Computational Materials Science 96 (2015) 237–245

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Computational Materials Science

journal homepage: www.elsevier.com/locate/commatsci

DFT studies on Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh) clusters for CO oxidation
Xin Lian a, Wenlong Guo a, Feila Liu a, Yang Yang a, Peng Xiao b, Yunhuai Zhang a,⇑, WeiQuan Tian c
a
College of Chemical Engineering, Chongqing University, Chongqing 400044, China
b
College of Physics, Chongqing University, Chongqing 400044, China
c
State Key Laboratory of Urban Water Resource and Environment, Institute of Theoretical and Simulational Chemistry, Academy of Fundamental and Interdisciplinary Sciences,
Harbin Institute of Technology, Harbin 150080, China

a r t i c l e i n f o a b s t r a c t

Article history: The reaction mechanism of CO oxidation catalyzed by several Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh) clusters
Received 8 July 2014 has been investigated with density functional theory calculations in the present work. The reaction pre-
Received in revised form 15 September 2014 fers to proceed via Langmuir–Hinshelwood mechanism. The calculated barriers for the reactions medi-
Accepted 20 September 2014
ated by bimetallic clusters are comparable with that catalyzed by monometallic Pt4 cluster. According
Available online 11 October 2014
to thermodynamics and kinetics results, CO oxidation can take place readily without thermal activation
and the O2 scission to form OCOO* is the rate-determining-step. Pt3Mo exhibits superior catalytic activity
Keywords:
for CO oxidation among all those investigated clusters and good adsorption for O2. The different perfor-
CO oxidation
Bimetallic clusters
mance of those bimetallic clusters for CO oxidation is scrutinized with aid of molecular orbital and nat-
Catalysis ural bond orbital population analysis.
Kinetics Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction the O2 concentration increases to 2%, the CO conversion increases

Catalytic oxidation of CO has been extensively studied due to its
importance for both fundamental research and industrial applica-
tions, e.g. tail gas processing [1] and purification of hydrogen for
proton-exchange membrane fuel cells (PEMFCs) [2]. Among vari-
ous heterogeneous catalysts, precious metals, Pt [3–6], Ru [7,8],
Pd [9–12], and Au [13–15] are efficient catalysts for oxidation of
CO with O2. In comparison with other noble metals, Pt catalysts
show the most promising performance and are considered as ideal
electrode materials in fuel cells. However, the limited Pt source and
deactivation by trace amounts of CO are two challenging issues for
its large scale application [16]. Therefore, it is well desirable to find
suitable Pt-based catalysts both economically and chemically effi-
cient for CO oxidation.
To this end, an alternative strategy to enhance the reactivity of
Pt nanoparticles, alloying Pt nanoparticles with a second metal to
form a bimetallic Pt catalyst (‘‘nano-alloy’’) has attracted signifi-
cant attention. Some Pt-based binary-alloy catalysts, such as
Pt–Ni [17,18], Pt–Mo [19–21], Pt–Sn [22,23], Pt–Co [24,25], Pt–Au
[26], and Pt–Ru [27,28], possess better activity and stability than
the corresponding monometallic catalysts for CO oxidation. Pt/Ru
with atomic ration of 2:1 achieves 90% CO conversion and 90%
CO2 selectivity at 150 °C [29]. The most active catalyst of Pt–Pd/
CeO2 has a composition of Pt/Pd = 1/7 [30]. On this catalyst, when
⇑ Corresponding author.
to 99% at 90 °C. A 4:1 ratio was proposed for PtMo alloy catalyst
[20], with this ratio, the PtMo catalyst displays the lowest onset
oxidation potential, i.e. the highest activity for CO oxidation.
Two possible mechanisms [31–35] have been proposed to
explain the activities for CO oxidation of Pt-based catalysts. One
is based on the promotion of CO oxidation on Pt atoms by a second
metal which produces OH-type species at lower potential. The
other one is the ligand mechanism, which is based on modification
of electronic property of the Pt by a second metal in the catalyst.
The modified electronic property results in the different chemi-
sorption (or lower desorption energy) of the catalyst for CO so that
the CO coverage on the Pt sites used for H2 oxidation is reduced.
Theoretical works have been devoted to investigate CO oxidation
on Pt-based alloys to study the possible mechanism for the
enhanced activity of Pt-based bimetallic catalysts for CO oxidation.
However, the possible mechanism is not yet clear. For example, Pt/
Ru [36,37] catalysts show superior activity toward methanol oxi-
dation, because dehydrogenation process occurs on Pt site while
Ru site provides oxygenated species for CO oxidation according
to the bifunctional mechanism. On the contrary, in Pt/Au [38] cat-
alysts, Au does not participate in reaction directly and its crucial
role is to stabilize Pt by enhancing the oxidation potential of Pt.
Extensive experimental studies found that the presence of sec-
ond metals (Ni, Mo, Ru, Pd, Rh), either alloyed or co-deposited with
Pt, yields significant improvement on the CO tolerance. However,
there are few reports on how these transition metals doped Pt

http://dx.doi.org/10.1016/j.commatsci.2014.09.025
0927-0256/Ó 2014 Elsevier B.V. All rights reserved.
238 X. Lian et al. / Computational Materials Science 96 (2015) 237–245

Table 1
The ground states for the complexes of Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh) with O2 or CO. The superscripts and values in square brackets
denote the electronic states and the binding energies, respectively. Pt, Ni, Mo, Ru, Pd, Rh, C and O atoms are represented by blue, violet,
turquoise, light-sea green, teal, dark-cyan, gray and red spheres.

>(E H9@ >(E H9@ >(E H9@ >(E H9@ >(E H9@ >(E H9@

>(DGV H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@

>(E H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@ >(DGV H9@

Fig. 1. Optimized geometries of intermediates and transition states involved in the CO oxidation in path I and path II on Pt4. Pt, C and O atoms are represented by blue, gray
and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

catalysts improve the activity on CO oxidation. The reactions of
Pt-based bimetallic clusters can provide useful information for
understanding the mechanisms involved in the realistic and
complicated catalytic systems [39,40].
In the present work, the reaction mechanism of CO oxidation on
Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh) clusters will be studied with den-
sity functional theory (DFT) based calculations. Reaction processes
via single-center pathway and two-center pathway approaching
the Pt and M atoms of Pt3M are considered. The most favorable
reaction pathways of CO oxidation on each bimetallic catalyst are
identified and the enhanced catalytic activity of those bimetallic
clusters is scrutinized.
2. Computational detail and models
Due to there are usually no more than 4 atoms on the top level
of surface participate in reaction of small molecules [41] and tetra-
hedral Pt3M used to be considered as the representative to illus-
trate catalytic problems [38,42], tetrahedral Pt3M (M = Pt, Ni, Mo,
 X. Lian et al. / Computational Materials Science 96 (2015) 237–245
Fig. 2. Potential energy curve for CO oxidation promoted by Pt4 along path I (black
line) and path II (red line). The energies include zero-point energy corrections. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
Ru, Pd, Rh) was used to model the subnanoscale particle catalysts
in this work. All calculations were performed with the Gaussian03
package [43]. DFT based method B3LYP [44–46] was used for reac-
tion pathway location and property analyses. The LANL2DZ [47]
effective core potential and basis set for metal atoms, and the 6-
311G+(d) [48] basis set for C and O atoms were employed. No sym-
metric constraints were imposed during geometrical optimizations
and various spin multiplicities were considered for metal clusters.
Frequency analysis for the all stationary points was performed at
the same level of theory to characterize the stationary points and
make the zero-point-energy (ZPE) corrections. Intrinsic reaction
coordinates (IRC) calculations were carried out to verify that each
saddle point links two desired minima.
The chemisorption energy of CO and O2 was calculated using
the following Eq. (1):
 
Eads ¼ ECO=O2 þ EPt3M  ECO=O2 Pt3M ð1Þ
Fig. 3. Optimized geometries of intermediates and transition states involved in the CO oxidation in paths I, II and III on Pt3Ni. Pt, Ni, C and O atoms are represented by blue,
violet, gray and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
239
3. Results and discussion
3.1. Adsorptions of CO and O2 on Pt3M clusters
Various geometries have been optimized for adsorption of O2
and CO on different adsorption sites of Pt3M (M = Pt, Ni, Mo, Ru,
Pd, Rh) clusters in different spin multiplicities. The most stable
conformations were chosen to study the possible complexes for
CO oxidation.
For CO adsorption, the molecule prefers the ‘‘end-on’’ [49] con-
formations with C atom binding to the metal atoms. As shown in
Table 1, the adsorption energies (Eads) of CO on the Pt sites are
much larger than those on the M sites, thus that CO prefers to bind
to the Pt sites when both Pt and M sites are available. Pt4 cluster
has the highest adsorption energy 2.38 eV, which is about
0.37 eV higher than that of Pt3Rh cluster (the weakest adsorption).
With the doping of M atom dope into Pt clusters, the CO adsorption
energy is lower than that on pure Pt cluster, and it results in less
CO poisoning of catalysts. The CO bond length elongates slightly
from initial 1.13 Å to 1.15 Å.
However, the O2 molecule prefers the ‘‘side-on’’ configurations
with both oxygen atoms binding to metal atoms. The calculated Eads
of O2 on both Pt and M sites are lower than those of CO. On Pt3Ru,
Pt3Ni and Pt3Rh, O2 binds the M sites while it binds to the Pt sites
on Pt3Pd and Pt3Mo. O2 has much lower adsorption energy on Pt3Pd
and Pt3Rh than on other investigated clusters. The small O2 adsorp-
tion energy, in comparison with CO, is attributed to the strong elec-
tronegativity of O atom [50], which enables O2 to attract electrons
strongly. This is also evidenced by the elongated O2 bond length sig-
nificantly from 1.20 Å to 1.30 Å activated upon adsorption.
From the above discussion, we demonstrated that both CO and
O2 molecules can adsorb on the various metal clusters which will
provide the initial stage for the catalytic reaction of CO oxidation.
Because CO has much stronger adsorption energy than that of O2,
240 X. Lian et al. / Computational Materials Science 96 (2015) 237–245

Fig. 4. Potential energy curve for CO oxidation promoted by Pt3Ni along path I Fig. 6. Potential energy curve for CO oxidation promoted by Pt3Mo along path I
(black line), path II (red line) and path III (blue line). The energies include zero-point (black line), path II (red line) and path III (blue line). The energies include zero-point
energy corrections. (For interpretation of the references to colour in this figure energy corrections. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.) legend, the reader is referred to the web version of this article.)

we can conclude that the active sites in bimetallic clusters would
be first occupied by the coming CO rather than O2, while O2 is more
easily activated by the metal clusters compared to CO.
3.2. CO oxidation on Pt3M (M=Pt, Ni, Mo, Ru, Pd, Rh) clusters
Due to the stronger adsorption of CO on those bimetallic clus-
ters that O2, the Langmuir–Hinshelwood mechanism is considered
in the present work [51,52]: the co-adsorbed CO and O2 firstly form
a peroxo-type complex intermediate, i.e., CO (gas) + O2 (gas) ?
OOCO* ? CO2 + O (ads). According to preference of adsorption of
CO and O2 on Pt3M, there are three possible pathways for CO oxi-
dation [38,53]. In path I, both CO and O2 adsorb on the same Pt site.
In path II, the adsorption of CO and O2 occurs on the two Pt sites. In
order to probe whether bifunctional mechanism works for CO oxi-
dation on these clusters, CO and O2 bind to Pt and M sites respec-
tively in path III.
Pt4 þ CO þ O2
In a previous work, Wang et al. [38] studied PtmAun (m + n = 4)
and CO oxidation on Pt4 cluster. Comparative studies on the CO
oxidation were carried out in the present work with those in
Wang’s work.
Fig. 2 displays the potential energy profiles of CO oxidation on Pt4
and the structures of all stationary points along this potential energy
curve are summarized in Fig. 1. IM1 and IM1* in paths I and II are
similar to those in a previous work [38], whereas they have lower
adsorption energies (52.92 and 64.46 kcal/mol). The breaking
of O–O bond goes through transition states of TS1–2 and TS1 —2
and the energy barriers are 21.25 kcal/mol and 38.74 kcal/mol
respectively. The conversion from IM2 (IM2*) to IM3 (IM3*) has to
overcome TS2–3 (TS2 —3 ), the energy barrier is much lower than
the one from IM1 (IM1*) to IM2 (IM2*). The overall potential energy
curve is similar to that in Wang’s work except for slight structure
and energy difference caused by the choice of method.

Fig. 5. Optimized geometries of intermediates and transition states involved in the CO oxidation in paths I, II and III on Pt3Mo. Pt, Mo, C and O atoms are represented by blue,
turquoise, gray and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
 X. Lian et al. / Computational Materials Science 96 (2015) 237–245
Fig. 7. Optimized geometries of intermediates and transition states involved in the CO oxidation in paths I, II and III on Pt3Ru. Pt, Ru, C and O atoms are represented by blue,
light-sea green, gray and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 8. Potential energy curve for CO oxidation promoted by Pt3Ru along path I
(black line), path II (red line) and path III (blue line). The energies include zero-point
energy corrections. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
Pt3 M ðM ¼ Ni; Mo; Ru; Pd; RhÞ þ CO þ O2
Figs. 3–12 show the predicted potential energy profiles and the
structures of all stationary points for CO oxidation promoted by
Pt3Ni, Pt3Mo, Pt3Ru, Pt3Pd and Pt3Rh bimetallic clusters.
Three models of CO and O2 co-adsorption on Pt3Ni are shown in
Figs. 3 and 4. In path I, CO and O2 initially are co-adsorbed on the
single Pt atom to form IM4 and the adsorption energy
(52.92 kcal/mol) is larger than that on Pt4. The CO bond length
is 1.14 Å, nearly the same as that in the adsorption of CO, but the
O–O bond slightly shrinks from 1.30 Å (single adsorption) to
1.25 Å (co-adsorption). Conversion from IM4 to IM5 takes place
through a transition state TS4–5 with a barrier of 21.08 kcal/mol,
slightly lower than that on Pt4. In TS4–5, the O–O bond elongates
to 1.35 Å, and the distance of C (CO)–O (O2) is shortened to
1.65 Å. After overcoming a relatively high energy barrier transition
241
state, the O–O bond breaks to form atomically adsorbed intermedi-
ate IM5. IM5 is a peroxide-like specie [54,55], where the O–O dis-
tance elongates to 1.51 Å and the net change on CO is still small.
This is similar to that on Pt4 while with smaller second reaction
barrier (12.12 kcal/mol). The O–O distance elongates to 1.91 Å
while C (CO)–O (O2) bond contracts to 1.27 Å in TS5–6. CO2 is
released upon further elongation of the O–O bond and IM6 forms,
IM6 is 93.16 kcal/mol more stable than the reactants.
In path II, CO and O2 approach two Pt atoms to form adsorption
complex IM4* with adsorption energy 64.45 kcal/mol, which is
more stable than IM4 by 11.53 kcal/mol. IM4* has to pass through
a five-membered ring transition state (TS4 —5 ) with an energy bar-
rier of 30.19 kcal/mol. Similar to path I, the formation of the per-
oxo-like intermediate IM5* is exothermic by 39.73 kcal/mol. The
O–O bond lengthens further to transition state TS5 —6 with an
energy barrier of 9.25 kcal/mol. A CO2 molecule forms upon the
formation of IM6*.
In path III, CO and O2 adsorb on Pt and Ni atoms respectively.
Adsorption of CO takes place on Pt atom while O2 in bridge position
on Ni atom to form IM4** intermediate, which is 78.79 kcal/mol
more stable than the reactants. IM4** converts into IM5** via tran-
sition state TS4 —5 with an energy barrier of 42.44 kcal/mol. With
the distance of O–O getting longer, IM5** further evolves into IM6**,
a complex of Pt3NiO with CO2 with 88.84 kcal/mol more stable
than the reactants.
The potential energy curve and the structure along the reaction
path of other clusters are very similar to those of Pt3Ni. The calcu-
lated barriers of the first transition state along path I are
20.58 kcal/mol, 20.29 kcal/mol and 21.02 kcal/mol for Pt3Rh, Pt3Ru
and Pt3Pd clusters, while those corresponding barriers into the
path II are 41.05 kcal/mol, 30.83 kcal/mol and 34.93 kcal/mol
respectively. Path I is energetically more favorable than path II.
However, in path III (CO on Pt and O2 on the doped metal), the bar-
rier of first transition state is higher than those in path I and path II
for all clusters, i.e. the bifunctional mechanism is not favorable.
242 X. Lian et al. / Computational Materials Science 96 (2015) 237–245
Fig. 9. Optimized geometries of intermediates and transition states involved in the CO oxidation in paths I, II and III on Pt3Pd. Pt, Pd, C and O atoms are represented by blue,
teal, gray and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 10. Potential energy curve for CO oxidation promoted by Pt3Pd along path I
(black line), path II (red line) and path III (blue line). The energies include zero-point
energy corrections. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
It is worth noting that in Pt3Mo, the first energy barriers in path
I and path II are similar to the other clusters. However, in path III,
the energy barrier is only 15.41 kcal/mol and it is lower than that
in path I (19.54 kcal/mol) and path II (30.93 kcal/mol), the lowest
one among all barriers. The bifunctional mechanism occurs feasi-
bly on Pt3Mo. Mo atom prefers to adsorb O2 molecule and activates
O2 at low energy when CO adsorbs on Pt site, and this facilitates
the oxidation of CO.
On all those clusters, the reaction intermediates and transition
states along the reaction path are all more stable than the reac-
tants, thus that the reaction proceeds readily without thermal acti-
vation [56]. The reaction takes two steps [55]: the first step
involves the O–O elongation and CO binding of CO to one O atom
of O2 to form a peroxide-like (OOCO) intermediate, and the second
step involves the cleavage of O–O bond of peroxide to produce
CO2.
The reactions barriers of three paths for all clusters are summa-
rized in Fig. 13. For path I, the reactions barriers on all clusters are
similar. The barriers in path I are much lower than the other two
pathways except path III on Pt3Mo. For path II, although the barri-
ers of the transition states are higher than that in path I for all clus-
ters, the barriers in bimetallic clusters are much lower than that on
Pt4 except for Pt3Rh. The comparison of reaction barriers in path III
with those in paths I and II finds that bifunctional mechanism work
only on Pt3Mo.
3.3. Reaction rate constants
The pre-exponential factors and rate constants of a reaction
can be determined according to transition-state theory (TST)
[57,58]:
 
kB T Q TS DH i
kTST ¼ exp  ð2Þ
h Q IM RT
kB T Q TS
A0;i ¼ ð3Þ
h Q IM
where DHi is the enthalpy difference between the initial stateand
the transition state, kB is the Boltzmann constant, T is temperature;
Q TS and Q IM are the partition functions of transition state and inter-
mediate, R is the gas constant and h is the Planck constant.
The predicted constants are presented in Table 2. In all cases,
the rate constants for the formation of the initial OCOO* interme-
diate outbalance the rate constants for dissociation of the O–O
bond from the OCOO*. A difference of more than 20 orders of
magnitude suggests that O2 scission to form OCOO* is the slow-
est step for CO oxidation. Thus, the dissociation of O–O is the
rate-determining step for CO oxidation. The rate constants of
rate-determing step in path I are larger than those of paths II
and III by over 10 orders of magnitude indicating the path I is
 X. Lian et al. / Computational Materials Science 96 (2015) 237–245 243

Fig. 11. Optimized geometries of intermediates and transition states involved in the CO oxidation in paths I, II and III on Pt3Rh. Pt, Rh, C and O atoms are represented by blue,
dark-cyan, gray and red spheres. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 12. Potential energy curve for CO oxidation promoted by Pt3Rh along path I
Fig. 13. The energy barrier of rate-determining step for CO oxidation on Pt3M
(black line), path II (red line) and path III (blue line). The energies include zero-point
(M = Pt, Ni, Mo, Ru, Pd, Rh).
energy corrections. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

to improve the performance of catalyst. As shown in Fig. 14, the

favored over paths II and III. The synergetic effect of binary
alloys plays a significant role in CO oxidation reaction except
path III in Pt3Ni and path II in Pt3Rh according to the predicted
rate constants. The doping metal M (Ni, Mo, Ru, Pd, Rh) exhibits
a positive ligand effect on the rate-determing step for CO oxida-
tion on Pt-based alloys, i.e. with improved catalytic activity.
Pt3Mo has the highest rate constants of rate-determing step for
CO oxidation among all clusters [59] judged from the rate con-
stants listed in Table 2.
3.4. Molecular orbital and nature bond orbital analysis
The O–O bond breaking is the rate-determining step for CO oxi-
dation according to reaction barrier and reaction rate constant
analyses. Further analysis on the bonding of O2 with catalyst helps
bimetallic clusters have similar HOMO (highest occupied molecu-
lar orbital) and LUMO (lowest unoccupied molecular orbital) ener-
gies and HOMO–LUMO energy gaps, thus they have similar
interactions with O2 to form adsorption complexes. The energy dif-
ference [42] between E (LUMO, O2) and E (HOMO, Pt3Mo) is the
smallest and that between E (LUMO, Pt3Mo) and E (HOMO, O2) is
larger than Pt4 and Pt3Pd. Therefore, the small energy difference
makes Pt3Mo easier to activate O2. The natural atomic charge for
O2 adsorption on bimetallic clusters is listed in Table 3. O2 gets
the largest amount of electrons when adsorbed on Pt3Mo, thus
with the highest activation on the O–O bond. The frontier molecu-
lar orbital and nature bond orbital (NBO) charge analyses reveal
the relative catalytic activities of those bimetallic clusters and
Pt3Mo is the best catalyst for CO oxidation among the clustered
investigated.
244 X. Lian et al. / Computational Materials Science 96 (2015) 237–245

Table 2
Pre-exponential factor and rate constants for CO oxidation on Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh). (At 298 K, PCO = PO2 = 0.1 bar).

O2(ads) + CO(ads) ? OOCO(ads) OOCO(ads) ? CO2(ads) + O(ads)

A (1/s) K (1/s) A (1/s) K (1/s)
Pt4 Path I 1.18  1011 3.07  105 2.41  1014 3.94  105
Path II 7.43  1010 2.87  1018 6.68  1013 2.09  1011
Pt3Ni Path I 1.05  1011 3.36  105 2.80  1014 3.61  105
Path II 8.18  1010 5.90  1012 7.74  1013 1.27  107
Path III 1.52  1012 2.33  1020 9.50  1015 1.87  103
Pt3Mo Path I 1.82  1011 8.49  104 6.61  1013 2.18  106
Path II 5.10  1011 1.05  1011 2.22  1014 3.10  109
Path III 5.29  1010 0.264 9.05  1013 1.18  1011
Pt3Ru Path I 1.03  1011 1.35  104 1.25  1014 3.36  104
Path II 1.25  1012 3.06  1011 5.38  1013 7.51  108
Path III 3.50  1011 8.72  1015 3.08  1013 1.69  109
Pt3Pd Path I 1.21  1011 4.60  105 6.97  1014 1.01  106
Path II 3.58  1011 8.62  1015 3.20  1014 3.28  1010
Path III 1.75  1011 1.07  1017 4.22  1013 6.63  108
Pt3Rh Path I 1.03  1011 8.27  105 1.99  1014 1.88  106
Path II 1.04  1012 8.12  1019 1.83  1013 9.10  1010
Path III 1.03  1012 1.92  1014 1.47  1014 1.46  109

the bifunctional mechanism, to catalyze CO oxidation with high

efficiency. The high catalytic efficiency of Pt3Mo (possibly Mo
doped Pt cluster) on CO oxidation deserves experimental trial.

Acknowledgments

WQT thank supports from the State Key Lab of Urban Water
Resource and Environment (HIT) (2014TS01) and the Open Project
of State Key laboratory of Supramolecular Structure and Materials
(JLU) (SKLSSM201404).

References

Fig. 14. Energies of HOMOs and LUMOs of O2 and Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh).
Table 3
Natural atomic charges of O2 adsorbed on Pt3M (M = Pt, Ni, Mo, Ru, Pd, Rh).
Pt4 Pt3Mo Pt3Ru Pt3Pd Pt3Ni
O2 0.343 0.711 0.439 0.428 0.465
4. Conclusions
Theoretical exploration on the reactivity of Pt3M (M = Pt, Ni, Mo,
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inducing more charge transfer to O2. Different from the other
bimetallic clusters, Pt3Mo takes path III (CO on Pt and O2 on Mo),
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