J Mol Model (2015) 21: 230
DOI 10.1007/s00894-015-2780-4
ORIGINAL PAPER
Catalytic mechanisms of Au11 and Au11-nPtn (n=12) clusters:
a DFT investigation on the oxidation of CO by O2
Xueli Cheng 1 & Yanyun Zhao 1 & Feng Li 3 & Yongjun Liu 2
Received: 18 April 2015 / Accepted: 28 July 2015 / Published online: 13 August 2015
# Springer-Verlag Berlin Heidelberg 2015
Abstract The oxidation of CO catalyzed by clusters of Au11,
Au10Pt and Au9Pt2 was investigated using the M06 functional
suite of the density functional theory. Au and Pt atoms were
described with the double- valence basis set Los Alamos
National Laboratory 2-double-z (LanL2DZ), whereas the
standard 6-311++G(d,p) basis set was employed for the C
and O atoms. Our theoretical model showed that (1) after
coordination to Au and Au-Pt cluster, O2 and CO are appar-
ently activated, and Mulliken charges show that the gold
atoms in the active sites of Au11 are negatively charged; (2)
Au-Pt clusters with 11 atoms can effectively catalyze the ox-
idation of CO by O2; (3) Au11 exhibits good catalytic perfor-
mance for the oxidation of CO; (4) oxidation of CO occurs
preferably on the AuPt active sites in Pt-doped clusters, and
the single-center mechanisms are more favorable energetically
than the two-center mechanisms; (5) after adsorption, an O2
molecule oxidates two CO molecules via stepwise mecha-
nisms; and (6) the catalytic processes are highly exothermic.
Keywords CO oxidation . Au11 clusters . DFT . Au10Pt .
Au9Pt2
* Xueli Cheng
ching108@sohu.com
* Yongjun Liu
yongjunliu_1@sdu.edu.cn
1
School of Chemistry and Chemical Engineering, Taishan University,
Taian, Shandong 271021, China
2
School of Chemistry and Chemical Engineering, Shandong
University, Jinan, Shandong 250100, China
3
School of Physics and Electronic Engineering, Taishan University,
Taian, Shandong 271021, China
Introduction
Catalytic oxidation of CO is important in several technologi-
cal applications such as environmental treatment, CO sensors
and closed-cycle CO2 pulsed lasers. Generally, gold (in bulk)
is regarded as a noble metal because of its resistance to oxi-
dation and corrosion; however, the pioneering work of Haruta
et al. [1, 2] showed that, in the form of nanoclusters, gold can
be exceptionally reactive and exhibit size-dependent low-tem-
perature catalysis [38]. Following this discovery, the catalyt-
ic oxidation of CO by clusters and surfaces of gold has be-
come a topic of intense research. The structural and electronic
spectroscopic properties of various clusters of Au [914], and
the adsorption of CO and O2 on clusters and the surfaces of
gold has been investigated both experimentally and theoreti-
cally [1523]. For the oxidation of CO, the high catalytic
activity and unique catalytic features of gold surfaces have
been the subject of sustained experimental and theoretical in-
vestigations [2426]. However, there is no general consensus
on the structural properties and the subsequent size-selectivity
of Au-based catalysts towards the oxidation of CO [9, 16, 27].
In fact, only a few theoretical investigations have focused on
the oxidation of CO on gold clusters at room temperature
[2830].
Liu et al. [31] reported that, for the oxidation of CO, a
cluster having a moderate stability was ideal when structural
differences were excluded and, in that regard, an Au75 cluster
with a decahedral structure was optimal. On comparison of
gold clusters of various sizes using cyclic voltammetry and
reaction kinetics, Chen and Chen [32] found that the Au11
cluster was the most effective oxygen-reduction catalyst.
Dong et al. [10] furthered this study by investigating the struc-
tural and thermodynamic properties of Au11 clusters using
global optimization and density functional theory (DFT).
However, the catalytic properties of Au11 clusters have not
230 Page 2 of 11
yet been studied. In this study, the mechanism of the oxidation
of CO catalyzed by an Au11 cluster was investigated based on
previous reports [10, 3234].
Small bimetallic clusters are often known to have proper-
ties that differ markedly from those of the atomic and bulk
states [3537]. In particular, the catalytic properties of bime-
tallic clusters depend excessively on the size and composition
of the system [38]. Recently, the bimetallic catalysts PtAu
have attracted a lot of interest owing to their unique activity
and selectivity towards the low-temperature oxidation of CO
[6, 26, 27, 29]. CO catalytic oxidation is a simple surfactant
bimolecular reaction, and is generally selected as a template
for transition-metal-catalyzed oxidation reaction systems. As
a result, further investigations on CO catalytic oxidation have
practical and theoretical significance. Therefore, in this study
we also explored the heterogeneous gas-phase mechanisms of
CO oxidation when one and two Au atoms in an Au cluster
were replaced with Pt. This work will provide helpful insights
into the catalysis of CO+O2 by noble metals.
Computational methods
The M06 [39] hybrid exchange-correlation functional suite of
DFT embedded in the G09 program package [40] was used to
fully optimize all the reactants, intermediates, transition states
and products in this study. The Hay and Wadt effective core
potentials (ECP) with a double- valence basis set (LanL2DZ)
[41, 42] was used to describe Au and Pt, while the standard 6-
311++G(d,p) basis set was applied for the C and O atoms.
DFT methods are probably the most versatile tools with which
to optimize molecular structures and elucidate reaction mech-
anisms, while the M06 functional suite has proven very effec-
tive in organometallic/inorganometallic chemistry and for
noncovalent interactions [39, 43, 44]. Because there are many
weak interactions in catalytic systems, the M06 functional
suite was selected.
Initially, frequency calculations were performed at the basis
set level to obtain thermodynamic parameters considering
zero-point-energy (ZPE) corrections, before classifying the
stationary points as minima (zero imaginary frequency) or
transition states (one imaginary frequency). The displacement
vectors of the imaginary vibrational modes were then used to
identify bond formation or rupture in transition states [45].
Furthermore, the transition states were checked by intrinsic
reaction coordinate (IRC) [46, 47] analyses to confirm wheth-
er they were indeed connecting two minima.
Results and discussion
The diamond-link Au11 structure was acquired from the work
of Dong et al. [10] based on DFT global optimization, and was
J Mol Model (2015) 21: 230
fully optimized with our theoretical model without any con-
straints. This three-dimensional geometry has also been re-
ported by others [3234]. In this work, the lowest frequencies
or the imaginary frequencies and their corresponding vibra-
tional mode assignments, differences of electronic and ZPEs
(E), Gibbs free energies (G) and thermal enthalpies (H)
of all species studied are listed in Table 1. The difference of
electronic and ZPEs (E) was used to elucidate the catalytic
mechanisms.
Activation of O2 by Au11
The adsorption of CO and O2 on Au11 is a requisite step in the
oxidation of CO. Chemisorption of O2 on bulk gold surfaces
does not occur below 773 K, so the surfaces were not used as
catalysts for the oxidation CO until the discovery of Haruta
and coworkers [4850]. Gold clusters normally exhibit good
catalytic performance for the oxidation of CO [51]. First, O2
adsorbed on Au11 and was activated. The geometries of O2
and Au11 were fully optimized for this step. The OO bond
length was 1.192 . Gu et al have reported earlier a GGA
result of 1.225 and a experimental result of 1.210 [52],
which suggests that our theoretical model is reliable in opti-
mizing geometrical structures.
Liu et al. had proposed that Au atoms having the lowest
coordination numbers can effectively activate O2 [53]. In the
case of Au11 clusters, Zhao et al. [34] advocated that the 3D
isomer structure of Au11 has the lowest-energy, however the
structure selected in this work was lower in energy than the 3D
structure by almost 28.9 kJ mol1. On the contrary, Sekhar De
et al. [33] had estimated the energy of our (selected) structure
to be higher than the most stable one of the Au11 cluster by
61.7 kJ mol1. These differences may originate from different
computational methods. In our structure, all the Au atoms
were positioned at the tricoordinate apexes on the surface of
the cluster. Therefore, electrical charges could be preferential-
ly concentrated at the interface/peripheral atoms [48], leading
to the enhanced catalytic performance towards the oxidation
of CO.
The shape of the gold cluster predicates its activity towards
the oxidation of CO [33]. To study this, we added O2 to the
three-coordinate Au1 and Au6 sites to produce the molecular
complexes IM1 and IM2, respectively. The interaction modes
observed were very similar to that of chemisorbed O2 on Au13
[19]. The optimized geometries of Au11 and these two com-
plexes are depicted in Fig. 1. In this and subsequent figures the
bond lengths are specified in ngstrom and the bond angles in
degrees. In Au11, the estimated bond lengths between the ver-
tex Au1 atom and Au3, Au8 were 2.794 and 2.828 , which
are much longer than the AuAu bond lengths reported in
Au2+ (2.671 ) and Au2 (2.697 ) [54]. Table 1 shows that
when O2 is coordinated with Au11, the energies decreased
significantly by 162.7 and 169.9 kJ mol1. However, these
J Mol Model (2015) 21: 230 Page 3 of 11 230

Table 1 The lowest vibrational frequencies and their corresponding mode assignments, differences of electronic and zero-point energies (ZPE; E),
Gibbs free energies (G) and thermal enthalpies (H) for all species

Frequency cm1 Vibrational mode assignment E (kJ mol1) G (kJ mol1) H (kJ mol1)

Au11 14 Molecule twist 0.0 0.0 0.0

O2 1700 O-O stretch
IM1 14 Molecule twist 162.7 133.6 160.7
IM2 11 Molecule twist 169.9 139.0 168.2
Au11 14 Molecule twist 0.0 0.0 0.0
O2 1700 O-O stretch
CO 2237 C-O stretch
IM3 11 Molecule twist 232.0 157.1 231.8
TS1 i464 C-O-O asymmetrical stretch 193.5 108.0 198.8
IM4 3 Molecule twist 468.5 397.7 470.3
P1 15 Molecule twist 455.2 411.6 459.1
CO2 693 O-C-O rock out of plane
P1 15 Molecule twist 0.0 0.0 0.0
CO 2237 C-O stretch
IM5 5 Molecule twist 32.8 2.8 33.5
TS2 i259 Au6-O-C asymmetrical stretch 12.4 22.6 13.4
IM6 1 Molecule twist 357.7 333.0 359.0
P2 14 Molecule twist 344.5 346.7 348.0
CO2 693 O-C-O rock out of plane
Au10Pt 8 Molecule twist 0.0 0.0 0.0
O2 1700 O-O stretch
CO 2237 C-O stretch
IM7 22 Molecule twist 200.0 122.7 201.3
TS3 i351 C-O-O asymmetrical stretch 158.8 78.5 163.3
IM8 15 Molecule twist 230.7 146.6 236.3
P3 10 Molecule twist 451.8 412.1 456.1
CO2 693 O-C-O rock out of plane
IM9 12 Molecule twist 276.7 195.7 280.6
TS4 i628 C-O-O asymmetrical stretch 96.9 17.3 100.8
IM10 14 Molecule twist 527.6 445.6 531.8
P4 18 Molecule twist 482.8 438.9 487.9
CO2 693 O-C-O rock out of plane
P3 10 Molecule twist 0.0 0.0 0.0
CO 2237 C-O stretch
IM11 14 Molecule twist 27.9 11.4 28.0
TS5 i170 C-O stretch 18.6 22.3 21.2
IM12 7 Molecule twist 361.2 327.7 362.0
P5 8 Molecule twist 348.0 345.9 351.1
CO2 693 O-C-O rock out of plane
Au9Pt2 12 Molecule twist 0.0 0.0 0.0
O2 1700 O-O stretch
CO 2237 C-O stretch
IM13 14 Molecule twist 372.7 299.0 374.0
TS6 i482 C-O-O asymmetrical stretch 280.5 195.0 286.6
IM14 10 Molecule twist 529.2 456.9 530.7
P6 20 Molecule twist 512.0 472.4 515.6
CO2 693 O-C-O rock out of plane
P6 20 Molecule twist 0.0 0.0 0.0
230 Page 4 of 11
Table 1 (continued)
Frequency cm1 Vibrational mode assignment
CO 2237 C-O stretch
IM15 19 Molecule twist
TS7 i521 C-O stretch
IM16 6 Molecule twist
P7 15 Molecule twist
CO2 693 O-C-O rock out of plane
bonding energies are much higher than the energies of O2
adsorption at the top (26.1 kJ mol1) and hole (35.7
kJ mol1) sites of Au19 [52] and on Au3 (95.5 kJ mol1)
[20] clusters. The coordination process was also highly exo-
thermic (H= 160.7 and 168.2 kJ mol1, respectively). of CO with Au4 initiated the catalytic reactions.
In IM2, the bond length of the newly formed AuO was
2.603 , which is much shorter than that in IM1 (2.726 ).
The OO bonds in IM1 and IM2 had extended from their
original value to 1.201 and 1.214 , respectively. Therefore,
O2 was effectively activated. Based on bond parameters and
thermodynamics, IM2 had a better activation performance
than IM1 so, as shown in Fig. 1, Au6 was a better bonding
site. On small metallic particles (34 nm in size [55]), the
bonding was stronger, the activity for oxidation of CO was
greater, and catalysis occurred mainly at the corner and edge
sites [48].
The HOMOLUMO energy gaps act as indicators of the
electronic stability of clusters because they represent the pos-
sibility of electrons jumping from the occupied orbitals to the
unoccupied orbitals. The elegant work of Sekhar De and co-
workers proved that the energy gap of the selected Au11 clus-
ter was much lower than those reported for Au2, Au6 and Au20
clusters [33]. Our theoretical model also showed a low energy
gap (110.2 kJ mol1). The LUMO energy of Au11 was nega-
tive (0.153 a.u.). For the selected Au11 cluster, all Au atoms
were on the surface. According to the frontier molecular or-
bitals (FMOs), O2 was bonded with Au6 and CO was coordi-
nated to the neighboring Au4 atom because the coordination
of O2 and CO to these sites was symmetry-adapted, as shown
Fig. 1 Structural parameters of
Au11, O2, CO, CO2, IM1 and
IM2. All molecular complexes
and intermediates in this work
were sequenced as IMn. Atoms
are numbered for differentiation.
Bond lengths are in ngstroms,
and bond angles in degrees
J Mol Model (2015) 21: 230
E (kJ mol1) G (kJ mol1) H (kJ mol1)
163.8 122.0 166.0
69.6 25.7 73.6
298.6 266.4 300.0
285.3 283.5 289.1
in Fig. 2. The d-type lone pair electrons of Au11 could fill the
anti-bonding 2* orbitals of O2 to activate the OO bond. The
following theoretical simulation probed into the catalytic
property of the Au4 and Au6 active centers. The coordination
Au11 + O2 + CO reaction
When O2 and CO bond with Au11 to form IM3, the electronic
and ZPEs as well as the free energy and thermal enthalpy
decreased markedly, as depicted in Fig. 3. Bond [48] reported
the chemisorption of small molecules such as CO on small
gold particles, wherein the AuC bonds in carbonyl com-
plexes were formed by the donation of charge from the 5
orbital of CO and back-donation of charge from the top of the
Au d-band into the vacant 2* anti-bonding orbital of CO. As
a result of this coordination, the CO bonds were weakened.
The AuC bond length in IM3 was 2.080 , which was slight-
ly longer than that involving an Au atom on the Au(110)
surface (1.983 ). [24]
Before the adsorption of CO on Au11, the vibrational fre-
quency estimated for CO was 2237 cm1, which was slightly
larger than the experimental gas-phase value of 2143 cm1
[17]. In IM3, the CO stretch mode was at 2227 cm1, red-
shifted slightly by 10 cm1, demonstrating that the CO bond
was weakened by attracting electrons from Au. The experi-
mental absorbance frequencies of CO at the low coverage
limit and at saturation on the Au(110) surface were 2118 and
J Mol Model (2015) 21: 230
HOMO (O2)
HOMO (CO)
LUMO (Au11)
Fig. 2 Selected catalytic sites in Au11
2108 cm1, respectively, which were also red-shifted from
their gas-phase values.
The bonding energy of the adsorption of CO on Au11 was
much lower than that of O2. The bonding energies of neutral
Ag2AuCO, AgAu2CO and Au3CO obtained from wave-
function-based coupled cluster singles doubles (CC-SD) are
Fig. 3 Reaction mechanism of Au11 +O2 +COP1+CO2. The energies
specified are the relative energies [difference between the electronic and
zero-point energies (ZPEs)]. Relative energies are in kJ mol1, bond
lengths are in ngstroms and bond angles in degrees. These units are
employed uniformly in all figures
Page 5 of 11 230
55.0, 68.5 and 95.5 kJ mol1 [21], which are comparable to
our theoretically determined values of CO adsorption on Au11.
O2 and CO co-adsorbed to the adjacent Au4 and Au6 sites to
facilitate oxygen transfer. In IM3, the Mulliken charge on C
decreased from 0.038 to 0.280 e, suggesting that charge was
transferred from CO to Au4.
Wang et al. [30] reported that the Pt4, Pt3Au1, Pt2Au2 and
PtAu3-mediated CO oxidation mechanisms involve both
single- and two-center pathways, while the Au4-mediated re-
action system does not exhibit a single-center pathway. In this
work too, a single-center reaction pathway was not observed.
First, in the Au11-mediated two-center CO oxidation mecha-
nism, the formation of IM3 decreased the relative energy (E)
by 232.0 kJ mol1, which was larger than that in the Au4-
mediated mechanism by 71.5 kJ mol1. Then the terminal
O13 atom on O2 transferred to CO via TS1 to produce IM4.
The imaginary frequency of TS1 at i464 cm1 was assigned to
the COO asymmetrical stretch mode, and the bond lengths
between the shifting O13C and O12 were 1.424 and 1.341 ,
respectively. In TS1, there was a COO structure, which has
been observed and validated by mass spectrometry in the CO
oxidation on Au(111) [7]. Both the potential-energy barrier
and free-energy barrier were very low at 38.5 and 49.1
kJ mol1, respectively, suggesting that this process was ener-
getically favorable. Figure 3 shows that the formation of IM4
also significantly reduced the E to 468.5 kJ mol1.
In IM4, CO2 linked with the adsorbed oxygen atom via a
very weak van der Waals interaction having a bond length of
2.819 . IM4 then decomposed into P1 and CO2 via a barrier-
less process, increasing the relative energy (E) slightly by
13.3 kJ mol1. In P1, the oxygen atom was positioned between
Au4 and Au6. This kind of bridging by oxygen on Au clusters
has been reported earlier [25, 26, 31, 51]. Table 1 also shows
that the oxidation process was strongly exothermic (459.1
kJ mol1).
Extraction of the oxygen atom in P1 by CO
In P1, the bond lengths between the adsorbed oxygen atom
and Au4, Au6 were 2.223 and 2.196 , respectively, showing
that the adsorption was weak. Calculated with the G09 pack-
age at the same basis set level, the Mulliken atomic spin den-
sity of the oxygen atom bonding with Au was 1.071 e, so this
atom seized the whole single electron and would have high
reactivity. So far, the reaction mechanisms that involve the
oxidation of CO molecules by adsorbed oxygen atoms on gold
clusters have seldom been investigated as catalyzed processes.
However, we have done so, as follows:
CO can seize the oxygen atom from P1. The geometrical
parameters and potential energy surface (PES) profile are il-
lustrated in Fig. 4. CO coordinated with Au4 and caused an
energy reduction of 32.8 kJ mol1, and the bond distance of
the newly formed AuC bond was 2.105 . Then CO
230 Page 6 of 11 J Mol Model (2015) 21: 230

mechanism of oxidizing residual CO-like products [6, 56].

Wang et al. [30] reported that the oxidation process occurs
on the Pt site, and Au is formally a spectator in bimetallic
Au-Pt clusters; moreover, both the single-center pathway
and two-center pathway start from the adsorption of CO on
the Pt site, as implied in theoretical investigations on the CO
oxidation by AumPdn (m+n=4) [30] and AumPdn (m+n=26)
[58]. In our case, since the selected Au4 site of Au11 had a
high catalytic performance, the Au4 atom in Au11 was re-
placed with Pt to yield the Au10Pt cluster. This cluster was
studied to investigate the two-center CO oxidation
mechanism.
The selected catalytic sites and the CO-oxidation mecha-
nism of Au10Pt are illustrated in Figs. 5 and 6. Figure 5 reveals
that CO bonded with Pt, and O2 coordinated with the neigh-
boring Au. The PtC and AuO bonds thus formed were
1.891 and 2.404 in length, respectively. The terminal oxy-
gen atom then transferred to the C atom via TS3 to produce
IM8, having a low barrier of 41.2 kJ mol1. The imaginary
frequency of TS3 at i351 cm1 corresponded to the COO
asymmetrical stretch. The bond length of the newly formed
CO bond was 1.875 , and the OO bond had extended to
1.288 . In IM8, the shifting oxygen atom linked to C, and the
OO was further extended to 1.453 , which was much lon-
ger than the OO bond in IM4 in the Au11-mediated CO
oxidation process. The whole oxidation process was also
highly exothermic (456.1 kJ mol1). Figure 6 shows that
P3 also bears a bridging oxygen atom with PtO and AuO
Fig. 4 Extraction of the oxygen atom on P1 by CO
bond lengths of 1.873 and 2.165 , respectively. In summary,
Fig. 5 illustrates that Au10Pt also exhibits an optimal catalytic
extracted the O atom via TS2 with a low barrier of 20.4
performance.
kJ mol1, forming IM6, where CO2 linked with Au6 via a
However, it is believed that the Pt atoms in PtAu bimetal-
weak van der Waals interaction. In TS2, the bond length of
lic catalysts act as active catalytic centers due to the strong
the newly formed CO bond was 2.001 , and its imaginary
adsorption of CO [30, 57], and the single-center pathway can
frequency at i259 cm1 was due to the Au6OC asymmetri-
compete with the two-center pathway. To verify this, we also
cal stretch, showing that carbon monoxide was extracting the
investigated the single-center CO oxidation mechanism on the
adsorbed oxygen atom from Au11. IM6 had a very low relative
Pt site of Au10Pt, as depicted in Fig. 7. Both CO and O2 were
energy (357.7 kJ mol1), and decomposed directly into P2
coordinated with Pt to form IM9, and the newly formed PtO
and CO2. Both Figs. 3 and 4 show that, after catalysis, the
structure of Au11 altered slightly, as implied in a previous
study [49].
Figures 3 and 4 attest that Au11 has a good catalytic per-
formance in the conversion of CO to CO2. Catalyzed by Au11,
one O2 molecule oxidates two CO molecules via stepwise
mechanisms. Moreover, the catalysis of CO by P1 was also
a strongly exothermal process. In the following calculations,
the catalytic performance of Pt-doped Au11 clusters will be
explored.

Catalytic mechanisms of Au10Pt

The most accepted explanation for the improved catalytic ac-

tivity of a bimetallic catalyst is based on the bi-functional Fig. 5 Selected catalytic sites in Au10Pt
J Mol Model (2015) 21: 230 Page 7 of 11 230

Fig. 6 Two-center mechanism of

Au10Pt+O2 +COP3+CO2

and PtC bonds were 2.094 and 1.872 in length. Then CO other part of IM12 via a weak coordination bond (2.818 ),
attracted an oxygen atom from O2 via TS4 to produce IM10. but was much stronger than the AuO coordination bond in
In TS4, the PtC bond was extended to 2.096 . The imagi- IM6. Figure 8 shows that IM12 and P5 are very stable species.
nary frequency of TS4 at i628 cm1 was due to the COO Our calculations suggest that O2 and CO should coordinate
asymmetrical stretch, and the newly formed CO bond dis- to different surface atoms of the AuPt clusters during the
tance was 1.812 . In IM10, CO2 linked with Pt via a weak
coordination bond of length 2.321 and the residual oxygen
atom was inserted over the PtAu bond on the surface of the
AuPt cluster, as depicted in Fig. 7. After the elimination of
CO2, the PtO and AuO bond lengths of P4 were 1.897 and
2.251 , respectively. In P1, P3 and P4 with a bridging O
atom, the O atom was on the surface in P1, but it was im-
planted between the PtAu bond in P3 and P4. Although the
relative energy of TS4 was lower than that of Au10Pt+O2 +
CO, the energy barrier of this process was 179.8 kJ mol1,
which was much higher than other barriers observed in this
work, implying that the single-center mechanism was energet-
ically unfavorable. Therefore, it will not be discussed further.
In P3, the AuO bond (2.165 ) was longer than the PtO
bond (1.873 ), so CO was added to this Au atom in order to
investigate the CO-oxidation mechanism of P3, as depicted in
Fig. 8. In IM11, the AuC bond was stronger than that in IM5,
and the PtO covalent bond (1.784 ) was normal, which
indicates that Pt has a higher adsorption activity than Au for
CO and O2. The formation of IM11 decreased the relative
energy by 27.9 kJ mol1, but increased the free energy slight-
ly. The barrier for oxygen extraction leading to IM12 via TS5
was very low (9.3 kJ mol1), indicating that the process was
highly feasible. In TS5, the AuO bond was extended from
1.784 to 2.827 , and the imaginary frequency at i170 cm1
belonged to the CO stretch mode. CO2 connects with the Fig. 7 Single-center mechanism of Au10Pt+O2 +COP4+CO2
230 Page 8 of 11
Fig. 8 Reaction mechanism of P3+COP5+CO2
oxidation of CO, and the two-center mechanisms are more
feasible. Compared to Au11, the bonding energies of Au10Pt
and CO are much lower, but both clusters exhibit good cata-
lytic performance. In the Au10Pt-catalyzed double-step two-
center mechanism, CO bonds to the Pt site, and the Au10Pt
cluster is distorted significantly because of the insertion of O
into the PtAu bond.
Liu et al. [31] have reported based on DFT calculations that
the Au75 cluster had the best catalytic activity among three
medium-sized decahedral Au clusters (Au 75 Au101 and
Au146). Our calculations also ratify that the Au11 cluster was
also the best catalyst for CO oxidation, as reported elsewhere
[32].
Catalytic mechanisms of Au9Pt2
In this case both Au4 and Au6 in Au11 were replaced with Pt
to form the Au9Pt2 cluster, and the adsorption and catalytic
mechanisms acting on these two Pt atoms were investigated,
as illustrated in Figs. 9 and 10.
To compare the catalytic activities of Au11 and Au9Pt2,
Au4 and Au6 in IM3 were substituted to obtain IM13 by full
optimization. In IM13, the PtC and PtO bonds were much
stronger than the corresponding AuC and AuO
J Mol Model (2015) 21: 230
Fig. 9 Reaction mechanism of Au9Pt2 +CO+O2 P6+CO2
coordination bonds in IM3, and the CO and O2 were activated
distinctly. Peng et al. [58] also demonstrated that CO and O2
adsorption the Pt atoms of AumPdn (m+n=26) bimetallic
clusters is stronger than on pure gold clusters. The imaginary
frequency of TS6 at i482 cm1 was due to the COO asym-
metrical stretch, denoting that an oxygen atom was transferred
from O2 to CO to yield IM14. Finally IM14 decomposed into
P6 and CO2 via a barrier-less process.
When the naked Pt atom in P5 was coordinated by CO to
produce IM15, P5 could oxidize another CO via the O-transfer
transition state TS7. In IM15, the PtO and PtC were 1.821
and 1.882 in length, so they were covalent bonds rather than
coordination bonds. In TS7, the newly formed C-O bond
length was 1.950 , and its imaginary frequency at i521
cm1 corresponded to the C-O stretch mode. After the catalyt-
ic cycle, the structure of Au9Pt2 changed significantly, as
shown in Fig. 10.
Although the catalytic mechanisms were analogous to
those of Au11 and Au10Pt, the potential energy barriers of
the two-step catalysis in Au 9 Pt 2 were 92.2 and 94.2
kJ mol1, respectively, which are higher than the above-
mentioned barriers. Therefore, in Pt-doped Au11 clusters, ox-
idation of CO will occur preferentially on the AuPt active
J Mol Model (2015) 21: 230
Fig. 10 Catalytic mechanism of P6+COP7+CO2
sites. However, in the CO oxidation mechanisms catalyzed by
Au9Pt2, the relative energies of transition states were much
lower than those of the reactants, so the reactants were on
the energy vertexes along the reaction coordinates, and the
reactions were all energetically favorable.
The adsorption of CO on the Au cluster is exothermic. Our
theoretical model revealed that, on Pt-doped Au clusters, larg-
er bonding energies are accompanied by higher energy bar-
riers, so an intermediate structure with a moderate bonding
energy and stability may be the ideal catalyst. Our calculations
also show that two-center mechanisms are energetically more
favorable. As a result, the oxidation of CO must occur on the
AuAu and AuPt centers.
Conclusions
The stepwise oxidation of CO catalyzed by Au11 and Pt-doped
Au11 clusters was investigated systematically by the hybrid
exchange-correlation M06 functional suite. It was found that
an O2 molecule oxidates two CO molecules via stepwise
mechanisms. In our theoretical model, the estimated differ-
ences between the electronic and ZPEs (E) were almost
equal to the corresponding relative thermal enthalpies (H).
The thermal enthalpies show that the oxidation of CO cata-
lyzed by Au11, Au10Pt and Au9Pt2 is highly exothermic.
Page 9 of 11 230
The adsorption of CO occurs on the active sites of doped
and undoped gold clusters, and a larger bonding energy may
denote a higher potential energy for the Pt-doped Au clusters.
Our calculations also reveal that CO is oxidized via two-center
mechanisms. In the two-center oxidation mechanisms cata-
lyzed by AuPt bimetallic clusters, the oxidation of CO occurs
on the AuPt centers and, after transfer of O from O2 to CO,
the residual oxygen atom is embedded into the AuPt bond on
the active sites.
Acknowledgments This work was supported by the National Natural
Science Foundation of China (No. 21173129 and 11174215), the Natural
Science Foundation of Shandong Province, China (No. ZR2012BL10)
and the University Science and Technology Planning Project of Shan-
dong Provincial Education Department (No. J13LD05).
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