of a supported metal particle? Does this depend on
the supported metal? Is it related to the size of the supported
nanoparticle? Does it affect only the O atoms at direct contact
with the nanoparticle or also the second or more distant
neighbors? In order to partially answer these questions, we have
performed some novel DFT calculations. The adoption of the
same computational setup allows us to compare on an equal
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case, the creation of a vacancy in two nonequivalent peripheral
O2c sites (VO2 and VO3) leads to rather different results. For
VO2, ΔEf is −1.75 eV, while for VO3 it is only −0.22 eV. This
strong site dependence can be explained by the remarkable
distortion that the Ru10 particle undergoes upon adsorption on
anatase (101).122 In the case of VO2, the closest Ru atom is
undercoordinated and is prone to bind strongly to the oxygen
vacancy, while in the case of VO3, the closest Ru atoms exhibit
less flexibility. At larger distances, there is even a mild
destabilizing effect of the supported nanoparticle (ΔEf =
+0.09 at 4.70 Å).
For more ionic oxides, MgO and BaO, the effect of the Ru10
particle on the VO formation energy is smaller than that in the
previous cases and vanishes quite rapidly on moving away from
the metal cluster. For Ru10/MgO, ΔEf = −1.60 eV is reported
for the vacancy underneath the cluster (VO1), which decreases
to −1.29 eV if the vacancy is located at a peripheral position
(VO2). At R = 3.04 Å (VO3), ΔEf is as small as −0.42 eV, while
the formation energy on the clean surface is almost recovered at
a distance of 5.53 Å (VO4). On BaO, the stabilizing effect of
Ru10 is weak. A gain in energy of −0.44 eV is found for VO1
(vacancy under the cluster), while in the peripheral site, VO2,
the oxygen vacancy is destabilized by 0.14 eV with respect to
the pristine oxide. We attribute this to the strain imposed by
the cluster by the surface ions, which hinders the lattice
distortion and polaron formation when the vacancy is created.
At R > 3 Å (VO3 and VO4), ΔEf is virtually zero (Table 2 and
Figure 12).
Interestingly, a very similar trend is reported for Aurod
supported on anatase TiO2 (101). Namely, the stabilizing
effect of the rod on the oxygen vacancy is larger when the
vacancy lies underneath the Au nanostructure (VO1, ΔEf =
−1.75 eV). On peripheral sites, there is a residual stabilization
of −0.90 eV (VO2) and −0.45 eV (VO3). At a distance R = 6 Å,
there is no sizable effect of the Au rod. This suggests that the
trend is independent of the metal, with small differences
between small metal clusters and metal nanostructures due to
the different structural flexibility.
The decrease in the formation energy of a VO center near a
metal cluster described above, however, is not universal. In a
study of small Pt clusters deposited on the CeO2(111) surface
Bruix et al. found, using a DFT+U approach, that the presence
of a Pt8 cluster has a rather small effect, reducing the cost of VO
formation by 0.2 eV only when the vacancy is directly under the
cluster.123 Along the same line are the results reported by
Negreiros and Fabris for the same system using the DFT+U
approach.124 These authors studied the stability of a Pt4 and a
Pt6 cluster deposited on the same CeO2(111) surface. They
compared the stability of the two Pt clusters on the surface with
and without an oxygen vacancy and studied the effect as a
function of the position of the vacancy from the cluster. The
cluster binding energies to the defective ceria surfaces are
reported in Figure 13 and clearly increase as the distance
between the cluster and the vacancy increases. Both Pt4 and Pt6
clusters show a clear preference to bind on the pristine ceria
surface. Formation of O vacancies at the Pt/CeO2 interface is
thus disfavored in comparison to that at the pristine surface, at
variance with other oxides. The computed driving force for
displacing the vacancy far from the metal/oxide interface is 1.20
eV for Pt4 and reduces to 0.45 eV for Pt6.
This behavior has its origin on the fact that Pt clusters
deposited on ceria reduce the oxide support by direct electron
transfer: i.e., without the need to change the oxide
between VO and the metal cluster. For this purpose, a general
descriptor R of the vacancy-cluster distance is introduced.
When a vacancy is formed on a surface of a generic XOn system
in the presence of a supported Mn′ metal particle, R is defined
as the minimum distance between any metal atom M of the
supported particle and a X cation surrounding the oxygen
vacancy (Figure 11).
Figure 11. Definition of the vacancy−cluster distance R.
In Table 2, we report the formation energy of a surface VO
defect (Ef, defined with respect to the pristine oxide and 1/2
O2) on clean surfaces or in the presence of supported metal
aggregates. On the clean surfaces, the VO formation energy
varies significantly, spanning from about 6 eV (MgO, ZrO2) to
about 5 eV (BaO, SiO2). In the case of anatase TiO2, the (101)
surface displays both two-coordinated and three-coordinated O
ions; Ef is 4.53 eV in the former case and 5.67 eV in the latter.
The nature of the reduced centers also differs from oxide to
oxide: while closed-shell F centers are formed on MgO, BaO,
and ZrO2, in the case of TiO2 the formation of Ti3+ is observed.
In SiO2 a covalent Si−Si bond is formed upon oxygen
removal.7
In Figure 12, the change in Ef, ΔEf, due to a supported metal
cluster is displayed as a function of the cluster−vacancy
distance R (see also Table 2). One can immediately see that, for
vacancy−cluster distances as large as 5 Å, ΔEf tends to 0 in all
cases. This means that the effect of the metal particle on the
formation of oxygen vacancies is a short-range effect. A certain
case dependence, however, emerges when the effect is analyzed
at small vacancy−particle distances. The strongest influence is
reported in the case of Ru10/SiO2, where at R = 2.28 Å Ef drops
from 4.85 eV (clean oxide) to either 1.87 or 3.11 eV, depending
on whether the vacancy site is located underneath the Ru10
particle (VO1) or at its boundaries (VO2). ΔEf drops to 0
already at a distance of 4.94 Å (VO3).
In addition, in the case of Ru10/ZrO2 the formation energy
remarkably decreases at short distances (ΔEf is −2.51 eV for
VO1 underneath the cluster and −0.94 eV for the boundary
case, VO2). At R = 3.93 Å (VO3), a moderate ΔEf value is still
found (−0.58 eV), while convergence to the clean-surface Ef
value is reached for R > 7 Å (VO4 and VO5). On the other
oxides, the effect of the Ru10 particle on Ef is smaller. For Ru10/
TiO2, for instance, the removal of a three-coordinated oxygen
under the cluster (VO1) costs 3.90 eV (in comparison to 5.67
eV on the clean oxide) with an energy gain of −1.77 eV. In this
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Table 2. Oxygen Vacancy Formation Energies (Ef, eV), Changes in the Formation Energy in the Presence of a Supported
Nanoparticle (ΔEf, eV), Vacancy−Metal Particle Distancse (R, Å) and Bader Charges of the Supported Metal Particles (qM, |e|)
oxide
MgO
BaO
ZrO2
SiO2
TiO2
a
system
Ef (eV)
ΔEf (eV)
R (Å)
qM (|e|)
+6.19
+4.59
+4.90
+5.77
+6.24
−1.60
−1.29
−0.42
+0.05
2.73
2.67
3.04
5.53
−2.00
−2.02
−0.82
−0.75
−0.75
VO1
VO2
VO3
VO4
+4.91
+4.47
+5.05
+4.82
+4.87
−0.44
+0.14
−0.09
−0.04
3.07
3.24
3.62
7.13
−1.75
−1.71
−1.21
−1.21
−0.83
VO1
VO2
VO3
VO4
VO5
+5.92a
+3.41
+4.98
+5.34
+5.87
+5.87
−2.51
−0.94
−0.58
−0.05
−0.05
2.74
2.66
3.93
7.07
8.97
−0.52
−0.59
−0.12
−0.07
−0.08
+0.23
SiO2‑x
Ru10/SiO2−x, VO1
Ru10/SiO2−x, VO2
Ru10/SiO2−x, VO3
Ru10/SiO2
+4.85
+1.87
+3.11
+4.77
−2.98
−1.74
−0.08
2.28
2.28
4.94
+0.30
−0.03
+0.11
+0.15
TiO2−x (O2c)
TiO2−x (O3c)
Ru10/TiO2−x, VO1 (O3c)
Ru10/TiO2‑x, VO2 (O2c)
Ru10/TiO2‑x, VO3 (O2c)
Ru10/TiO2−x, VO4 (O2c)
Ru10/TiO2
+4.53
+5.67
+3.90
+2.79
+4.32
+4.62
−1.77
−1.75
−0.21
+0.09
2.56
2.57
2.51
4.70
+0.83
+0.67
+0.88
+1.48
+1.53
Aurod/TiO2−x,
Aurod/TiO2−x,
Aurod/TiO2−x,
Aurod/TiO2−x,
Aurod/TiO2
+2.82
+3.68
+4.12
+4.58
−1.75
−0.90
−0.45
0
2.64
2.61
2.77
5.96
−0.76
−0.24
−0.34
−0.09
+0.09
MgO1−x
Ru10/MgO1−x,
Ru10/MgO1−x,
Ru10/MgO1−x,
Ru10/MgO1−x,
Ru10/MgO
BaO1−x
Ru10/BaO1−x,
Ru10/BaO1−x,
Ru10/BaO1−x,
Ru10/BaO1−x,
Ru10/BaO
ZrO2−x
Ru10/ZrO2−x,
Ru10/ZrO2−x,
Ru10/ZrO2−x,
Ru10/ZrO2−x,
Ru10/ZrO2−x,
Ru10/ZrO2
VO1
VO2
VO3
VO4
V O1
V O2
V O3
V O4
(O2c)
(O2c)
(O2c)
(O2c)
This value has been obtained with a three-layer slab of a 7 × 4 supercell (Zr168O336).
particle is −0.75 |e| for MgO and −0.83 |e| for BaO). On ZrO2
(qM = +0.23 |e|) and SiO2 (qM = +0.15 |e|) the charge transfer at
the interface is almost negligible. On TiO2, the Bader charge of
the Ru10 cluster is quite large and positive (qM = +1.53 |e|).
However, as previously discussed,122 it has not been possible to
stabilize any Ti3+ center in the oxide upon deposition of the
Ru10 particle, suggesting that the positive charge of the cluster is
due to the formation of covalent polar Ru−O bonds, rather
than to a net electron transfer to the Ti 3d empty states. More
details on the charge transfer at the oxide/cluster interface are
discussed in the Supporting Information.
stoichiometry. Removing oxygen leads to an additional
formation of Ce3+ ions, with local distortions and structural
relaxation costs. We can conclude that the reduction of the VO
formation energy is expected for oxides which are not already
highly reduced or where the deposition of the metal does not
lead to an electron-rich surface by the effect of metal to oxide
charge transfer.
This introduces another topic, the oxide reduction at the
metal/oxide interface due to the charge transfer or charge
polarization between the supported metal and the oxide surface.
In the cases discussed above, the deposition of Ru10 on the
stoichiometric oxide surfaces does not cause the effective
formation of reduced centers. From the Bader formalism
(Table 2), however, the charge transfer at the interface
significantly differs from oxide to oxide. On MgO and BaO,
the Ru10 cluster is reduced (the total Bader charge of the metal
4. OXIDE FILMS AND NANOSTRUCTURES ON
METALS: INVERSE CATALYSTS
A particular case of metal/oxide interfaces is represented by
ultrathin oxide films and oxide nanostructures grown on a metal
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Figure 12. Change in the oxygen vacancy formation energy (ΔEf, eV) as a function of the vacancy−metal cluster distance (R in Å; see text and
Figure 11 for definition).
(STM).125,126 Over the past 20 years, the progress in atomistic
characterization and understanding of thin oxide films has been
spectacular. However, the basic assumption behind this
approach, that a thin oxide film will keep the same electronic
and geometric structure of the bulk oxide and its surface, is not
always fulfilled. While in some particular but restricted cases
oxide ultrathin films closely resemble their bulk counterparts, in
many other cases they exhibit structures and properties that
have little in common with the parent oxide materials. The
reader is referred to a few specific reviews3,125−127 and books
for further info on this topic.128,129
There are several reasons why thin oxide films differ in
general from oxide surfaces. One is that there is a close contact
with the metal support, with formation of a metal/oxide
interface. This provides an infinite electron reservoir; if the
Fermi level of the metal is above the empty states of an
adsorbate, and the film is sufficiently thin, electrons can tunnel
from the metal to the adsorbate through the insulating
layer.125,126 The opposite is also possible: i.e., species adsorbed
on these insulating layers can donate electronic charge to a
metal support with high work function. This opens the
possibility of tuning the charge state and the surface dipole of
a metal/oxide interface. If metal clusters or other adsorbates are
deposited on the thin oxide films, additional possibilities arise
for the design of nanocatalysts with tailored properties.126
It is not surprising that defects such as oxygen vacancies,
created in the oxide phase, can also exchange electrons with the
metal support, resulting in a charging or discharging of the
Figure 13. Adsorption energies (in eV, right panel) of Pt4 and Pt6
clusters on a defective CeO2(111) surface with an O vacancy in three
different positions (see sites 1−3 in left panel). Reprinted with
permission from ref 124. Copyright 2014 American Chemical Society.
support.125−127 The field of oxide thin films on metals started
around 1990, with the aim of obtaining model systems suitable
for a better characterization of oxide surfaces. The initial idea
was that, by depositing a thin oxide film consisting of a few
atomic layers (with thickness typically below 10 nm), one can
produce realistic models of oxide surfaces with the advantage of
allowing the use of classical characterization tools used in
surface science for metals and semiconductors. In particular,
depositing ultrathin oxide films on a metal helps overcoming
problems connected to the insulating and brittle nature of most
oxides. Indeed, great advances have been done in the field by
characterizing oxide films with photoemission spectroscopy
(XPS, UPS, etc.) and scanning tunneling microscopy
Figure 14. Structures of a ZrO2−x ultrathin film supported on (a, b) Pt3Zr(0001) (3 × 3) supercell, (c, d) Pt(111) (5 × 5) supercell (A), and (e)
Pt(111) (√19x√19)R23.4° supercell (B). Color scheme: Pt, green; Zr, blue; O, red. The vacancy is indicated with an arrow. Reprinted with
permission from ref 133. Copyright 2017 Royal Society of Chemistry.
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the excess electrons associated with the oxide defect to the
metal cluster.
The theoretical results on ZrO2 films await experimental
confirmation. A system which, in contrast, has been extensively
studied with both theory and experiment in CO oxidation is
FeO films supported on Pt(111). On Pt metal, the strong
bonding of CO to the Pt metal catalysts results in poisoning
effects. FeOx/Pt catalysts have been studied because of their
potential to annihilate the CO poisoning problem and indeed
demonstrated a remarkable activity for the preferential
oxidation of CO. Model catalytic studies have shown that
FeO islands on Pt(111), exposing coordinatively unsaturated
ferrous centers at the interface, are the active structures for CO
oxidation at 300 K.141 Here, the active species are the O atoms
derived from the dissociation of O2 molecules at the periphery
of the FeO single-layer islands. Sun et al. studied an extended
FeO bilayer film on Pt(111) under high pressures and found
the formation of an active FeO2 phase on Pt(111).72 This new
phase consists of a O−Fe−O trilayer, with an O layer at the
interface with Pt, an intermediate Fe layer, and an O layer
exposed toward vacuum. This new phase, which only forms
under O2 pressure, enhances CO oxidation on Pt(111) at 450
K. Since interfacial oxygen in the FeO2 trilayer is bonded with
Pt, the electron transfer from Pt caused all of the iron ions in
FeO2 to have a formal Fe3+ (ferric) oxidation state, as
confirmed by DFT calculations (DFT) and X-ray photoelectron spectroscopy (XPS).142 Pan et al. later found that
reducing the surface coverage of FeO2 to submonolayer could
further boost the activity for CO oxidation at 450 K, and hence
they suggested the FeO2−Pt interface as the active phase for
CO oxidation.143 More recently, the problem has been
reconsidered in some detail by Giordano et al.,144 who analyzed
the oxygen trapping and extraction characteristics on a large
variety of sites, spanning from oxide terraces to different oxide−
metal and oxide−oxide boundaries. The calculated O
adsorption/desorption energetics is, to a large extent, specific
to the nanoscale nature of the supported oxides and is driven by
the electron exchange with the underlying metal substrate. In
particular, the oxygen removal is easier at the border sites of the
FeO2 islands, where oxygen vacancy formation is accompanied
by a substantial electron transfer toward the Pt substrate.144
The common denominator of these studies is that, due to the
direct contact with the metal support, the FeO layer becomes
particularly reactive and, in the presence of an O2 atmosphere,
results in the formation of active oxygen lattice species that play
a key role in the CO oxidation, following a classical MvK
mechanism.
There is another possible contribution that makes supported
oxide films more prone to be reduced. This is the strain that
originates in supported oxide due to the lattice mismatch with
the metal. The role of strain in reducing the cost of oxygen
removal has been discussed in an STM study of cerium oxide
films supported on Rh(111).77 By a combination of STM
images with DFT calculations it has been possible to show that
under reducing conditions the CeOx layers develop an ordered
array of defects that are identified as oxygen vacancies. The
metal/oxide interface creates preferential sites for the reduction
of ceria; the local surface strain is invoked as a cause of the
enhanced reactivity for vacancy formation.
These studies introduce the more general and broad topic of
inverse catalysts.145,146 This topic has received increasing
attention in recent years. There are two configurations to
combine oxides and metals: (a) the conventional configuration
defect states associated with the vacancies, depending on the
position of the Fermi level of the metal/oxide interface.130 This
effect has been studied, for instance, for the case of VO centers
created at the top or in interface layers of MgO films grown on
Ag(001) or Mo(001).131 The nature of the oxygen vacancy in
these systems, with two, one, or no electrons trapped in the
vacancy, depends on several factors, including the metal
support, the position of the vacancy in the oxide film, etc.
Furthermore, the VO formation energy in MgO/Ag ultrathin
films is lower than that on the regular MgO surface.132 This
shows that nanostructuring a nonreducible oxide such as MgO,
and creating a contact with a metal, can result in a change in its
intrinsic properties.
Another example is that of zirconia films.133 As we
mentioned before, zirconia is notoriously a hardy reducible
oxide. This is consistent with a relatively high formation energy
of VO either in the bulk (6.16 eV) or on the (101) surface of
the material (6.03 eV). Things change completely when a twodimensional (2D) film of zirconia is considered. 2D zirconia
does not exist in nature, but ZrO2/Pt3Zr and ZrO2/Pt films
(Figure 14) have been prepared and characterized experimentally.134−140 Using a DFT+U approach with inclusion of
dispersion corrections, the process of the chemical reduction of
these films by removing oxygen has been studied,133 showing
that the zirconia films exhibit a high reducibility, at variance
with the bulk material.
The general underlying principle is that the extra charge
introduced when a neutral O vacancy is formed is transferred to
the metal substrate. This leads to a dramatic drop in the cost of
formation of the vacancy (Table 3). In particular, there is a
Table 3. Formation Energies, Ef, of a Neutral O Vacancy in
ZrO2 bulk, ZrO2(101) Surface, and Pt3Zr- and Pt-Supported
ZrO2−x Thin Films133
system
ZrO2 bulka
ZrO2(101) surfacea
ZrO2−x/Pt3Zr(0001)
ZrO2−x/Pt(111)
Ef (eV)
VO
VO
VO,top
VO,interface
VO,top
VO,interface
+6.16
+6.03
+3.28
+2.92
+0.95
+1.17
a
These values have been obtained with a (1 × 1 × 1) supercell (bulk)
and a five-layer slab of a 3 × 2 supercell (Zr60O120) (surface).
decrease by a factor of 2 for zirconia films supported on Pt3Zr
and a factor of 6 for Pt supports. Depending also on the
position of the vacancy, top or interface layers, Ef(VO) can drop
by 3−5 eV (Table 3), with obvious dramatic consequences on
the chemical reactivity of the film that is expected to behave
completely differently from the extended zirconia surface.
The low formation energy of O vacancies (enhanced
stability) in the supported thin film in comparison to zirconia
bulk and surface is the combination of two contributions: (a)
the electron transfer from the vacancy to the metal Fermi level
(dominant) and (b) the local structural deformation around the
vacancy.133 The metal substrate acts as an electron scavenger,
accepting the extra charge from the O-deficient zirconia. The
formation of the ZrO2/Pt3Zr or ZrO2/Pt interfaces thus
promotes the formation of O vacancies. The mechanism is
similar to what is found when metal clusters are deposited on
oxygen vacancies, as also in this case the tendency is to transfer
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Precious metals supported on ceria (CeO2) are widely used
catalysts in oxidation reactions, due to the remarkable OSC of
ceria, which allows the catalyst to supply lattice oxygen in an
excess of reductants and become reoxidized in an excess of
oxidants.39 The underlying mechanism for this transient
behavior may be facilitated by the presence of metal particles,
involving oxygen reverse spillover from the ceria to the metal.
Pt particles supported on ceria have been widely studied,
whereby also the role of the CeO2 morphology was taken into
account. Lykhach et al.152 have shown in STM and XPS
experiments that 1.5 nm thick ceria films supported on
Cu(111) are easily reduced by the deposition of Pt particles,
due to the reverse spillover of lattice oxygen. They suggested
that the oxygen reverse spillover is responsible for the selfcleaning behavior of Pt/CeO2 after the formation of carbon
deposits on Pt. In a DFT+U study on Pt8/CeO2(111), Bruix et
al.153 found that oxygen reverse spillover to Pt8 has an energetic
cost of only 1.0 eV, substantially lower than the oxygen vacancy
formation energy of 2.3 eV. Vayssilov et al.42 showed in a DFT
+U study that the oxygen reverse spillover to Pt8 becomes even
exothermic when the Pt particles are deposited on a ceria
nanoparticle. This shows that nanostructured ceria, in the form
of thin films and nanoparticles, exhibits an enhanced tendency
to give rise to oxygen reverse spillover, a conclusion supported
by a combined DFT+U and resonant photoelectron spectroscopy (RPES) study.41
Using global optimization algorithms in combination with
DFT+U, Negreiros et al.154 have shown how oxygen reverse
spillover affects the morphology of Pt3−Pt6 clusters supported
on CeO2(111). Happel et al.155 adsorbed CO on a Pt/
CeO2(111)/Cu(111) model catalyst and observed a blue shift
of the stretching frequency of CO adsorbed on Pt when the
catalyst was thermally treated. They assigned this effect to
reverse oxygen overspill from ceria to Pt and the consequent
oxidation of the metal particle. Similar effects were also
observed for subnanometer Pt clusters on ceria nanowires.156
In addition to Pt, oxygen reverse spillover was also observed
for other ceria-supported metal particles. For instance, Zafiris et
al.151,157 found experimental evidence for this type of
mechanism for Rh/CeO2 using TPD and steady-state reaction
measurements. Smirnov et al.158 demonstrated via XPD and
XRD that under mild heating in UHV (100−144 °C), Pd
particles supported on a mixed ceria−zirconia support become
oxidized, although no O2 was supplied via the gas phase,
indicating oxygen reverse spillover. Matolin et al.159,160
observed the formation of Ce3+ centers upon deposition of
Au and Pd particles on 1.5 nm CeO2 films supported on
Cu(111) via XPS, UPS, and RPES. They assigned the reduction
to the formation of Au−O−Ce species. On the basis of
mechanistic studies on steam re-forming of methanol over Cu/
CeO2/Al2O3, Men et al.161,162 suggested that oxygen reverse
spillover from the ceria to the Cu particles is part of the
catalytic cycle. Rh, Co, and Rh−Co bimetallic nanoparticles
supported on ceria were investigated in an experimental
multitechnique study by Varga et al.163 They observed reverse
oxygen spillover for Rh at elevated temperatures. For the Co
particles, encapsulation was observed. The bimetallic particles
were less prone to oxygen reverse spillover and encapsulation.
́
Ševčiková
et al.164 found in a combined TPR, TPD, and XPS
study that the occurrence of the oxygen reverse spillover in Rh/
CeO2 depends on the oxidation state of the ceria substrate,
whereby the spillover was inhibited for reduced ceria: i.e.,
CeO2−x. Oxygen reverse spillover to Rh was also observed
consisting of metal nanoparticles supported on an oxide
support, as discussed at the beginning of this Perspective, and
(b) the so-called inverse configuration in which oxide
nanoparticles are supported on a metal. In conventional
heterogeneous catalysts the metal is finely dispersed and
represents the active phase. A number of factors contribute to
the higher activity of the nanoparticles in comparison to the
extended surfaces, some already having been mentioned: (1)
nanosize effects (higher ratio of corners, vertex, edges, and
structural defects) and, for very small clusters, quantum-size
effects, (2) “fluxionality” of the metal nanoparticles, i.e. their
ability to easily undergo structural deformation, and (3) charge
transfer processes due to the interaction with the support. In
the inverse configuration, the role of the oxide is more
pronounced with respect to that of the metal, since now the
oxide is supported as nanoparticles on extended metal surfaces.
An additional important factor that contributes to increasing
the reactivity is the reducibility of the supported oxide
nanoparticle, which generally increases by reducing the size of
the nanostructure (see also the discussion above on the role of
oxide nanoparticles). Of course, strain in the nanoparticle can
also play a role.
The field is very broad, and we restrict our discussion here to
one illustrative example, that of CeOx/Cu(111) (inverse) vs
Cu/CeO2(111) (conventional) catalyst in the WGS reaction.147 In this work it has been shown that the activity is
significantly higher in CeOx/Cu(111) than in Cu/CeO2(111).
The detailed mechanism of the WGS on these inverse catalysts
and the precise role of the metal/oxide interface are still a
matter of debate.148 However, a recent study shows that the
excellent performance of a CeOx/Cu catalyst is related to the
beneficial role of a high concentration of oxygen vacancies
anchored at interfacial sites of the hybrid catalyst.149 The
vacancies play a mediating role in electron transfer and copper/
oxygen species activation. In this respect, it seems that
concentrating attention on the role of the oxide phase could
be more promising than improving the metallic component of
the catalyst. This also confirms that the oxide may play a role
even more important than that of the metal in the whole
catalytic process.
5. OXYGEN REVERSE SPILLOVER
The formation of oxygen vacancies at the boundary between a
supported metal particle and an oxide surface is related to
another important phenomenon, oxygen reverse spillover. It
consists of the diffusion of oxygen atoms (either those adsorbed
or those from the support) to a supported metal nanoparticle
that, eventually, can be covered by a more or less thick oxide
layer. The phenomenon occurs in a variety of reactions. It was
deduced from experimental observations already in the early
1990s.150,151 Generally, two cases of oxygen spillover can be
distinguished. In the first case, oxygen from the gas phase
adsorbs on the oxide support and is spilled over to the metal
particles. In the second case, oxygen from the oxide lattice is
spilled over to the metal, resulting in a reduction of the support
and an oxidation of the particle. The latter case can be seen as a
first step in what is sometimes referred to as a strong metal−
support interaction (SMSI). Under these conditions, an oxide
layer grows over the metal particle which, in some cases, can
become completely encapsulated, losing its chemical properties
and leading to catalyst deactivation. In the context of this
Perspective, we focus on the second case and examine just a few
illustrative examples.
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compensate the relatively high cost to create an anion vacancy
in an oxide. In this respect, the structural flexibility of the
supported nanoparticle plays an essential role. In addition, the
contribution of the metal counterpart in delocalizing the excess
electrons arising from the creation of a neutral vacancy is very
important. This effect has crucial consequences in all oxidation
reactions, but here two cases have been considered in detail:
CO oxidation and the water-gas shift reaction.
The study of these two processes has provided compelling
evidence of the direct involvement of oxygen atoms at the
interface region and of a MvK mechanism. The interesting
aspect is that the presence of a supported metal can deeply
change locally the chemical behavior of an oxide, to the point
that even nonreducible oxides can become partly reducible
thanks to this cooperative effect. Since the reducibility of an
oxide can also be varied by nanostructuring (nanoparticles,
nanowires, ultrathin films, etc.), the potential of metal/oxide
interfaces on the nanoscale opens up interesting and largely
unexplored possibilities for heterogeneous catalysis.
The phenomenon of higher reducibility at the metal/oxide
interface, however, is of general interest and broader impact.
Remaining in the field of catalysis, the interplay between metals
and oxides plays a key role in the growing field of inverse
catalysts or in the more traditional processes of oxygen reverse
spillover. Outside catalysis, generation of vacancies at the
metal/oxide interface is relevant in the area of memristors.173
Memristors are systems with several potential applications in
microelectronics and can be used for information storage or as
logic gates. The interfaces between the metal electrodes and the
oxide play a crucial role, especially for bipolar switches. A
typical memristor consists of a thin (50 nm) TiO2 film between
two 5 nm thick electrodes (e.g. Ti, Pt, etc.). The deposition of
the metal layer on the oxide can result in the formation of
oxygen vacancies. These defects are at the basis of the working
principle of this kind of memristor. Under an applied electric
field, in fact, oxygen vacancies can drift into the interface region,
reducing the electronic barrier and resulting in a low-resistance
state. Under an electric field with the opposite polarity, the
oxygen vacancies are repelled away from the interface region,
recovering the electronic barrier to regain the high resistance
state. The process is fully reversible, and the device can be used
to store or elaborate information. Staying in the field of
inorganic semiconductor applications, such as metal oxide
semiconductor field-effect transistors (MOS-FETs), chemical
reactions and defects at a metal/oxide interface can cause an
oxide gate dielectric to have high leakage current, with
deterioration of the properties. These simple examples
demonstrate that a better understanding of the nature of the
metal/oxide interface is essential in a variety of technological
areas, not only in catalysis.
when the Rh particles were supported on mixed ceria−zirconia
(Ce0.56Zr0.44)O2−x.165 The spillover of ceria lattice oxygen has
also been observed for Zr particles supported on CeO2(111)/
Cu(111): Shanwei et al.166 demonstrated the reverse spillover
of oxygen to the Zr particles via XPS and STM. Similar effects
have been observed for Cu particles supported on ceria: Chen
et al.,167 using XPS, IRAS, Raman, and HRTEM, have shown
that oxygen vacancies are generated as a consequence of
electron donation from metal copper atoms to CeO2 and
subsequent reverse spillover of oxygen.
Oxygen reverse spillover also occurs on oxides other than
ceria. In the following, a few examples are summarized. Martin
et al.168 have shown that the exchange rate of 18O isotopes
(from gas-phase 18O2) with 16O isotopes from the supporting
oxide is strongly enhanced in the presence of the Rh
nanoparticles supported on SiO2, Al2O3, ZrO2, MgO, CeO2,
and CeO2−Al2O3, respectively. Using AFM and XPS, Ono et
al.169 found that, upon heating of silica-supported Au clusters to
elevated temperatures (T > 1300 K), the silica decomposes at
the Au perimeter. The results revealed a Au-assisted oxygen
desorption from the support via reverse oxygen spillover to the
Au nanoparticles. Chen et al.170 have shown in a DFT+U study
that for Ru10 clusters supported on titania anatase and
tetragonal zirconia, respectively, the energetic cost for oxygen
reverse spillover is relatively low, i.e. 0.2 eV for titania, and has a
moderate cost (0.6 eV) for zirconia. Similarly, the energetic
cost for oxygen reverse spillover for Ni10 supported on the same
surfaces was found to be thermoneutral for titania and only
slightly endothermic for zirconia (0.6 eV).171
These results clearly indicate that the phenomenon of oxygen
reverse spillover is very common, when the catalytic process
implies high thermal treatments. It is only another manifestation of the same phenomenon, higher oxide reducibility in the
proximity of the metal/oxide interface.
6. CONCLUSIONS
In this Perspective, we have analyzed several examples of
processes that are directly affected by the formation of a metal/
oxide interface. This is common in heterogeneous catalysts
based on supported nanoparticles. The atoms of the oxide
support in direct contact with the metal particle, and in
particular the O atoms at the boundary region, exhibit a
different reactivity in comparison to the other O atoms of the
surface. In particular, they can be more easily removed by an
adsorbed species that is thus oxidized, leaving behind an oxygen
vacancy. This important conclusion has been predicted by
various theoretical studies and, more recently, verified and
supported by specific experiments, as shown in Table 1. The
higher reactivity of lattice oxygen at the metal/oxide boundary
can be used to design better catalysts in oxidation reactions on
going from pure oxide materials to oxide surfaces where metal
nanoparticles have been deposited. Of course, the efficiency of
such a catalyst will depend also on the resistance toward
sintering of the small particles. An aspect that is important and
has received relatively little attention so far is how the depletion
of oxygen at the metal/oxide boundary affects the subsequent
removal of oxygen atoms. Most of the results reported in the
literature in fact are dealing with the cost of removing the first
O atom from the interface, while this cost can be significantly
different once the surface starts to be reduced.172
The main reason for the easier removal of the oxygen atoms
at the cluster boundary is that the metal atoms from the
supported cluster can refill the vacancy and partially
■
ASSOCIATED CONTENT
S Supporting Information
*
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b01913.
Computational details (methods used, supercell sizes,
etc.) for the original calculations described in section 3
together with an analysis of the charge distribution at the
metal/oxide interfaces (PDF)
6510
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AUTHOR INFORMATION
Corresponding Author
*E-mail for G.P.: gianfranco.pacchioni@unimib.it.
ORCID
Philomena Schlexer: 0000-0002-3135-9089
Sergio Tosoni: 0000-0001-5700-4086
Gianfranco Pacchioni: 0000-0002-4749-0751
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work has been supported by the European Community’s
Seventh Program FP7/2007-2013 under Grant Agreement
No.607417−European Marie Curie Network CATSENSE,
Grant Agreement No. 604307 (CASCATBEL) and by the
Italian MIUR through the PRIN Project 2015K7FZLH
SMARTNESS “Solar driven chemistry: new materials for
photo- and electro-catalysis”. The unpublished calculations
included in this paper were realized on the CINECA
supercomputing facilities (Grants HP10BD69EF and
HPL13PKBV5).
■
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DOI: 10.1021/acscatal.7b01913
ACS Catal. 2017, 7, 6493−6513