Article

pubs.acs.org/JPCC

Graphene Oxide: An Ideal Support for Gold Nanocatalysts

Ming Yang,† Miao Zhou,† Aihua Zhang,† and Chun Zhang*,†,‡
†
Department of Physics and ‡Department of Chemistry, National University of Singapore, 2 Science Drive 3, Singapore, 117542

ABSTRACT: Via ab initio calculations, we predict that compared with pristine

graphene, graphene oxide (GO) is a much better candidate for support of metal (in
particular, gold) nanocatalysts in terms of activity and feasibility. Using Au8 clusters
supported on GO as model catalysts, we show that the reaction barrier of the catalyzed
CO oxidation can be greatly reduced from around 3.0 to 0.2 eV without the need of
defects or strain in the underlying support. The origin of the substantially enhanced
activity of Au catalysts is the charge transfer between the GO and supported Au clusters,
resulting in activated positively charged Au8 clusters. Both Langmuir−Hinshelwood and
Eley−Rideal mechanisms of the reaction are investigated. We expect our theoretical
predictions to stimulate new experiments in the application of GO, one of the most important chemical derivative of graphene, in
nanocatalysis.

C atalytic activity of gold nanoclusters has attracted

tremendous interest in the last several decades because
of their high catalytic activity and selectivity for various
chemical reactions.1−6 As for the support-induced heteroge-
neous gold catalysis, it has become a common knowledge that
the catalytic properties of gold catalysts (clusters) are closely
related to the interaction between the clusters and the
underlying substrate.7−11 Metal oxides such as MgO and
TiO2 are often used substrates for Au nanocatalysts.12,13 Effects
of inert supports such as h-BN on reactivity of Au clusters have
been discussed also.14 More recently, graphene, a single atomic
layer of graphite that exhibits many exceptional electronic,
mechanical, and chemical properties,15,16 was found to be a
promising support for Pt nanocatalyst,17 which triggered much
interest in graphene-supported metal nanocatalysis. However,
the situation for graphene-supported gold catalysis is not
encouraging. A number of theoretical and experimental studies
have shown that because graphene itself is chemically inert the
interaction between the supported gold clusters and graphene is
quite weak. Consequently, the gold clusters are highly mobile
on graphene,18,19 which is not desired for real applications, and
also, the catalytic activity of gold clusters on graphene is not
expected to be as high as that of metal oxide supported ones. In
very recent studies, it was proposed that carbon-vacancy defects
or mechanical strain in graphene can significantly increase the
chemical reactivity of graphene and in turn greatly enhance the
stability and activity of graphene-supported gold clusters.20,21 In
real industrial applications, controlling the defects or strain in
graphene is still a challenging issue. In current work, via high
level ab initio calculations, we suggest that graphene oxide
(GO) is an ideal support for gold nanocatalysts that can be
used to overcome all aforementioned limitations of graphene
substrate. We expect our theoretical predictions to stimulate
new experiments along this direction and pave the way for
future applications of graphene-supported gold nanocatalysis.
GO is probably the most studied chemical derivative of
graphene. GO contains reactive oxygen atoms, which make it
easy to be chemically modified. As a result, GO is believed to be
a good candidate for various applications such as sensors, field-
effect transistor (FET), and biomedical applications through
chemical functionalizaitons.22 Recently, GO has also been
considered for applications of catalysis. It was found in an
experiment that the composition of GO and oxide nano-
particles such as TiO2 may show improved photoelectronic and
photocatalytic performance.23 Another experimental work
demonstrated that Co2O3 nanoparticles can be adsorbed on
GO sheet with high stability and catalytic activity.24 These
results triggered our interest in studying effects of GO substrate
on gold nanocatalysis, which has not been discussed before.
Here we report first-principle calculations on catalytic proper-
ties of Au clusters adsorbed on GO. The goal of the research is
to show whether GO is a better substrate than pristine
graphene for gold nanocatalysts.
All calculations are based on density functional theory
(DFT) by using Vienna ab initio simulation package
(VASP).25,26 The frozen-core all-electron projector-augmented
wave (PAW) method27 with the generalized gradient
approximation (GGA) in PW91 format28 for the exchange-
correlational functional was used in all calculations. A plane-
wave basis set with the kinetic energy cutoff of 400 eV and 5 ×
5 × 1 k sampling was employed. In GO plane, the supercell was
set to be (3√3 × 5) primitive graphene unit cells with 60 C
and 12 O atoms, and in the direction perpendicular to the GO
plane, a vacuum region of larger than 20 Å was adopted in the
supercell to minimize the interaction between different slabs. In
the current study, we chose the reaction of CO oxidation as the
probe for catalytic activity of gold clusters supported on GO
substrate because this reaction is important in chemical
engineering and has been very intensively studied in nano-
catalysis. The reaction barrier was calculated by constrained
Received: May 31, 2012
Revised: September 28, 2012
Published: September 28, 2012

© 2012 American Chemical Society 22336 dx.doi.org/10.1021/jp3053218 | J. Phys. Chem. C 2012, 116, 22336−22340
The Journal of Physical Chemistry C
energy minimization method that is incorporated into VASP.29
In all calculations, the structures were fully optimized with a
force convergence criteria of 0.01 eV/Å.
In literature, there are quite a few different structure models
for GO.22,30−32 A common fact of these models is that GO
contains epoxy (mainly bridge site oxygen) or hydroxyl (−OH)
groups adsorbed on graphene basal plane, of which the
component, structure, and O/C ratio depend much on different
oxidation processes.22 Recently, first-principle studies predicted
that the GO structure with partial oxidation is thermodynami-
cally favorable, and structures with pure oxygen and C are
energetically favored under high oxygen chemical potential.30
Therefore, in our calculations, we chose the GO structure
model with oxygen atoms bonded to graphene at bridge sites
(the most stable adsorption sites), as shown in Figure 1a,
Figure 1. (a) Atomic structure of GO. (b) Variation of temperature as
a function of MD time step. (c) Time-dependent averaged variation of
the bond length between the O and the nearest C atom, where the
variation is defined as the difference between C−O bond length and its
equilibrium value. C, O, and Au atoms are in gray, red, and yellow,
respectively.
making the system hybrid of sp2 and sp3 bonding. This
structure is similar to the model proposed by Boukhvalov et
al.,31 but with a lower O/C ratio of 1:5. The low O/C ratio
(1:5) was recently verified in GO films by electron energy loss
spectroscopy.32 As shown in Figure 1a, in the relaxed structure,
the oxygen atoms deviated from the center of C−C bond
slightly, forming inequivalent C−O bonds with the adjacent C
atoms. The thermal stability of this GO structure was examined
by ab initio molecular dynamics (MD) calculations. Results of
MD simulations are shown in Figure 1b,c. The temperature
fluctuation becomes stable after 50 time steps (in our
calculations, one time step was set to 1 fs) and oscillates
slightly around room temperature (Figure 1b). From Figure 1c,
it can be seen that the maximum fluctuation of C−O bond
length (deviation from the equilibrium value) at the temper-
ature 300 K is <0.1 Å after 4.5 ps, suggesting that the GO is
stable at room temperature.
We chose Au8 clusters as model catalysts because first Au8 is
a very stable gold cluster that can be detected in low-
temperature combustion and second it is one of most
commonly used Au nanocatalysts in theoretical studies.33 Au8
clusters have three different isomers:34 two planar islands (P1
and P2) and one 3D tetrahedral structure, as shown in Figure
2a. When supported on pristine graphene, our calculations
agree with previous studies that all three isomers weakly
interact with graphene, and two planar structures are more
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Figure 2. (a) Three isomers of Au8 clusters in gas phase: Two planar
structures P1, P2, and a 3D configuration. The most stable adsorption
configurations of P1 (b), P2 (c), and 3D Au8 (d) on GO substrate. In
panel d, the isosurface of electron density redistribution is also
superimposed with the orange (blue) color denoting depletion
(accumulation) of electrons. The electron density redistribution is
defined by δρ = ρGO+Au8 − (ρGO+ρAu8). (e) Density of states (DOS)
projected on the “bonded” O and Au atoms for the 3D Au8 adsorbed
on GO. For comparisons, DOS of these two atoms before the
adsorption are also shown. The Fermi Level is shifted to 0 eV.
energetically favored than the 3D one by 0.4 eV,20 whereas
when adsorbed on GO, our calculations show that the 3D
isomer is more stable than two planar ones by more than 0.4
eV, and also in this case, the 3D cluster strongly binds to the
substrate with the adsorption energy of 1.7 eV. Here the
adsorption energy was calculated by Ea = EAu8 + EGO − EAu8+GO,
where EAu8+GO is the energy of the combined system and EAu8
and EGO are energies of the isolated gold cluster and GO
substrate, respectively.
The most stable configurations of planar (P1 and P2) and 3D
Au8 clusters adsorbed on GO substrate are shown in Figure
2b−d, respectively. Because of the strong interaction between
GO and the adsorbed 3D Au8 cluster, the Au atom bonds to the
nearest O atoms at the interface with a short bond length of
2.02 Å, resulting in a tilted 3D Au8 cluster on GO, as shown in
Figure 2d. In the Figure, the electron density redistribution
after the adsorption of the Au8 cluster on GO substrate is also
shown, from which we can see that there are “excess” electrons
accumulated around “bonded” O atoms, and the “depletion” of
electrons mainly occurs around “bonded” Au atoms. The Bader
charge analysis35 confirmed that there are ∼0.7 electrons
transferred from the Au cluster to GO substrate in this case.
The partial density of states (PDOS) projected on bonded O
and Au atoms (Figure 2e) shows the change of electronic
structures of these atoms before and after the adsorption. The
significant electron transfer from Au 5d orbital to O atoms can
be clearly seen from the PDOS.
Because of the charge transfer at the interface of Au8 and
GO, the Au8 cluster becomes positively charged. This is also
confirmed by its projected DOS. In Figure 3a, the partial
density of states of Au8 (blue solid line) on GO is plotted in
comparison with that of the free-standing Au8 cluster (red dash
line). It can be clearly seen from this Figure that the electron
transfer from Au8 to GO mainly happens near Fermi energy
(the energy range inside the green box in the Figure). We then
examine the chemical reactivity of this positively charged Au8
dx.doi.org/10.1021/jp3053218 | J. Phys. Chem. C 2012, 116, 22336−22340
The Journal of Physical Chemistry C
Figure 3. (a) Projected DOS (PDOS) of the Au8 cluster with (blue
solid line) and without GO substrate (red dash line). The green box
indicates the energy range within which the electron transfers from
Au8 to GO. (b) PDOS of O2 adsorbed on Au8 supported by GO; the
pink box indicates the energy range of continuous DOS originating
from hybridization. The Fermi level is shifted to 0 eV.
cluster by calculating the adsorption of O2 molecule on the
cluster. When supported on the pristine graphene, previous
studies20 pointed out that the O2 molecule does not bind to the
Au8 cluster (our calculations confirmed this finding) because of
the weak interfacial interaction. However, when supported on
GO, we found that the O2 molecule strongly binds to the
cluster with an adsorption energy of 1.6 eV. The adsorption
energy here is estimated by Ead = EO2 + EAu8+GO − EO2+Au8+GO.
The adsorption of O2 molecule on Au8/GO can be attributed
to strong orbital hybridization between O2 molecule and Au8
cluster, as shown in Figure 3b. In this case, the π orbitals of O2
significantly hybridized with d orbitals of Au8, forming a wide
range of continuous PDOS of O2 around the Fermi energy.
This hybridization causes nearly 1.1 electrons transferred from
Au8 to antibinding 2π* orbital of O2 (suggested by both PDOS
in Figure 3b and the isosurface of electron redistribution in
Figure 4a), leading to an elongated O−O bond with a bond
length of 1.4 Å, in contrast with 1.25 Å of the calculated O−O
bond length in gas phase. The significantly elongated O−O
bond suggests that the O2 molecule is activated after adsorption
on Au8 cluster/GO.
We next simulate the chemical reaction of CO oxidation
catalyzed by the GO-supported Au8 cluster. The full circle of
the catalyzed CO oxidation has two steps. The first step is the
reaction that breaks the O−O bond of O2 and forms a CO2
molecule, which is the major rate-limiting step and can be
described as CO + O2 → CO2 + O. The second step is the
oxidation of another CO molecule that brings away the leftover
O atom and restores the catalyst to its original configuration
before the reaction. The reaction barrier of the second step
normally is low. Both Langmuir−Hinshelwood (LH) and
Eley−Rideal (ER) types of reactions are considered in our
calculations. We first studied the ER mechanism of the first step
of the reaction. In this mechanism, the CO molecule
approaches O2 from vacuum. From previous experiences, we
know that in this case, the reaction barrier is dependent on the
initial position of the CO molecule in vacuum and also the
reaction trajectory. We have tested several different cases and
found that all of them have low reaction barriers less than 0.3
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Figure 4. ER mechanism of CO oxidation catalyzed by Au8/GO. (a)
Initial state of the reaction. The O−O bond length of the O2 molecule,
d(O−O), is 1.4 Å. The C−O bond length of CO molecule is 1.14 Å.
The distance between the C atom in CO molecule and the nearest O
atom of the O2 molecule, d(C−O2), is 3.0 Å. The isosurface of
electron density redistribution due to the O2 adsorption on Au8 is also
shown (the color scheme is the same as that in Figure 2), where we
can see that electrons are transferred from Au8 to antibinding 2π*
orbital of O2 molecule. The electron density redistribution here is
defined as δρ = ρGO+Au8+O2+CO − (ρGO + ρAu8 + ρO2 + ρCO). (b)
Transition state of the reaction: d(O−O) = 1.65, d(C−O2) = 1.8, and
d(C−O) = 1.16 Å. (c) Final state with the formation of CO2. (d)
Energy profile along the reaction path. S1, S2, and S3 are initial,
transition, and final states, respectively. The reaction barrier is
estimated to be 0.25 eV.
eV. In Figure 4, we presented one of these cases. The initial
state (denoted as S1) is shown in Figure 4a, where the distance
between the C atom and the nearest O atom of O2 (the
reaction coordinate) is 3.0 Å. In the Figure, the electron density
redistribution due to the adsorption of the O2 molecule is also
superimposed, from which we can clearly see that the electrons
transfer from the Au8 to the 2π* orbital of O2, leading to
elongated O−O bond as aforementioned. The transition state
(S2) and the final configuration (S3) (the formation of CO2)
are shown in Figure 4b,c, respectively. In the transition state,
the reaction coordinate is 1.8 Å. The energy profile along the
reaction path is presented in Figure 4d, where the reaction
barrier is estimated to be 0.25 eV. Note that the catalyzed CO
oxidation with a reaction barrier less than 0.5 eV is believed to
be able to occur at room temperature.
Figure 5 shows the LH type of the first step of the reaction.
After the adsorption of O2 the CO molecule can be coadsorbed
on the Au8 cluster (binding on the nearest site) with an
adsorption energy around 1.0 eV. The adsorption energy is
calculated according to Ead = ECO + EO2+Au8+GO − ECO+O2+Au8+GO.
The adsorption geometry is shown in Figure 5a. After
adsorption, the C−O bond length is 1.16 Å, slightly longer
than the calculated gas-phase value of 1.14 Å. The O−O bond
length of O2 remains almost unchanged (1.38 Å), and the
distance between the C atom and the nearest O atom of O2 is
3.0 Å. In this Figure, the electron redistribution caused by the
coadsorption of O2 and CO is also superimposed, from which
we can see the similar electron transfer from Au8 to 2π* orbital
of O2 and also slight electron transfer to 2π* orbital of the CO
dx.doi.org/10.1021/jp3053218 | J. Phys. Chem. C 2012, 116, 22336−22340
The Journal of Physical Chemistry C
Figure 5. LH mechanism of CO oxidation catalyzed by Au8/GO. (a)
Initial state of the reaction. In this case, the O2 and CO molecules are
coadsorbed on Au8. The O−O bond length of the O2 molecule, d(O−
O), is 1.38 Å, and the C−O bond length of CO molecule, d(C−O), is
1.16 Å. The distance between these two molecules as defined in Figure
3, d(C−O2), is ∼3.0 Å. The isosurface of electron density
redistribution due to the coadsorption of O2 and CO is superimposed
(the color scheme is the same as before), where we can see that
electrons are transferred from Au8 to 2π* orbital of both O2 and CO
molecules. The electron density redistribution here is defined as δρ =
ρGO+Au8+O2+CO − (ρGO + ρAu8 + ρO2 + ρCO). (b) Transition state of the
reaction: d(O−O) = 1.61, d(C−O2) = 1.7, and d(C−O) = 1.17 Å. (c)
Final state with the formation of CO2. (d) Energy profile along the
reaction path. S1, S2, and S3 are initial, transition, and final states,
respectively. The reaction barrier is estimated to be 0.2 eV.
molecule. The energy profile along the reaction path is shown
in Figure 5d, where S1, S2, and S3 denote the initial, transition,
and the final stale, respectively. In this case, the reaction barrier
is calculated to be 0.20 eV. The atomic configurations of the
transition and the final state are given in Figure 5b,c, from
which we can see that the transition state occurs when the
distance between the C atom and the nearest O atom of O2 is
1.7 Å. We then calculated the second step of the reaction and
confirmed that for both mechanisms the reaction barriers of the
second step are very low (∼0.16 eV), as expected. Some other
reaction mechanisms of oxidizing CO discussed in literature
might even be more energetically favorable,10,36 whereas our
results have been enough to demonstrate the high activity of
Au8 adsorbed on GO. It is worth mentioning here that although
the GO structure with single C−O bond is much more
energetically favorable than that with double CO bond, we
also performed calculations for O2 adsorption on Au8 clusters
supported on GO with CO double bonds and found that in
this case the O2 molecule also strongly binds to Au8 with an
adsorption energy around 1.54 eV and an elongated O−O
bond length of 1.37 Å, suggesting the high reactivity of Au8.
In summary, via first-principle calculations, we investigated
effects of GO substrate on support-induced catalytic properties
of Au8 clusters. The chemical reaction of CO oxidation was
chosen as a probe for the catalytic activity of the supported Au
clusters. These results were compared with the case of pristine
graphene support. For pristine graphene, our calculations agree
with previous studies that the planar isomers of Au8 clusters are
more stable than the 3D one. However, when supported on
GO substrate, the 3D one is the lowest energy configuration.
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This difference should be able to be examined by experiments.
Furthermore, the adsorption energy of the 3D Au cluster on
GO is ∼1.7 eV, much higher than the case of pristine graphene
(∼0.6 eV), indicating the significantly higher stability of the Au
clusters on GO. When on pristine graphene, previous studies
have shown that without defects or strain the O2 molecule does
not bind to the Au cluster. In the case of GO substrate, our
calculations found that the O2 strongly bonded to the Au
cluster with an adsorption energy >1.5 eV. Finally, we showed
that the reaction barrier of the CO oxidation catalyzed by Au8
cluster supported on GO substrate is lower than 0.25 eV for
both LH and ER mechanisms, clearly demonstrating the high
catalytic activity of the system. All of these results make us
believe that the GO is an ideal support for Au nanocatalysis.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: phyzc@nus.edu.sg.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by NUS Academic Research Fund
(grant nos.: R-144-000-237-133 and R-144-000-298-112).
Computations were performed at the Center for Computa-
tional Science and Engineering at NUS.
■
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