Computational Materials Science 138 (2017) 255–266

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Computational Materials Science

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

A DFT study of transition metal (Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)-
embedded monolayer MoS2 for gas adsorption
Yuehua Fan a, Jinyan Zhang a, Yuzhi Qiu a, Jia Zhu a,⇑, Yongfan Zhang b,c,⇑, Guoliang Hu a
a
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, China
b
College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China
c
State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou, Fujian 350002, China

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

Article history: The structures and electronic properties of diverse transition metal (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt
Received 3 February 2017 and Ir)-embedded monolayer MoS2 in the S-vacancy and the adsorption of various gas molecules (CO, NO,
Received in revised form 12 May 2017 O2, NO2, NH3) have been systematically investigated using density functional theory (DFT). Our results
Accepted 21 June 2017
show that strong interactions between the different transition metal atoms and S defect site in monolayer
MoS2 suggest that the transition metal-embedded monolayer MoS2 should be stable. The embedded tran-
sition metal atoms can effectively modulate the electronic structures and magnetic properties of inert
Keywords:
monolayer MoS2, and drastically enhance the adsorption and the activation of CO, NO, O2, NO2 and
DFT
Transition metal-embedded monolayer
NH3 gas molecules, with respect to that on pristine monolayer MoS2 with weak physisorption. The elec-
MoS2 tronic structure analysis reveals that introduced nd orbital impurity states of embedded transition metals
Electronic properties in the band gap play an important role in the adsorption and effectively activation of gas molecules. In
Gas adsorption addition, obvious charge transfer occur from TM-MoS2 to oxidizing gas molecules (NO2, O2) acting as
acceptors, whereas the direction of charge transfer is reversed for the adsorption of the reducing gas
(NH3) as donor. Particularly, among all transition metal elements, embedded Fe and Co have better ther-
mal stability, adsorption properties and chemical activities for gas molecules adsorption. Our results open
new perspectives for the design and the study of high active MoS2-based 2D-nanomaterials.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
Recently, monolayer MoS2 as one of the most extensively stud-
ied material in the transition metal dichalcogenides (TMDs), has
received great interest because of its supernormal physical, chem-
ical, optical and mechanical properties [1–3]. It has been widely
applied in catalysis [4,5], gas sensing [6–9] and lithium ion batter-
ies [10,11], due to large surface areas and abundant active sites
[12]. A monolayer MoS2 sheet is composed of honeycomb atomic
structure in the plane and S-Mo-S sandwich structure in the verti-
cal direction, with the Mo atom strong covalently bonded to six S
atoms [13,14]. However, the facets of the intrinsic monolayer
MoS2 are chemically inert and can only physisorb most of gas
molecules and have no spin polarization [15].
To further improve the performance of monolayer two-
dimensional materials, a new design strategy has been developed
⇑ Corresponding authors at: College of Chemistry and Chemical Engineering,
Jiangxi Normal University, Nanchang, Jiangxi 330022, China (J. Zhu). College of
Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China (Y. Zhang).
E-mail addresses: jia_zhu@jxnu.edu.cn (J. Zhu), zhangyf@fzu.edu.cn (Y. Zhang).
and explored to modulate the properties in past few years [16–
18]. Embedding appropriate transition metal elements can modu-
late the properties of the 2D materials, including the enhanced
chemical activity and sensitivity toward small molecules [19–21].
Yuan et al. have found that the metal atoms (Al, Si, Cr and Mn) dop-
ing in graphene is an effective way to tune the electronic and mag-
netic properties of graphene due to the stronger bonding between
metals and neighboring carbon atoms, which is very important to
the improvement of sensitivity to O2 molecule using density func-
tional theory [22]. Lu et al. predicted that Au, Cu and Fe-embedded
graphene are highly active catalyst for CO oxidation, which can be
attributed to the partially occupied d orbital localized in the vicin-
ity of the Fermi level due to the interaction of the metal atom with
graphene [23–25]. The adsorption of gas molecules (O2, CO, NO2
and NH3) on transition metal embedded graphene suggested that
embedded transition metal elements can significantly enhance
the interactions between gas molecules and graphene [26]. Lin
et al. also reported that Co doped hexagonal boron nitride
nanosheets (h-BNNSs) can enhance the catalytic activity of CO oxi-
dation [27]. Therefore, doping metal atoms, especially transition
metal atoms in two-dimensional materials, can further improve

http://dx.doi.org/10.1016/j.commatsci.2017.06.029
0927-0256/Ó 2017 Elsevier B.V. All rights reserved.
256 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
the chemical properties and catalytic activities of the inert basal
plane. Like other 2D materials, the presence of single atom substi-
tutions of Cr and V in monolayer MoS2 has been experimentally
demonstrated by a combination of ADF-STEM and EELS mapping.
It was found to be useful for improving the electronic, mechanical
and interfacial properties [28,29]. Theoretically calculations reveal
that the doped monolayer MoS2 exhibits enhanced chemical activ-
ity and sensing sensitivity toward various gas molecules compared
with the pristine MoS2 basal plane [30,31]. However, a thoroughly
and systematically research about the effects of various transition
metal atoms embedded monolayer MoS2 on the adsorption of gas
molecules is not clear, which represent a great advancement in
the design of MoS2-based catalysts and gas sensors.
In this work, using first-principles calculations based on density
functional theory, we investigate the structures and electronic
properties of various transition metal (Fe, Co, Ni, Cu, Ag, Au, Rh,
Pd, Pt and Ir)-embedded monolayer MoS2 surface, and the gas
(CO, NO, O2, NO2 and NH3) adsorption properties of MoS2 with
and without the inclusion of van der Waals (vdW) forces. This arti-
cle is organized as follows. Firstly, we study the structural stability
and electronic properties of diverse transition metal atoms (Fe, Co,
Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)-embedded monolayer MoS2. Then,
for the sake of the effects on chemical property and catalytic activ-
ity of different transition metal-embedded monolayer MoS2, small
gas molecules (CO, NO, O2, NO2 and NH3) adsorption on transition
metal-embedded monolayer MoS2 are investigated.
2. Computational methods
The plane-wave density functional theory (DFT) calculations
were performed using the Vienna ab initio simulation package
(VASP) [32–34] and the projector augmented wave (PAW) method.
The exchange and correlation energy was calculated with the gen-
eralized gradient approximation of Perdew-Bruke-Ernzerh (PBE)
functional [35]. Spin polarization was adopted in all calculations.
The cutoff energy for the plane-wave expansion was set to
400 eV. A 3  3  1 Monkhorst-Pack grid was used for the k-
point sampling of the Brillouin zone. A vacuum region of 15 Å
was applied along the z axis to avoid the adjacent MoS2 (0 0 1)
interlayer interactions. The role of the vdW interaction was inves-
tigated using DFT-D2 method including the pairwise force field
implemented by Grimme [36].
The optimized lattice parameter of MoS2 was 3.18 Å, which is in
good agreement with the experimental (3.20 Å [33,37]) and theo-
retical values (3.18 Å [38], 3.20 Å [39]). A (4  4) supercell mono-
layer MoS2 that contains 32 S and 16 Mo atoms was simulated as
a periodically repeated hexagonal unit cell. All the atoms in slab
structure including adsorbates were allowed to relax in three
dimensions during the optimization.
3. Results and discussion
3.1. Structural stability and electronic properties of TM-MoS2 (TM = Fe,
Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)
Since the experiments have shown that monosulfur vacancy is
the most common point defect structure due to its lower formation
energy than that of Mo vacancy, and then the vacancies are filled
with substitutional impurity atoms [40–43]. In this section, we
investigate the geometry and stability of various transition metal
atoms (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir) embedded
monolayer MoS2. Table 1 listed the M-Mo average distance, verti-
cal height between metal atom and the plane for the metal-
embedded MoS2 with the S-vacancy. The results show that all
the metal atoms are located in the center of the defect by forming
three TM-Mo bonds, and the average bond lengths of TM-Mo bond
increase with the order of Co = Ni < Fe < Ir < Cu < Rh = Pt < P-
d < Au < Ag. The longest bond length is AgAMo bond length
(2.84 Å) while the shortest are CoAMo and NiAMo bond lengths
(2.52 Å). Due to the large sizes, these metal atoms are out of the
MoS2 plane compared with the S atom in the defect-free MoS2 sur-
face. Accordingly, the vertical distances between the metal atoms
and the MoS2 plane are calculated with a range from 0.61 Å to
1.04 Å (Table 1). In addition, the bond lengths of TMAMo bonds
are all longer with a range from 0.10 Å to 0.42 Å than that of SAMo
bond (2.42 Å) in pristine MoS2 surface.
In order to test the stability of transition metal-embedded
monolayer MoS2, the binding strength between metal atom and
defective monolayer MoS2 is investigated. As shown in Table 1,
the binding strength increases in the order of Ag < Au < Cu < Fe <
Co < Pd < Ni < Rh < Ir < Pt with the binding energies of 1.98 eV,
2.44 eV, 2.73 eV, 3.61 eV, 3.77 eV, 3.79 eV, 4.23 eV, 4.52 eV,
5.12 eV and 5.21 eV, respectively, which is good agreement with
previous results[44]. The binding strength of Pt-MoS2 is the stron-
gest (5.21 eV) while the binding strength of Ag-MoS2 is the weak-
est (1.98 eV). The interaction between the single transition metal
atom and the perfect MoS2 surface is also studied. According to
the corresponding adsorption energies (0.49 eV, 0.62 eV, 1.32 eV,
2.25 eV, 2.08 eV, 2.78 eV, 2.95 eV, 3.40 eV, 3.13 eV, 2.80 eV for Ag,
Au, Cu, Fe, Pd, Co, Rh, Ni, Ir, Pt, respectively), it is obvious that
the binding energies of various metal atoms-embedded monolayer
MoS2 are much higher ranging from 0.83 eV to 2.42 eV in energy
than that of the defect-free monolayer MoS2, indicated stronger
interaction between the metal atoms and defective monolayer
MoS2. Therefore, it is suggested that stabilities of TM binding to
defective monolayer MoS2 are drastically improved with respect
to that on the pristine monolayer MoS2.
To better investigate the effects introduced by transition
metals-embedded monolayer MoS2, in this section, we will focus
on the electronic structures of those embedded monolayer MoS2.
Firstly, the Bader charges are calculated and the results are sum-
marized in Table 1. In here, the negative value means that the
embedded transition metal atoms obtain electrons. For Fe, Co, Ni,
Cu and Ag atoms, electrons are transferred from the embedded
metal atoms to the defect monolayer MoS2 (about 0.36 e, 0.16 e,
0.04 e, 0.11 e, 0.13 e, for Fe, Co, Ni, Cu, Ag, respectively). Whereas
for Au, Rh, Pd, Pt and Ir atoms, the embedded noble metal atoms
gain electrons (about 0.19 e, 0.11 e, 0.13 e, 0.34 e, 0.24 e
for Au, Rh, Pd, Pt and Ir atoms, respectively) from the defect mono-
layer MoS2. As all we know, an element with high electronegativity
tends to attract electrons from a lower one in most cases. Known
from the Pauling electronegativity, the electronegativity of Mo is
2.16, which is higher than Fe (1.83), Co (1.88), Ni (1.91), Cu
(1.90) and Ag (1.93). Therefore, after Fe, Co, Ni, Cu and Ag atoms
embedding the defect surface, Fe, Co, Ni, Cu and Ag atoms lose
about 0.36 e, 0.16 e, 0.04 e, 0.11 e and 0.13 e, respectively. In con-
trast, the electronegativity of Mo (2.16) is lower than Au (2.54), Rh
(2.28), Pd (2.20), Pt (2.28) and Ir (2.20). Thus, when Au, Rh, Pd, Pt
and Ir atoms embedded the defect surface, Au, Rh, Pd, Pt and Ir
atoms gain about 0.19 e, 0.11 e, 0.13 e, 0.34 e and 0.24 e, separately.
In addition, the magnetic properties of monolayer MoS2 can be
modulated by the embedded transition metals. The ground state
of single-layer MoS2 is nonmagnetic, while the transition metal-
embedded monolayer MoS2 show total spin magnetic moments
of 2.21 lB, 1.01 lB, 1.00 lB, 1.00 lB, 1.00 lB, 1.01 lB and 1.00 lB,
for Fe, Co, Cu, Ag, Au, Rh and Ir, respectively, as shown in Table 1.
To gain a deeper understanding of the interaction between the
embedded metal atoms and the defect center of monolayer MoS2,
we take Fe and Co embedded monolayer MoS2 as examples, to fur-
ther investigate the spin-polarized density of state (DOS) curves of
Fe-MoS2 and Co-MoS2 systems, as displayed in Fig. 2. Fig. 2a and b
in the upper panels show the total DOS of Fe-MoS2 and Co-MoS2
 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266 257

Table 1
Binding energy (Eb in eV) for metal atom at the S-vacancy. Height (h in Å) between metal atom and the plane. M-Mo average distance (dM-Mo in Å) for the metal-embedded MoS2
with the S-vacancy. Net bader charge for metal atom (qM in e) at the S-vacancy and total magnetic moments (Mag in lB) for the transition metal-embedded monolayer MoS2 with
the S-vacancy.

Metal(M) Fe Co Ni Cu Ag Au Rh Pd Pt Ir
Eb(M)a 3.61 3.77 4.23 2.73 1.98 2.44 4.52 3.79 5.21 5.12
h 0.68 0.61 0.62 0.73 1.04 0.94 0.78 0.85 0.78 0.71
dM-Mo 2.58 2.52 2.52 2.62 2.84 2.77 2.64 2.69 2.64 2.59
qMb 0.36 0.16 0.04 0.11 0.13 -0.19 -0.11 -0.13 -0.34 -0.24
Mag 2.21 1.01 0 1.00 1.00 1.00 1.01 0 0 1.00
a
The Eb in Table 1 is defined as E = Emetal atom + Efree sheet Eadsorbate sheet, where Emetal atom, Efree sheet and Eadsorbate sheet represent the metal atom, the MoS2 with the S-Vacancy
surface and metal atom embedded MoS2 surface.
b
The negative value means that the embedded transition metal atoms obtain electrons, respectively.

systems. Clearly, the system of Fe or Co atom-embedded mono-
layer MoS2 is spin polarized with total magnetic moment of 2.21
lB and 1.01 lB, respectively. A distinct feature is that asymmetric
DOS peaks appear near the Fermi level, which is significantly dif-
ferent from the case that on the perfect monolayer MoS2. Accord-
ing to the partial density of states (PDOSs) of metal atom (Fe or
Co) and neighboring Mo atoms (in the lower panels of
Fig. 2a and b), we can further find that above asymmetrical peaks
are mainly derived from metal atom (Fe or Co atom) 3d orbitals.
Moreover, since the asymmetrical DOS peaks in the gap are domi-
nated by the metal 3d state, it can be expected that spin charge
densities are distributed mainly over the metal atom. Therefore,
as shown in Fig. 1b and d, the spin charge densities of Fe-MoS2
or Co-MoS2 systems are mainly localized around the Fe atom or
Co atom. The results of magnetization also show that magnetic
moment for the whole system mainly attributes to magnetization
of metal atom (2.68 lB, 1.34 lB for Fe and Co, respectively). In addi-
tion, Fig. 2a and b also show that the 3d states of metal atom (Fe or
Co atom) is strongly mixed with Mo 4d orbitals above and below
the Fermi level (EF), indicating a very strong interaction between
the metal atom and S-vacancy.
we further investigate the adsorption behaviors of some small
gas molecules (CO, NO, O2, NO2 and NH3) on diverse transition
metal (Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)-embedded mono-
layer MoS2. To obtain the most favorable adsorption configura-
tions, the gas molecules are initially placed at different sites and
directions above the TM-MoS2 systems. Then, the most stable
adsorption configurations of small gas molecules (CO, NO, O2,
NO2 and NH3) on diverse TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au,
Rh, Pd, Pt and Ir) are obtained at PBE level. In gas phase, the bond
lengths of CO, NO, O2, NO2 and NH3 molecules are 1.14 Å, 1.17 Å,
1.23 Å, 1.21 Å and 1.02 Å, separately, and corresponding bond
angles of NO2 and NH3 are 133.8° and 106.4°, respectively, which
are agree with the previous results [45–47]. In the following parts,
we will discuss the adsorption behaviors of gas molecules (CO, NO,
O2, NO2 and NH3) on TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd,
Pt and Ir), separately. Known that the earth-abundant Fe and Co are
cheap and widely used among the metals we discussed. Mean-
while, Fe-MoS2 and Co-MoS2 are stable with the high binding ener-
gies of 3.61 eV and 3.77 eV. Therefore, we will further discuss the
geometries and adsorption properties of gas molecules on Fe and
Co-embedded MoS2 surfaces detailly.

3.2. Adsorption of small gas molecules (CO, NO, O2, NO2 and NH3) on
TM-MoS2
In order to study the effect of transition metal-embedded
monolayer MoS2 on adsorption properties and catalytic activities,
3.2.1. Adsorption of CO on TM-MoS2
For the adsorption of CO on TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag,
Au, Rh, Pd, Pt and Ir), CO molecule via its carbon atom binds at
the metal site with a tilted angle. Compared with the bond length
of CO molecule in gas phase (1.14 Å), the CAO bond lengths of

Fig. 1. Top and side views of the geometric structures and the spin charge density for Fe-embedded monolayer MoS2 (a) and (b). Top and side views of the geometric
structures and the spin charge density for Co-embedded monolayer MoS2 (c) and (d). Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo. The light green and light
yellow regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)
258 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266

Fig. 2. The spin-polarized total densities of states (TDOS) (upper panels) and corresponding DOS projected on 3d state of Fe atom and 4d state of Mo atoms (lower panels) for
Fe-MoS2 (a), The spin-polarized total densities of states (TDOS) (upper panels) and corresponding DOS projected on 3d state of Co atom and 4d state of Mo atoms (lower
panels) for Co-MoS2 (b). The Fermi level was set to zero.

adsorbed CO molecule have been slightly elongated (range from
1.15 Å to 1.17 Å), indicating slightly activation of CO molecule.
Now let us discuss the stability of CO/TM-MoS2 (TM = Fe, Co, Ni,
Cu, Ag, Au, Rh, Pd, Pt and Ir) system. From Table 2, it can be seen
that the order of the adsorption energies is Ag < Au < Pd <
Cu < Rh < Pt < Ni < Fe < Co < Ir (Eads = 0.68 eV, 0.95 eV, 0.96 eV,
1.13 eV, 1.28 eV, 1.40 eV, 1.42 eV, 1.44 eV, 1.51 eV and 1.81 eV,
respectively). The strongest adsorption (Eads = 1.81 eV) comes from
Ir-MoS2 while the weakest one (Eads = 0.68 eV) is from Ag-MoS2.
Specially, when comparison to other TM-MoS2 systems, the
adsorption energy for CO/TM-MoS2 (TM = Fe, Co) is much higher
than that on the most of TM-MoS2 systems including Ag, Au, Pd,
Cu, Rh, Pt, Ni, except Ir, indicated better adsorption properties
expected for Fe, Co-MoS2. The interaction between CO molecule
and perfect monolayer MoS2 is also explored in this work. We
found that the adsorption of CO on perfect monolayer MoS2 is rel-
atively weak with physisorption energy of 0.01 eV, which is signif-
icantly smaller from 0.67 eV to 1.80 eV in energy than those at the
embedded metal sites. It is suggested stronger adsorption proper-
ties for CO molecule anchored at the embedded metal site, com-
pared with that on the pristine MoS2 basal plane. To determine
the charge transfer occurring between CO molecule and TM-
MoS2 system, the Bader charge is calculated and the results are
summarized in Table 3 and Fig. 9. In here, the negative value means
that the adsorbed gas molecule obtains electrons. It can be seen
that, for all the TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt
and Ir) systems, small charge transfer occurs from TM-MoS2 sur-
face to CO molecule ( 0.22 e, 0.19 e, 0.15 e, 0.04 e, 0.01 e,
0.01 e, 0.13 e, 0.07 e, 0.07 e and 0.16 e for Fe, Co, Ni, Cu,
Ag, Au, Rh, Pd, Pt and Ir, respectively). And the further analysis of
atomic Bader charge shows that the obtained electrons for
adsorbed CO mainly come from the embedded transition metal
atoms, indicated that the embedded metal atoms are vital in stabil-
ity and electronic properties of CO/TM-MoS2 (TM = Fe, Co, Ni, Cu,
Ag, Au, Rh, Pd, Pt and Ir) systems.
To gain more insight into how CO interacts with TM-MoS2, the
structures and electronic properties of CO/TM-MoS2 (TM = Fe, Co)
systems are further analyzed. Fig. 3a and c are displayed the most
stable adsorption configurations for CO adsorption on Fe or Co-
embedded monolayer MoS2, CO molecule interacts with TM-
MoS2 (TM = Fe, Co) by forming one CATM bond (1.86 Å and
1.80 Å for CAFe bond and CACo bond, respectively). The CAO bond
length of adsorbed CO molecule (about 1.16 Å) is slightly elongated
with respect to that in gas-phase CO molecule (1.14 Å), indicating
somewhat activation of CO molecule. And the corresponding
adsorption energies are 1.44 eV and 1.51 eV for CO/Fe-MoS2 and
CO/Co-MoS2, respectively, which is much higher than that of CO
adsorption on perfect monolayer MoS2 (Eads = 0.01 eV), indicating

Table 2
Adsorption energies (Eadsa in eV) for CO, NO, O2, NO2 and NH3 adsorption on the transition metal-embedded MoS2 with the S-vacancy at the metal site, respectively, the values in
the parentheses are obtained by using DFT-D2 method.

Metal(M) Eads/CO Eads/NO Eads/O2 Eads/NO2 Eads/NH3

Fe 1.44(1.60) 2.64(2.84) 1.92(2.10) 2.10(2.29) 1.33(1.52)
Co 1.51(1.71) 2.73(2.95) 1.45(1.61) 1.60(1.79) 1.18(1.38)
Ni 1.42(1.69) 1.69(1.88) 0.84(0.98) 1.11(1.32) 1.13(1.33)
Cu 1.13(1.27) 1.41(1.54) 1.02(1.16) 1.69(1.88) 1.28(1.47)
Ag 0.68(0.79) 0.87(0.98) 0.54(0.62) 1.35(1.49) 0.97(1.12)
Au 0.95(1.06) 1.12(1.24) 0.65(0.74) 1.56(1.70) 0.99(1.17)
Rh 1.28(1.49) 2.53(2.74) 1.13(1.29) 1.45(1.64) 1.02(1.20)
Pd 0.96(1.13) 0.93(1.05) 0.29(0.39) 0.61(0.77) 0.78(0.94)
Pt 1.40(1.60) 1.24(1.36) 0.37(0.47) 0.83(0.99) 0.89(1.08)
Ir 1.81(2.04) 3.12(3.36) 1.49(1.68) 1.81(2.08) 1.14(1.33)
a
The Ea in Table 2 is defined as E = Efree molecule + Efree sheet Eadsorbated sheet, where Efree molecule, Efree sheet and Eadsorbate sheet represent the free molecule, the metal-embedded
MoS2 surface and CO, NO, O2, NO2 and NH3 adsorbed on the metal-embedded MoS2 with the S-vacancy at the metal site, respectively.
 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266 259

Table 3
Net bader charge (qgasa in e) of gases for CO, NO, O2, NO2 and NH3 adsorbed on the metal-embedded MoS2 with the S-vacancy at the metal site, respectively, the values in the
parentheses are obtained by using DFT-D2 method.

Metal(M) q/CO q/NO q/O2 q/NO2 q/NH3

Fe 0.22( 0.27) 0.32( 0.32) 0.65( 0.70) 0.66( 0.66) 0.13(0.16)
Co 0.19( 0.19) 0.25( 0.25) 0.55( 0.54) 0.61( 0.62) 0.13(0.14)
Ni 0.15( 0.16) 0.22( 0.22) 0.44( 0.44) 0.42( 0.42) 0.14(0.15)
Cu 0.04( 0.02) 0.22( 0.22) 0.46( 0.46) 0.64( 0.64) 0.17(0.18)
Ag 0.01( 0.01) 0.21( 0.20) 0.38( 0.38) 0.60( 0.61) 0.14(0.14)
Au 0.01( 0.02) 0.20( 0.20) 0.39( 0.39) 0.54( 0.54) 0.22(0.23)
Rh 0.13( 0.16) 0.20( 0.20) 0.44( 0.45) 0.31( 0.29) 0.18(0.19)
Pd 0.07( 0.06) 0.14( 0.14) 0.17( 0.17) 0.34( 0.34) 0.11(0.11)
Pt 0.07( 0.08) 0.17( 0.17) 0.27( 0.26) 0.34 ( 0.31) 0.13(0.16)
Ir 0.16( 0.16) 0.26( 0.26) 0.53( 0.55) 0.39( 0.40) 0.17(0.17)
a
The negative value means that the doped transition metal atoms obtain electrons.

Fig. 3. Top and side views of the geometric structures (a) and the spin charge density (b) for CO adsorption on Fe-MoS2 system. Top and side views of the geometric structures
(c) and the spin charge density (d) for CO adsorption on Co-MoS2 system. Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo; C, black; O, red. The light green and light
yellow regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

a stronger interaction between CO and TM-MoS2 (TM = Fe, Co).
Then, the electronic structures of CO adsorption on Fe-MoS2 and
Co-MoS2 are further investigated. Fig. 4a and b displayed the
spin-polarized total densities of states (TDOS) (upper panels) and
corresponding DOS projected on 3d states of metal atom, adsorbed
CO gas molecules and the isolated CO gas molecules (lower panels)
after CO adsorption on Fe, Co-embedded monolayer MoS2. It can be
seen that the molecular orbital of adsorbed CO is delocalized with
respect to the isolated CO in gas phase. The 3d orbital of Fe or Co
atoms slightly mixed with the 2p⁄ antibonding of CO molecule.
And partially occupied 2p⁄ antibonding of CO near the Fermi level
are observed, result in small electron transfer ( 0.22 e, 0.19 e for
Fe and Co, respectively) occurring from 3d orbital of Fe or Co atom
to 2p⁄ antibonding of CO molecule. We further analysis the mag-
netic properties, it is clear that adsorption of CO has almost not
changed the total magnetic moments of Fe or Co-MoS2 (1.99 lB,
1.04 lB for CO/Fe-MoS2, CO/Co-MoS2, respectively), even though
the magnetic moments of embedded Fe or Co atoms (2.43 lB,
1.26 lB for Fe, Co, respectively) are slightly reduced due to the
interaction with the CO molecule. The further analysis of the spin
charge density (Fig. 3b and d) can also show that the spin magnetic
moments are mainly localized on the doped Fe and Co atoms, as
well as some on the adsorbed CO molecule.
3.2.2. Adsorption of NO on TM-MoS2
For the adsorption of NO molecule on TM-MoS2 (TM = Fe, Co, Ni,
Cu, Ag, Au, Rh, Pd, Pt and Ir), NO is adsorbed on various TM-MoS2
via the N atom bound to the metal atom with a tilted angle. After
adsorption, the NAO bond lengths of absorbed NO molecule are
slightly elongated about 0.01–0.02 Å with respect to that of NO
in gas phase, indicated slightly activation of NO molecule. As
shown in Table 2, the adsorption energies are in accordance with
the order Ag < Pd < Au < Pt < Cu < Ni < Rh < Fe < Co < Ir with the
adsorption energies of 0.87 eV, 0.93 eV, 1.12 eV, 1.24 eV, 1.41 eV,
1.69 eV, 2.53 eV, 2.64 eV, 2.73 eV and 3.12 eV, respectively. It can
be seen clearly that the adsorption energies (2.64 eV, 2.73 eV) for
NO adsorption on Fe, Co-MoS2 system are higher in the range of
0.11–1.86 eV in energy than that on other metals-embedded
monolayer MoS2, including Ag, Au, Pd, Cu, Rh, Pt, Ni, except Ir, sug-
gested better adsorption properties for embedded Fe and Co atom.
In addition, all the adsorption energies of NO/TM-MoS2 (TM = Fe,
Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir) are higher range from
260 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266

Fig. 4. The spin-polarized total densities of states (TDOS) (upper panels) and corresponding DOS projected on 3d states of Fe atom, adsorbed gas molecules and the isolated
gas molecules (lower panels) for CO/Fe-MoS2 (a), NO/Fe-MoS2 (c), O2/Fe-MoS2 (e), NO2/Fe-MoS2 (g), and NH3/Fe-MoS2 (i), respectively. The spin-polarized total densities of
states (TDOS) (upper panels) and corresponding DOS projected on 3d states of Co atom, adsorbed gas molecules and the isolated gas molecules (lower panels) for CO/Co-MoS2
(b), NO/Co-MoS2 (d), O2/Co-MoS2 (f), NO2/Co-MoS2 (h), and NH3/Co-MoS2 (j), respectively. The Fermi level was set to zero. The orbitals of the adsorbed gas molecules are
marked in underlined font. The orbitals of the isolated gas molecules are marked in normal type.
 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
Fig. 4 (continued)
0.82 eV to 3.07 eV in energy than that on perfect monolayer MoS2
(Eads = 0.05 eV), suggesting obviously improvement of adsorption
properties after NO adsorbing on TM-MoS2 in which the metals
atom embedded into the defect site. Then, the charge transfer
between adsorbed NO molecule and TM-MoS2 is investigated by
the Bader charge analysis (Table 3 and Fig. 9). Similar to the
adsorption of CO, the direction of the charge transfer is from tran-
sition metal-embedded monolayer MoS2 to adsorbed NO molecule
( 0.32 e, 0.25 e, 0.22 e, 0.22 e, 0.21 e, 0.20 e, 0.20 e, 0.14
e, 0.17 e and 0.26 e for Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir,
respectively). The analysis on Bader charge of atom further found
that the transferred electrons obtained by adsorbed NO molecule
mainly come from the surface embedded metal atoms, indicated
electronic properties and adsorption behaviors can be improved
by the introduction of appropriate metal dopants.
Since better adsorption properties are observed from Fe and Co
atom embedded monolayer MoS2, the structures and electronic
properties of NO/Fe, Co-MoS2 are further discussed in detailed.
As shown in Fig. 5a and c, NO molecule is adsorbed on TM-MoS2
system by one NATM bond (1.68 Å, 1.64 Å for Fe and Co, respec-
tively) with a tilted angle (about 70°). After adsorption, the NAO
bond length (about 1.18 Å) of adsorbed NO molecule is slightly
261
elongated compared with that of the NO molecule in the gas phase
(1.17 Å). The corresponding adsorption energies for CO adsorption
on Fe-MoS2 and Co-MoS2 (2.64 eV, 2.73 eV for Fe, Co, respectively)
are much higher than that on perfect monolayer MoS2 (0.05 eV),
indicating stronger adsorption ability at metal site. Then, the elec-
tronic properties of NO adsorption on Fe-MoS2 and Co-MoS2 are
studied. Fig. 4c and d are displayed the spin-polarized total densi-
ties of states (TDOS) (upper panels), corresponding partial DOS
projected onto 3d orbital of Fe or Co atom, adsorbed NO and the
isolated NO gas molecules (lower panels). It shows that after
adsorption 2p⁄ antibonding orbital of NO becomes delocalized.
The 3d orbitals of Fe or Co atom are slightly mixed with the 2p⁄
antibonding orbital of NO around the EF, implying a weak interac-
tion between NO molecule and the substrate. This also results in
small electron transfer from 3d orbital of Fe or Co to 2p⁄ antibond-
ing orbital of NO molecule ( 0.32 e, 0.25 e for Fe, Co, respec-
tively). As for the magnetic properties, after adsorption, the total
magnetic moments (1.16 lB, 0 lB for NO/Fe-MoS2, NO/Co-MoS2,
respectively) are significantly decreased. The analysis of magnetic
moments of atom shows that the magnetization of Fe and Co atom
are 1.94 lB and 0 lB, respectively. This is agreed well with the spin
charge density as shown in Fig. 5b and d. It can be seen that, for the
262 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
Fig. 5. Top and side views of the geometric structures (a) and the spin charge density (b) for NO adsorption on Fe-MoS2 system. Top and side views of the geometric
structures (c) and the spin charge density (d) for NO adsorption on Co-MoS2 system. Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo; N, blue; O, red. The light green
and light yellow regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)
NO/Fe-MoS2, the spin charge density mainly localizes on the Fe
atom and NO molecule, while the NO/Co-MoS2 becomes non-spin
polarization.
3.2.3. Adsorption of O2 on TM-MoS2
For the adsorption of O2 molecule on TM-MoS2 (TM = Fe, Co, Ni,
Cu, Ag, Au, Rh, Pd, Pt and Ir), mostly, O2 molecule prefers to
adsorbed on TM-MoS2 with parallel mode by forming two TMAO
bonds. Compared with isolated O2 molecule (1.23 Å), the OAO
bond lengths of adsorbed O2 molecule have been significantly
elongated 0.03–0.15 Å, indicating the strong activation for
adsorbed O2 molecule by metal center. Then, we analyze the
adsorption energies for O2/TM-MoS2. As shown in Table 2, the
order for the adsorption energies is Pd < Pt < Ag < Au < Ni <
Cu < Rh < Co < Ir < Fe with the adsorption energies of 0.29 eV,
0.37 eV, 0.54 eV, 0.65 eV, 0.84 eV,1.02 eV, 1.13 eV, 1.45 eV,
1.49 eV and 1.92 eV, respectively, indicated a strong interaction
between O2 and TM-MoS2. Specially, O2/Fe-MoS2 has the highest
adsorption energy (1.92 eV), which is higher 0.43 eV to 1.63 eV in
energy than those on other O2/TM-MoS2 (TM = Ir, Co, Rh, Cu, Ni,
Au, Ag, Pt, Pd). And O2/Co-MoS2 also has much higher adsorption
energy (1.45 eV). The high adsorption energies suggested that
embedded Fe and Co center can drastically enhance the adsorption
properties of O2 molecule. To compare the adsorption behaviors of
TM-MoS2 and pristine monolayer MoS2, the binding between O2
and pristine-MoS2 is also considered. We found the interaction
between O2 and pristine-MoS2 is physisorption with corresponding
adsorption energy of 0.01 eV, which is obvious lower 0.28 eV to
1.91 eV in energy than that adsorption at the embedded metal
sites. It is indicated that the adsorption properties and catalytic
activities can be significantly improved by transition metal atom
embedded monolayer MoS2. To illustrate the charge transfer occur-
ring between O2 and TM-MoS2, the Bader charge is analyzed
(Table 3 and Fig. 9). Although the direction of the charge transfer
is still from the O2 to substrate, oxidizing gas O2 acting as acceptor
obtained more electrons from TM-MoS2 ( 0.65 e, 0.55 e, 0.44 e,
0.46 e, 0.38 e, 0.39 e, 0.44 e, 0.17 e, 0.27 e and 0.53 e for
Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir, respectively), which is dif-
ferent from the adsorption of CO and NO molecules on TM-MoS2
(TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir) system, Further
analysis on Bader charge of atom shows that obtained electrons
of adsorbed O2 mainly come from the embedded transition
metal atoms in TM-MoS2, suggested that the embedded metal
atoms play an important role in stability and electronic proper-
ties of O2/TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)
systems.
To further explore the interaction between O2 and TM-MoS2, we
analyze the structures and electronic properties of O2/Fe-MoS2 and
O2/Co-MoS2. Fig. 6a and c show the most stable adsorption config-
urations of O2/Fe-MoS2 and O2/Fe-MoS2, respectively. Clearly, O2
molecule interacts with TM-MoS2 (TM = Fe, Co) by forming two
O-TM bonds. While the OAO bond length of adsorbed O2 is signif-
icantly elongated from 1.23 Å to 1.38 Å with respect to the isolated
O2 in gas phase. The significant elongation of OAO bond length
suggested that O2 molecule is strongly activated by the metal cen-
ter (Fe or Co atom). The corresponding adsorption energy (1.92 eV,
1.45 eV for Fe, Co-MoS2, respectively) is much higher 1.91 eV,
1.44 eV in energy than that on pristine-MoS2, respectively, sug-
gested a stronger interaction between O2 and Fe, Co-MoS2 sub-
strate. Then, the electronic structures of O2 adsorption on Fe, Co-
MoS2 are investigated. Fig. 4e and f displayed the spin-polarized
total densities of states (TDOS) (upper panels) and corresponding
DOS projected on 3d states of metal atom, adsorbed O2 and the iso-
lated O2 gas molecules (lower panels) for O2 adsorption on Fe, Co-
MoS2. As displayed by the PDOS plots in the lower panels of
Fig. 4e and f, the 2p⁄ antibonding orbital of O2 is delocalized, and
is overlapped with 3d orbitals of Fe or Co atom at a wide energy,
indicating a strong hybridization between metal atom and O2
molecule. It results in more electron transfers from Fe or Co atom
3d state to O2 2p⁄ antibonding orbital (0.65 e and 0.55 e for Fe, Co,
respectively). The result also leads to the stronger activation of O2
molecule and agreement with the obvious elongation of the O-O
bond (Fig. 6a and c). As for the magnetic properties, it is shown that
O2 adsorption has almost not changed the total magnetic moments
of Fe-MoS2 (1.96 lB), but increased the spin magnetic moment of
Co-MoS2 (2.75 lB). Fig. 6b and d also shows that the spin charge
densities are mainly localized on the adsorbed O2 and the embed-
ded Fe, or Co atoms.
 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
Fig. 6. Top and side views of the geometric structures (a) and the spin charge density (b) for O2 adsorption on Fe-MoS2 system. Top and side views of the geometric structures
(c) and the spin charge density (d) for O2 adsorption on Co-MoS2 system. Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo; O, red. The light green and light yellow
regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
3.2.4. Adsorption of NO2 on TM-MoS2
For the adsorption of NO2, the most favorable adsorption config-
urations of NO2/TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and
Ir) are investigated. There are two different adsorption modes for
the adsorption of NO2 on diverse transition metals-embedded
MoS2. For embedded Fe, Co, Cu, Ag and Au systems, NO2 molecule
is prefer to adsorb on TM-MoS2 (TM = Fe, Co, Cu, Ag and Au) via
two O atoms bound to metal site by forming a TMAOANAO
four-membered ring. Corresponding NAO average bond lengths
have been elongated about 0.07 Å compared with that of NO2
molecule in gas phase (1.21 Å), indicating strong activation of
adsorbed NO2 molecule. While for Ni, Rh, Pd, Pt and Ir atoms,
NO2 molecule is preferentially via N atom binding to the embedded
metal atoms (TM = Ni, Rh, Pd, Pt, Ir). After adsorption, the NAO
average bond lengths have just slightly elongated about 0.02 Å
compared with that of NO2 molecule in gas phase (1.21 Å), indicat-
ing weak activation of adsorbed NO2 molecule. The adsorption
energies of NO2/TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt
and Ir) are listed at Table 2. The high adsorption energies exhibit
a strong interaction between embedded atom sites and NO2, in
accordance with the sequence of Pd (0.61 eV) < Pt (0.83 eV) < Ni
(1.11 eV) < Ag (1.35 eV) < Rh (1.45 eV) < Au (1.56 eV) < Co
(1.60 eV) < Cu (1.69 eV) < Ir (1.81 eV) < Fe (2.10 eV). Specially, after
NO2 molecule adsorption on Fe-MoS2, the adsorption energy of
NO2/Fe-MoS2 (Eads = 2.10 eV) is the highest among all of NO2/TM-
MoS2, indicating embedded Fe center has better adsorption proper-
ties for adsorption of O2 molecule. We also considered the adsorp-
tion behavior of NO2 on perfect monolayer MoS2. Our results show
that the adsorption between NO2 and pristine-MoS2 is rather weak
with corresponding adsorption energy of 0.04 eV, which is lower
(0.57–2.06 eV in energy) than those of NO2/TM-MoS2 (TM = Fe,
Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir). Thus, it further proves that
transition metal atoms embedded monolayer MoS2 have obvious
effect on adsorption of NO2. In order to illustrate the charge trans-
fer occurring between NO2 and TM-MoS2, the Bader charge is ana-
lyzed (Table 3 and Fig. 9). Similar to adsorption of oxide gas O2,
after the NO2 adsorption on TM-MoS2 (TM = Fe, Co, Ni, Cu, Ag,
Au, Rh, Pd, Pt and Ir), more electrons are transferred from TM-
MoS2 system to adsorbed NO2 molecule, especially for embedded
263
Fe, Co, Cu, Ag and Au systems ( 0.66 e, 0.61 e, 0.64 e, 0.60
e, 0.54 e, for Fe, Co, Cu, Ag, Au, respectively) This is consistent
with the adsorption mode, in which NO2 molecule interacts with
TM-MoS2 via two O atoms bound to metal site. Further analysis
of atomic Bader charge suggests that obtained electrons by
adsorbed NO2 mainly come from the embedded transition metal
atoms in TM-MoS2, indicating the importance of embedded transi-
tion metal atoms on the stability of NO2/TM-MoS2 (TM = Fe, Co, Ni,
Cu, Ag, Au, Rh, Pd, Pt and Ir).
We further analyze the structures and electronic properties of
NO2/Fe-MoS2 and NO2/Co-MoS2 for example. The most stable
adsorption configurations of NO2/Fe-MoS2 and NO2/Co-MoS2 are
displayed in Fig. 7a and c. Two O atoms of NO2 molecule are
bonded to embedded Fe site by forming two OAFe bonds (2.11 Å
and 2.09 Å for Fe, and 2.04 Å, 2.12 Å for Co, respectively). While
the NAO bond length of adsorbed NO2 are elongated about
0.07 Å with respect to that in NO2 gas molecule (1.21 Å), suggest-
ing activation for NO2 molecule. The corresponding adsorption
energy (2.10 eV, 1.60 eV for Fe and Co, respectively) is much higher
than that of NO2/pristine-MoS2 (0.04 eV), suggesting significantly
enhancement of adsorption properties by embedding transition
metal atoms. To explore the interactions between embedded metal
atom and NO2 molecule, the electronic structures of NO2 adsorp-
tion on Fe-MoS2 and Co-MoS2 are studied. The total DOS and PDOSs
for Fe, Co atom and adsorbed NO2 molecule are shown in the lower
panels of Fig. 4g and h. It can be seen that the molecular orbital of
adsorbed NO2 molecule is mixed with the Fe or Co 3d state at a
wide energy, indicating a strong hybridization between 6a1, 1a2
and 4b1 orbitals of adsorbed NO2 molecule and the 3d orbital of
metal atoms. In particular, the unoccupied spin-down orbital 6a1
(1.0 eV) of the NO2 gas molecule is significantly lowered to
0.5 eV and consequently becomes occupied. It results in more
electron transfers ( 0.66 e and 0.61 e for Fe, Co, respectively)
from substrate to adsorbed NO2 molecule. As for the magnetic
properties, the total spin magnetic moment is significantly
increased after NO2 adsorption on the Fe-MoS2 and Co-MoS2 sys-
tem (2.90 lB and 1.95 lB for Fe-MoS2 and Co-MoS2, respectively).
Further spin charge densities of NO2 on Fe-MoS2 and Co-MoS2
(Fig. 7b and d) further show that the spin magnetic moments are
264 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
Fig. 7. Top and side views of the geometric structures (a) and the spin charge density (b) for NO2 adsorption on Fe-MoS2 system. Top and side views of the geometric
structures (c) and the spin charge density (d) for NO2 adsorption on Co-MoS2 system. Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo; N, blue; O, red. The light green
and light yellow regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)
mainly localized on the adsorbed NO2 and the embedded Fe, or Co
atoms.
3.2.5. Adsorption of NH3 on TM-MoS2
For the adsorption of NH3 molecule on the TM-MoS2 (TM = Fe,
Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir), NH3 molecule is anchored at
embedded metal site by forming one NATM bond. We found that
after adsorption, the N-H average bond lengths (1.02–1.03 Å) are
almost not changed compared with that of NH3 in gas phase
(1.02 Å). Corresponding adsorption energies are with the order of
Pd < Pt < Ag < Au < Rh < Ni < Ir < Co < Cu < Fe (0.78 eV, 0.89 eV,
0.97 eV, 0.99 eV, 1.02 eV, 1.13 eV, 1.14 eV, 1.18 eV, 1.28 eV,
1.33 eV, for Pd, Pt, Ag, Au, Rh, Ni, Ir, Co, Cu, Fe, respectively). Among
them, NH3/Fe-MoS2 has the highest adsorption energy (1.33 eV),
which is higher 0.05–0.55 eV in energy than that on other NH3/
TM-MoS2. Compared with the weak interaction between NH3
molecule and perfect monolayer MoS2 with the adsorption energy
of 0.01 eV, the interaction between NH3 molecule and TM-MoS2
are much stronger with the adsorption energies ranging from
0.78 eV to 1.33 eV, suggested that transition metal atom embedded
monolayer MoS2 is vital for adsorption of NH3 molecule. To analyze
the charge transfer occurring between NH3 and TM-MoS2, the
Bader charges are calculated as shown in Table 3 and Fig. 9. In con-
trast to other adsorption of small gas molecules (CO, NO, O2 and
NO2), the direction of charge transfer is reversed for the deposition
of the NH3 molecule, in which small charge transfer occurs from
reducing gas molecule NH3 to TM-MoS2 surface (0.13 e, 0.13 e,
0.14 e, 0.17 e, 0.14 e, 0.22 e, 0.18 e, 0.11 e, 0.13 e and 0.17 e for
Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir, respectively) after NH3
adsorption on TM-MoS2.
In order to further analyze the interaction between NH3 and
TM-MoS2, we analyze the structures and electronic properties of
NH3 on Fe-MoS2 and Co-MoS2. As shown in Fig. 8a and c, NH3
molecule adsorbed on Fe-MoS2 and Co-MoS2 by forming one
NATM bond (2.12 Å, 2.07 Å for NAFe bond and NACo bond, respec-
tively). Compared with the NH3 in gas phase, the NAH bond
lengths of adsorbed NH3 molecule have almost not changed
(1.02–1.03 Å). Corresponding adsorption energies are 1.33 eV and
1.18 eV for NH3/Fe-MoS2 and NH3Co-MoS2, respectively, which
are much higher than that of the NH3/pristine-MoS2 with the
physisorption energies of 0.01 eV. The results suggested much
stronger adsorption behaviors for NH3/Fe-MoS2. Then the elec-
tronic structures of NH3/Fe-MoS2 and NH3/Co-MoS2 are further
investigated. Fig. 4i and j are displayed the spin-polarized total
densities of states (TDOS) (upper panels) and corresponding DOS
projected on Fe or Co 3d state, adsorbed NH3 and the isolated
NH3 molecule (lower panels) for NH3 molecule adsorption on Fe,
Co-MoS2. It can be seen that the DOS curves of adsorbed NH3 are
overlapped with 3d orbitals of Fe or Co atom, showing a weak
interaction between the NH3 and TM-MoS2. It results in 0.13 e
transfer from adsorbed NH3 molecule to the substrate. As for the
magnetic properties, after NH3 adsorption on the TM-MoS2
(TM = Fe, Co), the total magnetic moments for whole adsorption
system are almost not changed (2.11 lB, 1.02 lB for NH3/Fe-MoS2
and NH3/Co-MoS2, respectively). The further analysis of the spin
charge density shows that spin magnetic moments are mainly
localized on the embedded Fe, or Co atoms and a slight contribu-
tion of NH3 molecule (Fig. 8b and d).
As all we known, van der Waals (vdW) forces are ubiquitous in
the binding of atoms and molecules [48–50]. Therefore, we further
consider the effect of van der Waals (vdW) forces on the adsorption
of small gas phase molecules using Grimme’s DFT-D2 method. As
expected, when the long-range terms are included, the adsorption
energies are increased around 0.1–0.2 eV for all the adsorption
configurations, as shown in Table 2. Among them, for Pd-MoS2
and Pt-MoS2, the effect of vdW correction on gas molecules adsorp-
tion is more pronounced with an increase in the adsorption ener-
gies around 10–34%. Whereas, a smaller effect on embedded Fe,
Co, Ni, Cu, Ag, Au, Rh and Ir systems, with an increased adsorption
energy by about range of 8–19%. In addition, the preference
adsorption configurations, magnetic moments have almost not
changed in a significant way when the vdW forces are included.
And the inclusion of van der Waals forces also has no significant
effects on the Bader charges, the largest difference being 0.05 e.
 Y. Fan et al. / Computational Materials Science 138 (2017) 255–266
Fig. 8. Top and side views of the geometric structures (a) and the spin charge density (b) for NH3 adsorption on Fe-MoS2 system. Top and side views of the geometric
structures (c) and the spin charge density (d) for NH3 adsorption on Co-MoS2 system. Color scheme: Mo, green; S, yellow; Fe, purple; Co, indigo; N, blue; H, white. The light
green and light yellow regions represent the electron accumulation values. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)
0.2 NH3
Net Bader Charge (e)
0.0
-0.2 CO
-0.4 NO
O2
-0.6 NO2
Fe Co Ni Cu Ag Au Rh Pd Pt Ir
Embedded Atom Type
Fig. 9. Net bader charge (qgas in e) of gases for CO, NO, O2, NO2 and NH3 adsorption
on the transition metal-embedded monolayer MoS2 with the S-vacancy at the metal
site, respectively.
4. Conclusions
We have investigated the structures and electronic properties of
various transition metal atoms (Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and
Ir) embedded monolayer MoS2, and the effect on adsorption and
activation of some small gas molecules (CO, NO, O2, NO2 and
NH3) based on the density functional theory (DFT), with and with-
out the inclusion of van der Waals (vdW) forces. The strong inter-
actions between various transition metal atoms and S defect site in
monolayer MoS2 indicated that the transition metal atoms embed-
ded monolayer MoS2 should be stable. The electronic properties of
TM-embedded monolayer MoS2 are significantly changed due to
the induced transition metal impurity states in the band gap.
And the magnetic properties of monolayer MoS2 can be modulated
by the embedded transition metals. In order to study the effects of
the different TM-embedded monolayer MoS2 on the adsorption
properties and catalytic activities, the adsorption of gas molecules
(CO, NO, O2, NO2 and NH3) on the perfect and various transition
metal atoms (TM = Fe, Co, Ni, Cu, Ag, Au, Rh, Pd, Pt and Ir)-
265
embedded monolayer MoS2 were investigated. The results sug-
gested that the transition metals-embedded monolayer MoS2
improve the adsorption properties of gas molecules on TM-MoS2
with high adsorption energies in the range of 0.29–3.12 eV, com-
pared with that on pristine monolayer MoS2. The electronic struc-
ture analysis reveals that the high adsorption properties and
chemical activities of TM-MoS2 are attributed to the strong mix-
ture between TM-nd orbital and molecular orbital of gas molecule,
which effectively activates the adsorbed gas molecule. In addition,
obvious charge transfer occur from TM-MoS2 to oxidizing gas
molecules (NO2, O2) acting as acceptors, whereas the direction of
charge transfer is reversed for the adsorption of the reducing gas
(NH3) as donor. While in the case of NO and CO molecules, the
magnitude of charge transfer is small. In particular, among all
the TM-embedded monolayer MoS2, small gas molecules adsorp-
tion on the earth-abundant Fe and Co atom embedded monolayer
MoS2 have better thermal stability, adsorption properties and
chemical activities. The inclusion of van der Waals (vdW) forces
is also considered. Our calculated results show the adsorption
energies are increased around 0.1–0.2 eV in energy for all adsorp-
tion configurations, when the long-range terms are included.
Therefore, given the high thermal stability and chemical activities,
our study provides a path to improve the applications for high
active MoS2-based two-dimensional catalyst and gas sensors.
Acknowledgements
This work was supported by National Natural Science Founda-
tion of China (Grant Nos. 21403094, 21373048), Natural Science
Foundation of Jiangxi Province (No. 20142BAB216031), and the
Independent Research Project of State Key Laboratory of Photo-
catalysis on Energy and Environment (No. 2014A02). We are grate-
ful for the generous allocation of computer time on the National
Supercomputer Center in Guangzhou houses Tianhe-2.
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