Applied Surface Science 328 (2015) 71–77

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Applied Surface Science

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

CO catalytic oxidation on iron-embedded monolayer MoS2

Dongwei Ma a,∗ , Yanan Tang b , Gui Yang a , Jun Zeng a , Chaozheng He c , Zhansheng Lu d
a
School of Physics, Anyang Normal University, Anyang, Henan 455000, China
b
Department of Physics and Electronic Science, Zhengzhou Normal University, Zhengzhou, Henan 450044, China
c
Physics and Electronic Engineering College, Nanyang Normal University, Nanyang 473061, China
d
College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, Henan 453007, China

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

Article history: Based on first-principles calculations, the CO catalytic oxidation on the Fe-embedded monolayer MoS2
Received 15 October 2014 (Fe-MoS2 ) was investigated. It is found that Fe atom can be strongly constrained at the S vacancy of mono-
Received in revised form 3 December 2014 layer MoS2 with a high diffusion barrier. The CO oxidation reaction proceeds via a two-step mechanism
Accepted 3 December 2014
with the highest energy barrier of 0.51 eV, which is started by the Langmuir–Hinshelwood reaction and
Available online 10 December 2014
ended by the Eley–Rideal reaction. The high catalytic activity of the Fe-MoS2 system may be attributed
to the charge transfer and the orbital hybridization between the adsorbates and the Fe atom. This study
Keywords:
proposes that embedding transition-metals is a promising way for making the basal plane of monolayer
First-principles calculations
CO oxidation
MoS2 catalytically active.
Fe-embedded monolayer MoS2 © 2014 Elsevier B.V. All rights reserved.

1. Introduction
As one of the most promising two-dimensional (2D) materials,
graphene, one-atom-thick layers of sp2 -bonded carbon, has shown
exceptional physical, chemical, optical, and mechanical proper-
ties [1,2]. Recently, other 2D materials have attracted increasing
attention [3]. In particular, great interest has been focused on
the monolayer transition-metal dichalcogenides [4,5], such as
monolayer molybdenum disulfide (MoS2 ), which is proved to
be a versatile material for a wide variety of applications owing
to its unique physical, optical, and electrical properties [6–9].
Researchers have realized the growth of large high-quality MoS2
sheets [10–13] and have proposed and investigated possible appli-
cations, such as low-power transistors [14,15], phototransistors
[16,17], sensors [17–20], hydrogen evolution reactions [21,22], and
lithium ion batteries [5,23–25].
A monolayer MoS2 sheet consists of three atomic layers: a Mo
layer sandwiched between two S layers. Since there is no dangling
bond at the basal plane terminated by S atoms, the planes of MoS2
are chemically inert, like graphene, and these S atoms are not
expected to be chemical activity. The catalytically active sites of
MoS2 are considered to be their edges, containing undercooor-
dinated S or Mo atoms, which are expected to interact strongly
with adsorbates [21,26]. The MoS2 -based materials are used in
petrochemical hydrodesulfurization and hydrodenitrogenation
∗ Corresponding author. Tel.: +86 372 2900041.
E-mail address: dwmachina@126.com (D. Ma).
processes [27]. With the aid of alkali, MoS2 is also used for con-
verting synthesis gases (syngas) to alcohol [28]. The particular
optical direct band gap of the monolayer MoS2 also makes it a
potential candidate for an efficient and viable material for electro-
and photoelectrocatalytic hydrogen evolution [22,29,30].
Creation of S vacancy could provide a facile route for making
the basal plane of the MoS2 layer catalytically active. More impor-
tantly, if creation of S vacancy can be performed in a controlled
way, it would be possible to produce a large number of active
sites on the basal plane, far more than the number provided by
the edges [26]. The experiments have shown that controlled cre-
ation of S vacancy on MoS2 is possible by using low-energy argon
sputtering [31] or electron irradiation [32,33]. Furthermore, very
recently, the potential of S vacancies serving as catalytically active
sites has been explored theoretically by using density functional
theory (DFT) calculations [26,34]. Ciraci et al. suggested that the
MoS2 triple vacancies are suitable medium for the dissociation of
H2 O [34] and Rahman et al. [26] suggested that the S vacancies can
serve as the active sites for alcohol synthesis from syngas.
Furthermore, embedding impurity species by filling the S vacan-
cies into the monolayer MoS2 could be also a promising route for
making the basal plane of monolayer MoS2 catalytically active.
There have been numerous experimental and theoretical studies
on the doping of traditional oxide catalysts, such as CeO2 and TiO2
[35]. Transition-metal-embedded graphene and monolayer hexag-
onal boron nitride (BN) have also been theoretically predicted to be
good candidates for highly efficient catalysts with low cost [36–48].
Recently, we theoretically investigated the CO oxidation by Si [43]
and several transition-metals (such as Pt, Al, Zn, Co, and Ni) [39,44]

http://dx.doi.org/10.1016/j.apsusc.2014.12.024
0169-4332/© 2014 Elsevier B.V. All rights reserved.
72 D. Ma et al. / Applied Surface Science 328 (2015) 71–77
embedded graphene, which shows that these embedded external
elements can convert the inert graphene supports to highly active
catalysts. Furthermore, it has been experimentally [49,50] and the-
oretically [51,52] shown that metal subnanoclusters on graphene
have very high catalytic activity.
Inspired by the above findings, this work has investigated the
potential of embedding transition-metals into monolayer MoS2 as
a route for making its basal plane catalytically active, by which we
may significantly extend the application of this distinctive 2D mate-
rial. We have chosen Fe as the dopant, since it has several unique
characteristics: inexpensive, environmentally benign, readily avail-
able, and rich in the earth. The combination of Fe and MoS2 may
provide us with an earth-abundant and low-cost alternative to
the precious metals catalysts [22]. The CO oxidation reaction has
been investigated to examine the catalytic performance of the
Fe-embedded monolayer MoS2 (Fe-MoS2 ), as CO is one of the poi-
sonous and harmful gases in the air and its oxidation is often
regarded as an important prototypical reaction for heterogeneous
catalytic process [53]. Our calculated results show that Fe-MoS2
can exhibit the catalytic behavior similar to those of the transition-
metal embedded graphene or BN.
2. Computational details
All the calculations were performed with the projected
augmented wave (PAW) formalism of DFT, as implemented
in the Vienna Ab-initio Simulation Package (VASP) [54–56].
The generalized gradient approximation method with
Perdew–Burke–Ernzerhof (PBE) for the exchange-correlation
energy was used [57]. The cutoff energy for the planewave basis
set was taken as 450 eV. The Brillouin zone integrations were
performed by using Monkhorst-Pack grid of 3 × 3 × 1 [58] and a
Gaussian smearing of 0.1 eV. The convergence of the total energy
was considered to be achieved until two iterated steps with
energy difference less than 10−5 eV. Structure optimizations were
performed until the Hellmann–Feynman force on each atom
was less than 0.02 eV/Å. During the optimization, all the internal
coordinates were allowed to relax with a fixed lattice constant.
The climbing image nudged elastic band method [59] was used
to find the minimum-energy path (MEP) for the reactions. Four to
eight images were inserted in between the initial state (IS) and
final state (FS), and the spring force between adjacent images
was 5.0 eV/Å. The geometric optimization and the search for the
transition state (TS) are tested by means of frequency calculations.
The lattice parameter of monolayer MoS2 was optimized to be
3.19 Å, which is in good agreement with the experimental (3.20 Å
[60]) and theoretical values (3.18 Å [26]; 3.20 Å [61]). The bond
length (S S, 3.13 Å; S Mo, 2.42 Å), bond angle (S Mo S, 80.65◦ ),
and band gap (1.50 eV) of the monolayer MoS2 are in good agree-
ment with the results in Ref. [61]. To simulate the Fe-MoS2 system, a
4 × 4 supercell has been introduced, where a Fe atom is substituted
for one S atom for per cell. The distance between the monolayer
MoS2 sheet and its neighboring image is about 15 Å, which is suffi-
ciently large to avoid the interactions between them.
3. Results and discussion
3.1. Structures and stability of Fe-MoS2
Firstly, we present the results on the geometric and electronic
structures as well as the magnetic properties of Fe-MoS2 . As shown
in Fig. 1, the embedded Fe atom located on the S vacancy forms
three bonds with the neighboring three Mo atoms. The bond length
between the Fe and three Mo atoms are about 2.6 Å and the Fe
atom slightly protrudes above the S plane. Meanwhile, there is
about 0.37e transfer from the embedded Fe to monolayer MoS2
sheet according to the Bader charge analysis [62], which is mainly
accepted by the neighboring Mo atoms. The direction of electron
transfer is in agreement with the values of Pauling electronegativity
of two elements (Fe 1.83 vs. Mo 2.16) [63]. The electron trans-
fer can also be verified by the charge density difference (CDD) of
Fe-MoS2 . As shown in Fig. 1(a), the yellow and cyan regions repre-
sent the areas of electron accumulation and depletion, respectively.
Obviously, different electron affinities of Fe and Mo determine the
electron distribution around the dopants, and the transferred elec-
tron from the Fe is mainly located between the Fe Mo bonds. The
magnetic moment of the whole system is 2.29 B and is mainly
located on the Fe and its neighboring Mo atoms, which are antifer-
romagnetic coupling, as shown in Fig. 1(b).
To gain more insight into the electronic structure of Fe-MoS2 ,
the spin-polarized local densities of states (LDOS) projected on the
3d and 4s orbitals of the Fe as well as the 4d and 5s orbitals of its
neighboring Mo are plotted, as shown in Fig. 1(c). When Fe atoms
are located on the S vacancies, the Fe 3d and 4s orbitals are signif-
icantly broadened compared with the sharp peak of the isolated
atoms, which shows the strong interaction between the Fe and
its neighboring Mo atoms. Due to the charge transfer, the spin-up
and spin-down DOS of the 4d orbitals of the Mo atoms are slightly
asymmetric. Importantly, there are localized Fe 3d orbitals near the
Fermi level, which is important to activate the adsorbed reactants
as discussed later.
To see whether the S vacancy can strongly constrain the embed-
ded Fe atom, we also calculated the adsorption of Fe on the various
sites near the S vacancy. Here, the Fe adsorption energy is defined
as: Ead (Fe) = E(MoS2 ) + E(Fe) − Etot (Fe/MoS2 ), where E(MoS2 ), E(Fe),
and Etot (Fe/MoS2 ) are the total energies of the monolayer MoS2
with a S vacancy, the free Fe atom, and the defective MoS2 with
a adsorbed Fe atom, respectively. After optimization, we have
obtained two stable configurations, for which the Fe atom sits
on the top of the Mo atom (the FS in Fig. 2(a)) or the center of
the S Mo S hexagonal ring (the FS in Fig. 2(b)) of the defective
monolayer MoS2 . The adsorption energy for the Fe-MoS2 system is
4.00 eV, again indicating that Fe atom can interact strongly with
its neighboring undercoordinated Mo atoms. The energy barri-
ers for the diffusion of the trapped Fe to the top site of the Mo
atom (Fig. 2(a)) and the hollow site of the S Mo S hexagonal ring
(Fig. 2(b)) are 2.00 and 1.89 eV, respectively. The high adsorption
energy for the Fe-MoS2 system and the large energy barrier for
the diffusion of the trapped Fe in the S vacancy to the nearby sites
ensure the absence of the clustering problem of the embedded Fe
atoms and a stable catalyst at room temperature.
3.2. Adsorption of gas molecules on Fe-MoS2
Before investigating the CO oxidation reaction, we computed the
adsorption of CO, O2 , O, and CO2 on the Fe-MoS2 . Various adsorption
configurations have been considered in order to find the most stable
one for each adsorbate. The adsorption energy of the adsorbates is
defined as: Ead (ads) = E(Fe-MoS2 ) + E(ads) − E(ads/Fe-MoS2 ), where
E(Fe-MoS2 ), E(ads), and E(ads/Fe-MoS2 ) are the total energies of
the Fe-MoS2 system, the free adsorbates in the gas phase, and the
Fe-MoS2 with the adsorbates, respectively.
It is found that CO and O2 can only be physisorbed on the mono-
layer MoS2 plane without any defects, while they interact strongly
with Fe-MoS2 . The side views of the obtained most stable config-
urations for CO and O2 adsorption are shown in Fig. 3(a) and (c),
respectively. The calculated adsorption energies for CO and O2 are
1.40 and 1.84 eV (Table 1), respectively, indicating that both of them
can be readily adsorbed on Fe-MoS2 at room temperature. Both CO
and O2 are about 1.8 Å away from the Fe atom. The bond length of
the adsorbed CO (1.16 Å) is slightly changed compared with the free
 D. Ma et al. / Applied Surface Science 328 (2015) 71–77 73

Fig. 1. Top and side views of the geometric structures of Fe-MoS2 with the charge density difference (a) and the spin-density isosurface (b). In (a), the yellow and cyan
regions represent the electron accumulation and loss, respectively. In (b), the red and green regions represent the spin-up and spin-down electron densities, respectively.
The isosurface value is taken as 0.003 e/bohr3 . The brown, blue, and yellow spheres represent the Fe, Mo, and S atoms, respectively. (c) The spin-polarized local densities of
states (LDOS) projected on the Fe 3d and 4s orbitals (upper panel) as well as its neighboring Mo 4d and 5s orbitals (lower panel). The positive and negative LDOS denote the
spin-up and spin-down states, respectively. The vertical red line indicates the Fermi level. (For interpretation of the references to color in this figure caption, the reader is
referred to the web version of this article.)

Fig. 2. Atomic configurations for the diffusion of the Fe atom from the S vacancy to its neighboring Mo top site (a) and hollow site of the S Mo S hexagonal ring (b), including
the initial state (IS), transition state (TS), and final state (FS) along the minimum-energy path (MEP). The value (in eV) shows the energy change between neighboring states.

one (1.14 Å), while that of the adsorbed O2 is elongated to 1.38 Å the substrate not only accumulates on the C and O ions, but also
from 1.23 Å in the gas phase, due to the significant charge trans- mainly on the C Fe bond. Contrary to CO, as shown in Fig. 3(d),
fer (0.76e) from Fe-MoS2 to the 2␲* orbital of O2 . The CDD for the the transferred electrons from the substrate mainly accumulate
adsorbed CO (Fig. 3(b)) shows that the transferred electrons from around the O2 . For CO2 , the most stable adsorption site locates

Fig. 3. The side views of the CO and O2 adsorption on Fe-MoS2 are shown in (a) and (c), respectively. The top and side views of the charge density difference of the above
two configurations are shown in (b) and (d), respectively. The yellow and cyan regions denote the electron accumulation and loss, respectively. The isosurface value is taken
as 0.002 e/bohr3 . (For interpretation of the references to color in this figure caption, the reader is referred to the web version of this article.)
74 D. Ma et al. / Applied Surface Science 328 (2015) 71–77
Fig. 4. Atomic configurations of the IS, TS, MS, and FS along the MEP for the CO oxidation on Fe-MoS2 via the LH mechanism (CO + O2 → OOCO → CO2 + O). Both top (upper
panel) and side (lower panel) views are displayed, as well as the energy change (in eV) between neighboring states.
on the Fe atom with the adsorption energy of 0.34 eV, suggesting
that a CO2 molecule is weakly adsorbed on Fe-MoS2 and can easily
desorb from the reaction site at room temperature. As expected,
the atomic O strongly binds to the Fe atom with Ead (O) of 4.85 eV,
close to those of metal-embedded graphene systems [36,37]. As for
the magnetic properties, the embedded Fe and its neighboring Mo
atoms are still antiferromagnetic coupling for the systems with the
adsorbed O2 or CO. The magnetic moment (2.00 B ) for the Fe-MoS2
with the adsorbed CO or O2 is slightly reduced compared with that
of the bare sheet (2.29 B ), due to both the charge transfer and the
strong interaction between the adsorbates and Fe-MoS2 . For the
case of the O2 adsorption, the magnetic moment of the embedded
Fe atom is reduced by about 0.63 B and that of the adsorbed O2
is reduced to 0.23 B (2 B for the free O2 molecule), which is well
consistent with the significant charge transfer (0.76e) and strong
interaction between O2 and the substrate. For the case of the CO
adsorption, due to the charge transfer, the magnetic moment of
the Fe atom is reduced by 0.25 B and the adsorbed CO also carries
a small spin magnetic moment of 0.11 B . The properties presented
above suggest that Fe-MoS2 is a promising CO oxidation cata-
lyst with high efficiency, which will be discussed in the following
part.
Besides the monolayer MoS2 , the few-layer stacked MoS2 are
frequently observed in the experiments [24]. To check the thick-
ness effect, we also investigated the adsorption of CO, O2 , O, and CO2
on the Fe-embedded bilayer MoS2 (Fe-2MoS2 ), for which the van
der Waals density functional (vdW-DF) (optB86b-vdW) [64,65] was
used in order to treat the long-range dispersion between the layers.
The A–A/ stacking conformation for the bilayer MoS2 is adopted,
which was predicted to be the most stable in the previous calcula-
tions [66,67]. For this conformation, one type of atom is on top of the
other type. The calculated binding energy and interlayer distances
Table 1
The adsorption energy (Ead ) of various adsorbates on the Fe-embedded MoS2 , the
nearest distance (d) between the adsorbate and the Fe atom, and the electron trans-
fer (Q) from the Fe-embedded MoS2 to the adsorbate. For the Fe-MoS2 , the values
(out of the parentheses) are obtained by fully using the PBE functional. For the
Fe-2MoS2 , the values (in the parentheses) are obtained by fully using the vdW-
DF, except that the numbers in bold and italic are obtained by first optimizing the
structures by the vdW-DF and then calculating the total energy by the PBE.
Adsorbate Ead (eV) d (Å) Q (e)
CO 1.40 (1.56, 1.44) 1.86 (1.87) 0.29 (0.27)
O2 1.84 (2.03, 1.85) 1.80 (1.80) 0.76 (0.76)
O 4.85 (5.13, 4.87) 1.60 (1.59) 0.78 (0.70)
CO2 0.34 (0.55, 0.35) 2.16 (2.13) 0.00 (0.01)
for the bilayer MoS2 are 37.2 meV/atom and 6.16 Å, respectively, in
good agreement with the previous results [66,67].
The calculated adsorption properties are listed in Table 1. From
the table, we can see that the nearest distances and the electron
transfers between the various adsorbates and the substrates are
nearly same for the Fe-MoS2 and Fe-2MoS2 . However, the adsorp-
tion energies for the Fe-2MoS2 are always slightly larger than those
for the Fe-MoS2 , which is probably due to the different calculation
methods used. The calculations for the adsorption on the Fe-MoS2
were performed by using the conventional PBE functional, while
those for the adsorption on the Fe-2MoS2 were performed by using
the vdW-DF. In fact, if the structure optimizations are performed
by using the vdW-DF for the systems involved in the adsorption
on the Fe-2MoS2 and then the adsorption energies are calculated
by using the PBE functional, the results are almost same as those
for the Fe-MoS2 , as shown in Table 1. These discussions should be
applicable to the few-layer MoS2 with more layers, due to the weak
interlayer interaction. Therefore, the adsorption properties of the
main adsorbates and the main conclusions of our paper should be
robust with respect to the number of the layers of the few-layer
MoS2 .
3.3. CO oxidation on Fe-MoS2
Generally, there are two well-established mechanisms for the
reaction of CO and O2 , namely the Langmuir–Hinshelwood (LH)
and Eley–Rideal (ER) mechanisms [36–38]. For the ER mechanism,
the gas-phase CO molecules directly react with the preadsorbed
O2 molecules, producing a carbonate-like CO3 complex as inter-
mediate state (MS). The LH mechanism involves the coadsorption
of CO and O2 molecules before reaction, the formation of a peroxo-
type OOCO complex MS and the desorption of the produced CO2
molecule. In the present study, we find that the dissociative adsorp-
tion of O2 on Fe-MoS2 system is energetically unfavorable, which
is similar to the cases of CO oxidation on graphene doped with
Au [36], Cu [38], and several non-noble metal [44]. Besides, the
carbonate-like CO3 MS formed during the ER reaction on Fe-MoS2
is energetically more stable by 0.54 eV than the final product (the
physisorbed CO2 and chemisorbed atomic O), indicating that the
oxidation process by the ER mechanism involves the endother-
mic reaction and is thermodynamically unfavorable. Thus the ER
mechanism is hardly possible in our case as a starting point. As
previous studies [38,44], the complete CO oxidation reactions on
Fe-MoS2 may include a two-step process: the LH reaction as a
starting step (CO + O2 → OOCO → CO2 + O) and followed by the ER
 D. Ma et al. / Applied Surface Science 328 (2015) 71–77 75

Table 2
0 Structural parameters for the states along the MEP for the CO oxidation on Fe-MoS2 :
0.00 TS (a) CO + O2 → OOCO → CO2 + O and (b) CO + O → CO2 . The initial state (IS), transition
-1 state (TS), intermediate state (MS), and final state (FS) of the process (a) are displayed
IS MS
-1.12 in Fig. 4, and the IS, TS, and FS of the process (b) are displayed in Fig. 6. The units of
Energy (eV)

-2 the bond distance and angle are angstrom and degree, respectively.
-1.63 -1.75
(a) IS TS MS FS
-3
d(C O) 1.15 1.17 1.21 1.18
-4 d(C Fe) 1.96 2.04 2.08 4.45
d(C O1) 2.65 1.78 1.33 1.18
FS
d(O1 O2) 1.35 1.39 1.54 3.28
-5 -4.79 d(O2 Fe) 1.97 1.90 1.82 1.60
∠(O C O1) 117.9 113.4 124.3 178.8
Reaction Path
(b) IS TS FS
Fig. 5. Schematic energy profile corresponding to the states shown in Fig. 4. All
energies are given with respect to the reference energy, i.e. the sum of total energies d(C O) 1.14 1.15 1.17
of the Fe-MoS2 and individual free CO and O2 molecules. d(C O2) 3.08 1.88 1.18
d(O2 Fe) 1.60 1.66 2.16
∠(O C O2) 90.7 119.1 179.9
reaction (CO + O → CO2 ). To search for the MEP for CO oxidation, the
obtained most stable coadsorption configuration has been selected
as the IS, where CO and O2 are tilted and parallel to the Fe-MoS2 the local configurations for each state along the MEP are shown in
sheet, respectively. The FS consists of a physisorbed CO2 and a Fig. 6 and the corresponding structural parameters are displayed in
chemisorbed atomic O on Fe-MoS2 . Table 2(b). The configuration with a CO molecule about 3 Å away
The local configurations of each state along the MEP for the LH from the preadsorbed O on the Fe atom is chosen as the IS. The FS
reaction described above are displayed in Fig. 4 and the correspond- is simply set to the configuration of CO2 adsorption on Fe-MoS2 .
ing energies are schematically plotted in Fig. 5 with respect to the When the CO molecule approaches the preadsorbed O, the TS with
reference energy, which is the sum of the total energies of the Fe- the C O2 distance of 1.88 Å is formed. It is found that the ER process
MoS2 , and individual free CO and O2 molecules. In addition, the has an energy barrier of 0.26 eV, which is much smaller than that of
structural parameters for each state along the MEP are displayed the first CO oxidation through the LH mechanism. The adsorption
in Table 2(a). Once CO and O2 are coadsorbed on Fe-MoS2 , the dis- energy for the FS with respect to the free CO2 and Fe-MoS2 is only
tance between the adsorbed CO and O2 is about 2.65 Å, and both 0.34 eV (Table 1), therefore CO2 can be easily desorbed from Fe-
Fe CO and Fe O2 distances are about 2.0 Å. The bond length of MoS2 due to the weak interaction.
the adsorbed O2 is elongated to 1.35 Å, while that of the adsorbed To gain deep insight into the origin of high activity of Fe-MoS2 ,
CO is slightly changed. To proceed, the O2 molecule turns around we investigated the electronic structure of the coadsorption config-
with one of the O atom (O1) approaching the C atom of CO, while uration, i.e. the IS of the LH reaction shown in Fig. 4. Fig. 7 illustrates
the another O atom (O2) adsorbs on the Fe atom. Reaching TS, the the spin-polarized LDOS projected onto the C O (left panel) and
O O bond length of the adsorbed O2 is elongated to 1.39 Å, while O1 O2 atoms (right panel), as well as the Fe 3d orbital, which are
the distance between CO and O2 is shortened to 1.78 Å. Passing critical to understand the activation of the reactants. The spin-down
over the TS with an energy barrier of 0.51 eV, a peroxo-type OOCO component of the highest d orbital of the embedded Fe is partially
complex (MS) is formed over the Fe atom. The O-O bond length of occupied before CO and O2 coadsorption. Upon the CO and O2 coad-
the adsorbed O2 is further elongated to 1.54 Å, while the distance sorption, this d orbital shifts upward with respect to the Fermi
between CO and O2 is shortened to 1.33 Å. Passing over the MS level and becomes completely empty, due to the charge transfer
without an energy barrier, a physisorbed CO2 molecule is formed, between the Fe and the adsorbates. Bader charge analysis [62] fur-
leaving an atomic O adsorbed on the embedded Fe atom. ther shows that the CO and O2 gain 0.14 and 0.65e, respectively,
After the LH reaction, we further investigated the CO oxidation less than those of the adsorbed individual molecules (Table 1), and
by the preadsorbed atomic O through ER mechanism, for which these electrons are mainly donated by the embedded Fe atom. As

Fig. 6. Atomic configurations of the IS, TS, and FS along the MEP for the CO oxidation by the atomic O preadsorbed on Fe-MoS2 via the ER mechanism (CO + O → CO2 ). Both
top (upper panel) and side (lower panel) views are displayed, as well as the energy change (in eV) between neighboring states.
76 D. Ma et al. / Applied Surface Science 328 (2015) 71–77
Fig. 7. The upper panel shows the DOS of the free CO (left) and O2 (right) molecules in the gas phase. The lower panel shows the spin-polarized LDOS projected onto the
C O (left) and O1 O2 (right) atoms, together with the Fe 3d orbital of the IS shown in Fig. 4. The positive and negative LDOS denote the spin-up and spin-down states,
respectively. The Fermi level is set to zero. The orbital notations are assigned to the gas-molecule CO and O2 , and roughly indicated in the lower panel.
shown in the lower panel of Fig. 7, the transferred electrons to the
CO or O2 mainly occupy the 2␲* orbitals, which are unoccupied
for the free molecules in the gas phase. In addition, the interaction
between the adsorbates and the Fe atoms results in the broadening
of the orbitals of the adsorbates. For the CO molecule, the 2␲* and
5␦ orbitals are significantly broadened due to the strong hybridiza-
tion with the Fe 3d orbital, while for the O2 molecule, it is the 2␲*
orbital that has been significantly broadened. The electron transfer
between the adsorbates and Fe-MoS2 and the hybridization among
the orbitals lead to the elongation of the C O and O1 O2 bonds
lengths from 1.14 and 1.23 Å in the gas phase to 1.15 and 1.35 Å (the
IS in Fig. 4), respectively. These electronic structures characteristics
enable the strong interaction between the coadsorbed molecules
and Fe-MoS2 as well as the activation of the reactants, which facil-
itate the CO oxidation process. In addition, the magnetic moment
of the coadsorption configuration is increased to 4.00 B , which is
mainly contributed by the Fe atom and the adsorbed O2 molecule.
Overall, the highest energy barrier for the CO oxidation on Fe-
MoS2 along the whole MEP including the LH and ER reactions is only
0.51 eV, which is comparable to those of other metal-embedded
2D materials, such as the Fe–graphene (0.58 eV) [37], Cu–graphene
(0.54 eV) [38], and Co–BN (0.52 eV) systems [46]. Such a low energy
barrier allows the reaction to proceed rapidly at room temperature
[36,68,69]. As discussed above, the high thermal stability of Fe-
MoS2 system and its high catalytic activity toward the CO oxidation
reaction at room temperature suggest that embedding transition-
metals is a promising way for making the basal plane of monolayer
MoS2 catalytically active.
4. Conclusions
In summary, we have investigated the electronic structure,
structural stability, and catalytic activity of the Fe-MoS2 system.
It is found that the S vacancy can strongly constrains the trapped
Fe atom with a high diffusion barrier (∼2.0 eV), which ensures
the high stability of Fe-MoS2 at room temperature. The CO oxi-
dation most likely occurs with the LH reaction as the starting point
with a low energy barrier of 0.51 eV, which is followed by the ER
reaction with an energy barrier of 0.26 eV. The high catalytic activ-
ity of Fe-MoS2 may be attributed to the charge transfer and the
orbital hybridization between the adsorbates and the embedded
Fe atom, which leads to the strong interaction between them and
the activation of the reactants. This study suggests that embedding
transition-metals is a promising method for making the basal plane
of monolayer MoS2 catalytically active, through which the applica-
tion of monolayer MoS2 in catalysis may be significantly extended.
In addition, the adsorption properties for CO, O2 , O, and CO2 on
the Fe-2MoS2 are essentially same as those for these adsorbates on
the Fe-MoS2 , which suggests that the main conclusion of this work
should be robust with respect to the number of the layers of the
few-layer MoS2 .
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 11347186, 11147006, 11174070,
U1404216, and U1404109), the Science Fund of Educational
Department of Henan Province of China (Grant No. 14A140015).
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