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Bridging the gap in catalysis via

multidisciplinary approaches
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Guest Editors: Christophe Coperet and Rutger van Santen

Université de Lyon, France and Eindhoven University of Technology, The Netherlands

Published in issue 36, 2010 of Dalton Transactions

Image reproduced with the permission of Dieter Vogt

Articles in the issue include:

Molecular understanding of alkyne hydrogenation for the design of selective catalysts
Javier Pérez-Ramírez, Blaise Bridier and Nuria Lopez
Dalton Trans., 2010, DOI: 10.1039/C0DT00010H

Molecular weight enlargement–a molecular approach to continuous homogeneous catalysis

Michèle Janssen, Christian Müller and Dieter Vogt, Dalton Trans., 2010,
DOI: 10.1039/C0DT00175A

Structure Determination of Zeolites and Ordered Mesoporous Materials by Electron

Crystallography
Xiaodong Zou, Junliang Sun, Dalton Trans., 2010, DOI: 10.1039/C0DT00666A

Metal-Catalyzed Immortal Ring-Opening Polymerization of Lactones, Lactides and Cyclic

Carbonates
Noureddine Ajellal, Jean-François Carpentier, Clémence Guillaume, Sophie M. Guillaume, Marion
Helou, Valentin Poirier, Yann Sarazin and Alexander Trifonov, Dalton Trans., 2010, DOI:
10.1039/C001226B

Visit the Dalton Transactions website for more cutting-edge inorganic and organometallic research
www.rsc.org/dalton
 PAPER
Oxygen activation on gold nanoparticles: separating the influence of particle
size, particle shape and support interaction
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Mercedes Boronat and Avelino Corma*
Received 2nd February 2010, Accepted 16th April 2010
DOI: 10.1039/c002280b
The adsorption and dissociation of molecular O2 on extended gold surfaces, isolated gold nanoparticles
of different size and shape, and small gold clusters supported on TiO2 have been investigated by means
of DFT calculations. The influence of particle size and morphology on the mode of adsorption and
activation of O2 have been analyzed separately, and it has been found that O2 dissociation is very
sensitive to the arrangement of the gold surface atoms. The control of this variable through catalyst
preparation opens one way to improve the activity of gold catalysts.
1. Introduction
The exceptional catalytic activity of gold nanoparticles supported
on inorganic oxides initially reported by Haruta1 has attracted
increased interest during the last few years. The amount of infor-
mation published about CO oxidation by gold is impressive,2–19
and the field of gold catalysis has been opened to other re-
actions of practical interest such as selective alcohol, aldehyde
and olefin oxidations,20–27 C–C coupling reactions,28–31 water gas
shift,32 direct synthesis of hydrogen peroxide from H2 and O2 ,33,34
and selective hydrogenations of olefins,35–38 aldehydes39–43 and
nitroaromatics.44–46
There is general agreement concerning the direct relationship
between the catalytic activity of gold nanoparticles and a number
of morphological and electronic effects such as particle size
and shape, oxidation state of gold, or charge transfer between
the gold particle and the metal oxide support. For instance, it
is widely accepted that the activity for hydrogenation of gold
catalysts is directly related to the number of low coordinated gold
atoms where H2 , as well as other reactants like CO or NO, are
more strongly adsorbed and activated.47–57 In this sense, it has
been suggested that the increasing activity of gold catalysts with
decreasing gold particle size is related to the higher concentration
of low coordinated gold atoms in the smallest particles. It has also
been demonstrated that the morphology of gold nanoparticles
and therefore the number of low coordinated gold atoms can be
modified by interactions with CO,58–60 which could explain the
strong influence of the method of preparation and the calcination
or reduction pre-treatments on the activity of supported gold
catalysts.1,2,5,6,61,62,63 There is also general agreement concerning
the higher catalytic activity of gold nanoparticles supported on
reducible oxides such as TiO2 , Fe2 O3 , or CeO2 ,1,2,3,4,5,6,10,11,64 but
whether the role of the support is limited to the stabilization
of small particles or is involved in the formation of cationic
gold surface sites or in the activation of reactants is still under
debate.65–68
Instituto de Tecnologı́a Quı́mica (UPV-CSIC), Av. de los Naranjos s/n,
46022, Valencia, Spain. E-mail: acorma@itq.upv.es; Fax: +34 96 3879444;
Tel: +34 96 387 7800
8538 | Dalton Trans., 2010, 39, 8538–8546
www.rsc.org/dalton | Dalton Transactions
One of the key steps in the mechanism of gold catalyzed
oxidation reactions, and yet one of the least understood, is the
activation and dissociation of O2 . While there is general consensus
that dissociative adsorption of molecular O2 on gold single crystals
is energetically unfavourable, the ability of low coordinated gold
atoms to adsorb and even dissociate O2 has been proposed on
the basis of theoretical calculations.17,50,51,69,70 The high reaction
rate for CO oxidation observed on a highly ordered gold bilayer
structure in which the underlying oxide support is not accessible to
reactants4,71 and the experimental confirmation by XANES that
gold nanoparticles can be oxidized by molecular O2 13 are in line
with this proposal, and suggest that particle morphology rather
than particle size is a key parameter in the catalytic properties of
gold. On the other hand, the dominating role played by the gold-
support interface in the adsorption and activation of O2 has been
stressed by different authors.18,19,65,66,66,72,73
In this work we have investigated the interaction of molecular O2
with several models of gold catalysts, including extended surfaces,
isolated nanoparticles of different size and shape and small
nanoparticles supported on TiO2 . We intend to first disentangle the
influence of particle size and morphology on the way of adsorption
and activation of O2 , and to analyze the changes induced by the
metal oxide support on several properties chosen to characterize
the interaction: adsorption energy, molecular geometry, nOO
stretching frequency and charge transfer between the catalyst and
the adsorbate. In a second step, the complete reaction pathway
for O2 dissociation on the several gold catalysts considered has
been calculated, and a relationship has been established between
the degree of charge transfer in the adsorbed reactant and the
activation energy necessary to dissociate O2 . It is demonstrated
that O2 dissociation is sensitive to the structure of the gold surface,
opening a way to improve the activity of gold catalysts.
2. Model catalysts and computational details
The interaction of molecular oxygen with isolated and supported
gold nanoparticles was studied by means of periodic slab models
using super cells large enough to avoid interaction between the
periodically repeated gold particles or between the adsorbates.
Two isolated gold nanoparticles of different size were considered:
a Au38 cluster having a typical cuboctahedral shape and 1 nm
This journal is © The Royal Society of Chemistry 2010
 diameter, and a hemispherical Au13 cluster obtained by removing
four atomic layers parallel to (100) from the Au38 model. The Au38
cluster has been previously employed in our group45 and has been
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demonstrated by Roldán et al. that it is able to dissociate O2 .70
The smaller Au13 clusters have also been widely used as models
for gold nanoparticles, both isolated and supported on TiO2 .54,60
The isolated Au38 and Au13 clusters were placed in a 20 ¥ 20 ¥
20 Å cubic box, and the position of all atoms was always fully
relaxed. The TiO2 support was represented by a (4 ¥ 4) super
cell slab model of the most reactive (001) facet of the anatase
polymorph. This model contains nine atomic layers in the unit cell,
that is, 144 atoms, and a vacuum region larger than 20 Å between
vertically repeated slabs. Besides the stoichiometric surface (TiO2
model), a reduced surface containing a oxygen vacancy defect
(TiO2 –Ovac model) was also considered. The Au13 cluster was then
placed on the stoichiometric and reduced TiO2 surface models
described above, and the atomic positions of all Au atoms and of
the Ti and O atoms of the two uppermost layers of the support
were fully relaxed. Finally, extended Au(111) and Au(100) surfaces
were modelled by (2 ¥ 2) super cell slabs containing four atomic
layers and a vacuum region larger than 20 Å between vertically
repeated slabs. In the geometry optimization of these extended
gold surfaces, the atomic positions of the two innermost layers
were kept as in the bulk and the two uppermost layers were fully
relaxed.
Molecular O2 was then adsorbed on the different gold surfaces
and nanoparticles described above, and the atomic positions of
O2 , of all Au atoms in nanoparticles, of the two uppermost layers
of the gold extended surface models, and of the Ti and O atoms
of the two uppermost layers of the TiO2 support were in all cases
fully relaxed. Except when otherwise stated, adsorption energies
E ads were calculated by subtracting the energy of the relaxed gold
catalyst model E Au and of optimized O2 in its triplet state E O2 from
the total energy of the adsorption complex EAu-O2 according to:
E ads = E Au-O2 - (E Au + E O2 )
Taking into account the results of previous theoretical studies,
the three possible ways of adsorption of molecular O2 depicted
in Scheme 1 were initially considered: a end-on mode (eo) with
the O2 molecule situated approximately normal to the surface and
with only one oxygen atom directly bonded to a gold atom, a top-
bridge-top (tbt) conformation with each oxygen atom in O2 directly
bonded to a gold atom, and a bridge-bridge (bb) conformation in
which each oxygen atom is interacting with two gold atoms.
Scheme 1 Adsorption modes of O2 on gold.
All calculations are based on density functional theory
(DFT) and were carried out using the Perdew–Wang (PW91)74,75
exchange–correlation functional within the generalized gradient
approximation (GGA) as implemented in the VASP code.76,77 The
This journal is © The Royal Society of Chemistry 2010
Kohn–Sham orbitals used to obtain the electron density were
expanded in a plane wave basis set with a kinetic energy cut off of
500 eV, and the effect of the core electrons was taken into account
by means of the projected augmented wave (PAW) method.78 The
Brillouin zone of the (2 ¥ 2) super cell models was described using a
(5 ¥ 5 ¥ 1) Monkhorst–Pack mesh,79 and the rest of the calculations
(isolated nanoparticles and (4 ¥ 4) super cell models) were carried
out at the C k-point of the Brillouin zone. The atomic positions
were optimized by means of a conjugate-gradient algorithm until
atomic forces were smaller than 0.01 eV Å-1 . Transition states were
located using the DIMER algorithm80,81 and stationary points
were characterized by pertinent frequency analysis calculations.
Vibrational frequencies were calculated by diagonalizing the block
Hessian matrix corresponding to displacements of the O atoms of
O2 molecule and the Au, Ti or O atoms of the catalyst in direct
contact with O2 . Charge distributions were estimated using the
theory of atoms in molecules (AIM) of Bader using the algorithm
developed by Henkelman.82,83
3. Results and discussion
3.1. Adsorption of molecular O2
Molecular O2 was placed on the two extended gold surfaces and on
the several isolated and supported gold nanoparticles considered
in this work with the molecule initially adopting the three different
conformations depicted in Scheme 1. The geometry of these initial
structures was optimized as described in previous section, and
the most relevant information relative to the stable structures
finally obtained is summarized in Table 1. Only one minimum
was localized on Au(111) surface, corresponding to a top-bridge-
top conformation in which the two oxygen atoms are bonded
to neighbouring gold atoms. The optimized Au–O distances are
2.27 Å and the O–O bond is slightly elongated in relation to the gas
phase value, that is 1.235 Å. The same conformation was obtained
on Au(100) surface and, as shown in Table 1, the optimized
geometries and the calculated nOO stretching frequencies are
similar on both surfaces. However, the calculated adsorption
energies are positive, indicating that these tbt structures are not
stable species. A second conformation, with each of the two oxygen
atoms of O2 forming a bridge with two different gold atoms (bb),
was obtained on the Au(100) surface. The Au–O distances in this
structure are ~ 2.3 Å too, but the O–O bond length increases to
1.42 Å, and consequently the nOO frequency is shifted to lower
values. Although the calculated adsorption energy is negative, the
value obtained is very small, reflecting the experimental fact that
O2 does not interact with perfect gold surfaces. The last property
analyzed in this work is the charge transfer from the metal to O2 .
The calculated values for the tbt species are similar and less than
0.5 e, while the value obtained for the bb conformer is larger, 0.8
e. This suggests that the degree of metal-adsorbate charge transfer
depends mainly on the mode of adsorption of O2 , and not so much
on the structure of the metal surface. To check whether these results
vary with the degree of coverage of O2 we re-optimized the most
stable structure, that is the bb adsorption complex on Au(001),
using a 4 ¥ 2 super cell slab model. The values provided by the
new setup, corresponding to a degree of coverage q = 0.25, are
completely equivalent to those obtained for q = 0.5, showing the
Dalton Trans., 2010, 39, 8538–8546 | 8539
 Table 1 Adsorption of molecular O2 on different gold models. Optimized O–O and Au–O distances (in Å), and calculated adsorption energies (E ads ,
in eV), vibrational frequencies (n(OO), in cm-1 ) and total charge on O2 (qO2 , in e)
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E ads r(OO) r(Au–O) n(OO) qO2

Au(111) tbt +0.24 1.319 2.268 1074 -0.451

Au(100) tbt +0.09 1.325 2.200 1055 -0.462
Au(100) bb -0.10 1.422 2.287 749 -0.813
Au(100) 4 ¥ 2 bb -0.22 1.427 2.286 751 -0.843
Au38 tbta -0.99 1.367 2.123 928 -0.624
Au38 tbtb -1.04 1.364 2.111 936 -0.639
Au38 bb -0.98 1.459 2.288 714 -0.874
Au13 eo -0.10 1.293 2.127 1223 -0.367
Au13 tbt -1.08a 1.344 2.127 1005 -0.534
Au13 bb -0.74a 1.528 2.204 617 -0.906
Au13 /TiO2 eo -0.80 1.282 2.182 1270 -0.300
Au13 /TiO2 tbt -0.94 1.348 2.191 1005 -0.540
Au13 /TiO2 msi -2.15 1.343 1.994b 1122 -0.542
Au13 /TiO2 –Ovac eo -0.49 1.280 2.172 1280 -0.279
Au13 /TiO2 –Ovac tbt -0.75 1.334 2.167 1061 -0.502
Au13 /TiO2 –Ovac msi -2.41 1.450 2.131 867 -0.901
a
Calculated as E ads = (E Au13-O2 )fully relaxed geometry - [(E Au13 )fixed geometry as relaxed for the complex + (E O2 )fully relaxed ], b r(Ti–O).

validity of the 2 ¥ 2 super cell slab model for describing the studied
phenomenon.
The Au38 cluster chosen to simulate small gold nanoparticles has
a cuboctahedral shape and exposes a combination of Au(111) and
Au(100) facets. Fig. 1 shows the structures of the three most stable
O2 adsorption complexes obtained after complete relaxation of all
atoms in the model, and the most relevant information about them
is summarized in Table 1. There are two top-bridge-top adsorption
modes of similar stability that differ in the coordination of the gold
atoms to which oxygen atoms are directly bonded. In structure tbta
the two oxygen atoms of O2 are bonded to gold atoms belonging to
the Au(111) facet and having coordination number 9 and 6, while
in structure tbtb the O2 is bonded to two gold atoms belonging to
the interface between Au(111) and Au(100) facets, both of them
with coordination number 6. However, the different coordination
of the gold atoms has no influence on the adsorption properties
analyzed. The stability of both structures is the same, the optimized
Au–O and O–O distances are equivalent, and the nOO stretching
frequency is ~ 930 cm-1 in both cases. There is a third conformation
Fig. 1 Optimized structures of adsorption complexes of O2 on Au38 (top)
and Au13 (bottom) nanoparticles.
of similar stability, the bridge-bridge complex (bb) depicted in
Fig. 1. The O–O bond length in this species is larger, 1.46 Å,
and the nOO frequency shifts to 714 cm-1 . Analysis of the net
charge on the O2 molecule after adsorption indicates that, as in the
case of perfect gold surfaces, the degree of metal-adsorbate charge
transfer depends on the way the adsorbate interacts with the metal,
and is larger for the bb than for the tbt conformations. It should be
mentioned that all these structures were also obtained by Roldan
et al.,70 but only the properties of the bridge-bridge conformation
in relation to its ability to dissociate O2 were discussed in their
paper.
To check the effect of particle size, molecular O2 was adsorbed
on a small Au13 cluster that initially consisted of two layers of
four and nine atoms parallel to (100) and with (111) side facets.
This and other isomers of Au13 were described in detail in ref.
54. While adsorption of O2 in the bb conformation results in a
small deformation of the initial cluster structure, the interaction
of O2 in the eo or tbt modes causes a large geometry distortion
in the gold nanoparticle, as depicted in Fig. 1. The irregular
particle obtained after full optimization without any adsorbed
O2 is 0.79 eV more stable than the hemispherical model initially
considered. If adsorption energies were calculated with respect
to the most stable isomer of the Au13 cluster, as has been done
for the rest of the models considered in this work, the values
obtained would mainly reflect the energy involved in particle
deformation, and would not provide much information about the
interaction with O2 . Therefore, the adsorption energies reported
in Table 1 have been calculated with respect to the energy of the
isolated particle in the same conformation as in the adsorption
complex, without any further geometry optimization. The end-
on adsorption mode, with only one oxygen atom directly bonded
to gold, has been found to be stable only on steps and defects
involving low coordinated gold atoms.69,84 A stable structure with
only one O atom directly bonded to a gold atom with coordination
number 5 has been obtained here on the Au13 cluster (see Fig. 1,
bottom, left). The optimized Au–O distance in this structure is
similar to the values reported for the other complexes, but the
adsorption energy is almost negligible, and the changes in the

8540 | Dalton Trans., 2010, 39, 8538–8546 This journal is © The Royal Society of Chemistry 2010
 properties of O2 molecule upon adsorption are minor. The O–O
bond length is slightly shorter than in the isolated molecule, and
the nOO frequency is larger than 1200 cm-1 , not so different from
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the corresponding gas phase value (1574 cm-1 calculated, 1556 cm-1
experimental85 ). The interaction of O2 with the Au13 cluster in both
tbt and bb modes is stronger and energetically favourable. The
changes in the geometric and vibrational properties of O2 upon
adsorption are similar to those observed on the Au38 nanoparticle,
and the calculated adsorption energies are approximately in the
same range.
The most remarkable conclusion provided by the comparative
study of gold surfaces and isolated nanoparticles of different size
is that the mode of adsorption of O2 does not depend on particle
size, but on particle morphology. Thus, while the tbt conformation
is formed, although with different stability, on any gold surface or
particle having two gold atoms, the eo adsorption mode requires
the presence of low coordinated gold atoms, and only systems
exposing (100) facets are able to stabilize the bb conformation.
The metal oxide support modifies the properties of gold
nanoparticles deposited on it, and therefore the way in which
O2 adsorbs and is activated. It is known that there is a transfer
of electron density between gold and the support, and that
gold nanoparticles become positively charged when supported
on stoichiometric and oxidized TiO2 surfaces, and negatively
charged when adsorbed on reduced surfaces. Moreover, the low
coordinated gold atoms in the nanoparticle tend to increase their
coordination number by forming Au–Ti bonds, and as a result the
particle shape may be noticeably distorted. In this work, O2 has
been adsorbed on different positions of the two Au/TiO2 catalyst
models described in section 2, and that have been obtained by
placing a Au13 cluster on either a stoichiometric (Au13 /TiO2 model)
or a reduced (Au13 /TiO2 –Ovac model) TiO2 surface. The properties Fig. 2 Optimized structures of adsorption complexes of O2 on Au13 /TiO2
of these two models have been extensively described and discussed (left) and Au13 /TiO2 –Ovac (right) models.
in previous work.54,60
The optimized structures of the adsorption complexes finally initially placing molecular O2 with one oxygen atom bonded to a
obtained on Au13 /TiO2 and Au13 /TiO2 –Ovac models are depicted gold atom of the nanoparticle and the other one directly bonded
in Fig. 2, and relevant information is summarized in Table 1. to a Ti atom of the support, forming a Ti–O–O–Au bridge. On
Both end-on and top-bridge-top adsorption modes were found, the stoichiometric support, the Au–O interaction is weak, and the
with the difference in stability between them being smaller molecule is finally placed on a fivefold coordinated Ti atom of the
than on the non-supported clusters. The optimized geometries, anatase surface, forming two equivalent Ti–O bonds. The degree
vibrational frequencies and charge transfer to O2 are however quite of O2 activation in this situation, measured by the increase in the
similar to those obtained on the non-supported Au13 nanoparticle, O–O distance and in the net charge transfer from the catalyst, is
suggesting that the direct influence of the oxide support on the similar to that obtained for the tbt conformation. However, the
activating ability of gold-only sites is limited. An indirect effect, adsorption energy is considerably higher, and therefore it can be
mainly related to the morphology of the supported particle, concluded that O2 will preferentially adsorb on the oxide support
is however remarkable. As described in detail in a previous and not on the gold nanoparticle. The situation is similar, but not
theoretical study of the active sites for H2 adsorption in Au/TiO2 completely equivalent, on the reduced Au/TiO2 catalyst, simulated
catalysts,54 when the Au13 isomer exposing (100) facets is placed by the Au13 /TiO2 –Ovac model. In this case the Au–O interaction is
on either the stoichiometric or reduced TiO2 surface, its geometry strong enough to keep the O2 molecule in the initial conformation,
is highly distorted and the final particles do not contain any forming two Ti–O bonds with calculated Ti–O distances of 1.864
arrangement of atoms that could resemble the initial (100) facet. and 2.084 Å, and with one oxygen atom still directly bonded
As a consequence, the bridge-bridge mode of adsorption of O2 to gold at a Au–O distance of 2.131 Å. In this conformation,
could not even be obtained on these supported gold nanoparticles. which is by far the most stable on the Au13 /TiO2 –Ovac model,
On the other hand, new sites appear at the metal-support interface, the O2 molecule has received 0.9 e from the catalyst, and the
which have been labelled as msi sites. According to previous O–O distance has increased to 1.45 Å, indicating an important
theoretical studies on Au/TiO2 catalyst models,49,50,65,66,67,68 O2 is molecular activation. The calculated nOO vibration frequencies
highly activated when it is placed at the interface between the gold for the msi sites in stoichiometric and reduced Au/TiO2 catalyst
nanoparticle and the oxide support. Fig. 2c shows the structures models are quite different, reflecting the different geometry and
obtained after geometry optimization of complexes formed by degree of molecular activation on the two systems.

This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 8538–8546 | 8541
 A comparative analysis of the data summarized in Table 1 allows adsorption of O2 on the way it is activated. Thus, adsorption
us to extract some general trends and conclusions that are valid for in an end-on conformation causes small changes in the properties
all catalyst models considered in this work, including perfect gold studied, while the larger activation of O2 is found in the bridge-
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surfaces, isolated nanoparticles of different size and shape and
small nanoparticles supported on TiO2 . The first clear result is
that adsorption energies roughly depend on particle size; they are
negligible on extended surfaces and become significant on discrete
nanoparticles, no matter the number of gold atoms they contain
nor the fact of being supported on a metal oxide surface. It can also
be concluded that on real Au/TiO2 catalysts, O2 will preferentially
adsorb on the support or at the metal–support interface, not on
the gold particles.
But adsorption energy is not necessarily a good predictor of
molecular activation. Activation of adsorbed O2 occurs through
occupation of the p* molecular orbitals, that leads to a weakening
of the O–O bond. Therefore, the properties that could better
reflect the degree of molecular activation are the total electron
density transfer from the catalyst to O2 , the increase in the O–O
bond length caused by this transfer, and the nOO that reflects
the strength of the O–O bond. Fig. 3 shows the direct relation-
ship existing between these three variables: the nOO stretching
frequency linearly decreases with increasing O–O distance and
with increasing net charge on O2 . Moreover, and what is more
important, it puts forward the large influence of the mode of
bridge conformations. It is interesting to remark the position of
the points corresponding to O2 adsorption at the metal-support
interface (msi) in Au/TiO2 models, close to the tbt group for the
stoichiometric surface and among the most activated species in
the bb group for the reduced surface.
3.2. O2 dissociation
Once it has been established which is the most activating mode
of adsorption, the complete reaction path for O2 dissociation
on several catalyst models has been calculated, and a correlation
between activation energies and adsorption mode has been found.
Only the tbt and bb conformations have been considered as initial
reactants on gold surfaces and isolated nanoparticles, while for
supported nanoparticles the tbt and msi modes on the reduced
surface have been explored.
The energy profile for the process is depicted in Fig. 4, together
with the optimized structures corresponding to reactant (R),
transition state (TS) and reaction product (P) on the Au(100)
surface. Starting from the optimized geometry of O2 adsorbed in
a bridge-bridge conformation, the reaction pathway involves the
breakening of the O–O bond, that is, the reaction coordinate is
clearly associated to a lengthening of the O–O bond length. The
optimized value of this r(OO) in the transition state is 2.034 Å (see
Table 2) and each oxygen atom is forming a Au–O–Au bridge with
two gold atoms. The reaction product is a structure in which the
two O atoms are placed in hollow positions on the Au(100) surface,
which is slightly distorted by the presence of adsorbed oxygen
atoms. The reaction is exothermic, and the calculated activation
energy is 0.44 eV, considerably lower than that reported for O2
dissociation on Au(111) or stepped Au(211) surfaces, 2.33 and
0.93 eV, respectively,66 and comparable to that recently reported
for O2 dissociation on the (100) facet of a Au29 nanoparticle
supported on TiC.86 The dissociation of O2 initially adsorbed
on a bb conformation on isolated Au13 or Au38 nanoparticles is
analogous to that described for the Au(100) surface. The optimized
structures of the transition states shown in Fig. 5 are equivalent
to that depicted in Fig. 4, and only the optimized value of the
r(OO)TS shows a small variation with particle size, being shorter on
the smaller particle. A similar trend is observed on the activation
barriers, that slightly decrease with decreasing particle size and
reach a really low value, 0.18 eV, on the Au13 cluster. The reaction
is exothermic in all cases, but the differences in the calculated

Table 2 Optimized value of the O–O distance in the transition states for
O2 dissociation (r(OO)TS , in Å) and calculated adsorption (E ads ), activation
(E act ) and reaction (DE) energies (in kcal mol-1 ) for O2 dissociation on gold
nanoparticles

r(OO)TS E ads E act DE

Au(100) bb 2.034 -0.22 0.44 -0.24

Au38 bb 1.968 -0.98 0.36 -0.94
Au38 tbt 1.947 -0.99 0.97 -0.43
Au13 bb 1.849 -0.98 0.18 -0.73
Fig. 3 Correlation between calculated stretching frequencies n(OO) and Au13 tbt 1.935 -1.08 1.58 -1.27
Au13 /TiO2 –Ovac tbt 2.412 -0.75 1.30 -0.36
(a) r(OO) distances and (b) total charge on dioxygen qO2 in the adsorption Au13 /TiO2 –Ovac msi 2.401 -2.41 1.10 -0.71
complexes studied in this work.

8542 | Dalton Trans., 2010, 39, 8538–8546 This journal is © The Royal Society of Chemistry 2010
 to the dissociation of the O–O bond, but also involves breaking
and formation of Au–Au and Au–O bonds. It can be seen in the
optimized structures of the transition states shown in Fig. 5 that,
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like in the mechanism starting from the bb conformation, the two

oxygen atoms are separated by less than 2 Å, and are forming two
Au–O–Au bridges. But in this case the two bridges are sharing
one gold atom, that is directly bonded to the two oxygen atoms.
After dissociation, the two oxygen atoms occupy stable 3-fold
coordinated hollow positions on the two particles considered, and
therefore the reaction is again exothermic.
The complete mechanism of O2 dissociation on supported gold
nanoparticles was calculated using the Au13 /TiO2 –Ovac model
to simulate the catalyst, and considering two different sites for
initial O2 adsorption: on the gold nanoparticle adopting a tbt
conformation, and at the metal–support interface (msi). The
reaction mechanism starting from the tbt conformer on the
Au13 /TiO2 –Ovac model is similar to that described for the isolated
Au13 cluster, and involves an activation barrier of 1.3 eV. Not
only the O–O bond but also several Au–O and Au–Au bonds are
Fig. 4 Schematic energy profile for O2 dissociation on Au(100).
modified in the process, and some restructuring of the particle
shape is observed in the optimized structure of the transition state
depicted in Fig. 6. The reaction is exothermic and after dissociation
the two oxygen atoms are situated on the gold nanoparticle, one
of them occupying a bridge position and the other one bonded
to three different gold atoms. It has been proposed that the most
active sites for O2 dissociation on supported gold nanoparticles are
located at the metal-support interface, and the results presented in
Table 2 confirm this proposal. The activation energy obtained
for the msi site is 0.20 eV lower than that calculated for the
reaction happening on the gold particle. Since the same model
and computational setup have been employed, direct comparison
of the calculated values is possible and meaningful. The reaction
path at the msi site does not only involve oxygen and gold atoms,
but also a titanium atom of the support. As described in previous
section, the two oxygen atoms of O2 molecule in the reactant
complex are interacting with a 5-fold coordinated Ti atom of the
oxide surface, and only one of them is directly bonded to a Au
atom of the particle. In the transition state, the intramolecular
O–O and one of the two Ti–O bonds are broken, while the Au–O
bond remains intact and no important restructuring is observed on

Fig. 5 Optimized structures of reactants (R), transition states (TS)

and products (P) involved in the dissociation of O2 on isolated gold
nanoparticles.

reaction energies are pronounced, and can be related to the

different geometrical arrangement of the O atoms in the reaction
product. While after dissociation the two O atoms occupy bridge
positions on the Au13 cluster, they are situated in the most stable
3-fold coordinated hollow positions on the Au38 nanoparticle, as
shown in Fig. 5.
The reaction path for dissociation of O2 initially adsorbed on
a tbt conformation is energetically less favourable, with calculated Fig. 6 Optimized structures of reactants (R), transition states (TS)
activation barriers equal to or larger than 1 eV in all cases. The and products (P) involved in the dissociation of O2 on supported gold
reaction coordinate describing this pathway is not only associated nanoparticles.

This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 8538–8546 | 8543
 the gold nanoparticle. In the final state, a Ti–O–Au bond has been
formed at the interface, and only one oxygen atom is adsorbed on
a hollow position at the gold nanoparticle.
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From these results it can be initially concluded that dissociation

of O2 involves low activation barriers (lower than 0.5 eV) when
the reactant molecule is adsorbed on (100) facets of gold in a
bridge-bridge mode. In this conformation, the charge transfer
from the metal surface to O2 and therefore the degree of molecular
activation is the highest. While the influence of particle size
on O2 dissociation by gold nanoparticles and the existence of
a critical size has been recently discussed,70 to the best of our
knowledge this is the first time that the structure-sensitivity of
this reaction is proposed. According to our results it seems that
O2 should easily dissociate on Au(100) single crystals, what is
contrary to experiment. However, it should be taken into account
that O2 dissociation and O2 desorption from the metal surface are
competitive processes, and the first one will only occur when the
activation energy is lower than the desorption energy. Analysis
of data in Table 2 allows us to conclude that dissociation is
energetically more favourable than desorption on isolated Au13
and Au38 nanoparticles, but not on Au(100), in agreement with the
experimental evidence that bulk gold is catalytically inactive. If the
same analysis is applied to the supported nanoparticles it is found
that, although the activation energy for O2 dissociation is higher
than 1 eV on the two cases studied, the adsorption/desorption
energy at the metal–support interface is considerably larger,
2.41 eV, and therefore the reaction will take place.
In order to find some general trends that could work both
for isolated and supported gold nanoparticles, the calculated
activation energies were plotted against a number of different
variables, and the most interesting relationships are shown in
Fig. 7. It should be mentioned that we do not observe a dependence
between activation and adsorption energies. Instead, there is a
linear relationship between the activation energy and the net
charge on adsorbed O2 , thus validating the hypothesis that the
degree of charge transfer determines the molecular activation.
The situation is different only in the case of O2 adsorbed at the
metal-support interface, where other interactions, such as Ti–O
bonds, exist. Finally, and most interesting from the point of view
of experimental characterization, a linear relationship has been
found between activation energy and nOO stretching frequency
of the adsorbed reactant, that is valid for all the catalyst models
studied in this work. The plot in Fig. 7 suggests that O2 molecules
whose nOO stretching frequency appears at values lower than
~900 cm-1 are sufficiently activated to dissociate. It can be argued
that in some cases, as for instance O2 adsorbed on Au(100), the
calculated nOO frequency is low, 750 cm-1 , but O2 desorption takes
place before dissociation. In these cases the condition is still valid,
because if O2 adsorption is weak and the molecule desorbs very
rapidly, the band corresponding to this vibrational mode will not
appear in the IR spectra.
Fig. 7 Correlation between calculated activation energies for O2 dissoci-
ation E act and adsorption energy E ads (top), total charge qO2 (middle) and
4. Conclusions
stretching frequency n(OO) (bottom) of the corresponding O2 adsorbed
Adsorption and dissociation of molecular O2 on different gold reactant species.
surfaces and nanoparticles has been theoretically investigated
in order to separate the effect of particle size, morphology and only existing on small particles with low-coordinated gold atoms
support on the mechanism of O2 activation. Three modes of O2 and which is not interesting from the catalytic point of view; (b) a
adsorption have been found: (a) a weakly interacting end-on mode top-bridge-top mode stable on all gold surfaces and particles, and

8544 | Dalton Trans., 2010, 39, 8538–8546 This journal is © The Royal Society of Chemistry 2010
 (c) a bridge-bridge mode that requires the presence of four gold
atoms arranged as in Au(100) surface. Adsorption energies roughly
depend on particle size. The properties that could better reflect the
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degree of molecular activation towards dissociation, such as total
electron density transfer from the catalyst to O2 , lengthening of the
O–O bond and shift in the nOO stretching frequency, are clearly
related among them and with the geometrical conformation of
adsorbed O2 . Thus, the highest degree of molecular activation is
always found in bridge-bridge conformers and, accordingly, the
lowest activation barriers for O2 dissociation are also obtained
for these species. Since bridge-bridge conformers are only stable
on Au(100) facets, this indicates that particle morphology is a
key factor influencing O2 dissociation. On the other hand, when
the gold nanoparticles are supported on TiO2 , the most stable
positions for O2 adsorption and the most active sites for O2
dissociation are found at the metal-support interface, and not on
the gold particle.
Acknowledgements
The authors thank CICYT (MAT 2006-14274-C02-01),
Consolider-Ingenio-2010 (project MULTICAT) and Fundación
Areces for financial support, and Red Española de Supercom-
putación (RES) and Centre de Càlcul de la Universitat de València
for computational resources and technical assistance.
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