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PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
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Room-temperature SO2 gas sensing properties based on metal-

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doped MoS2 nanoflower: an experimental and density functional

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
theory Investigation
Dongzhi Zhang,*a Junfeng Wu, a Peng Li *b and Yuhua Cao a
This paper demonstrates a sulfur dioxide (SO2) gas sensor based on transition metal doped molybdenum disulfide (MoS2)
nanocomposite synthesized via a facile single-step hydrothermal route. The Ni-doped, Fe-doped, Co-doped and pristine
MoS2 film sensors were fabricated on a FR4 epoxy substrate with interdigital electrodes (IDEs). The morphologies,
microstructures and compositions of as prepared samples were fully examined by using X-ray diffraction (XRD), energy
dispersive spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscope (TEM), and X-ray
photoelectron spectroscopy (XPS). The gas-sensing properties of the four samples were systematically investigated at
room-temperature, and Ni-doped MoS2 film sensor was screened out as the optimal SO2 sensor among the four sensors,
which exhibits relatively high response value, quick response/recovery time, and excellent stability toward SO2 gas.
Furthermore, to explain the experimental results, we used Materials Studio to construct the molecular models of
adsorption systems and calculate the geometry, energy, and charge parameters via density functional theory (DFT) based
on the first-principles, and the sensing mechanism was profoundly discussed. This work suggests that the Ni-doped MoS2
film sensor is qualified to detect SO2 gas at room temperature by a comprehensive research approach of combining
experiment with DFT simulation.

species of nanosized semiconductor material to fabricate SO2 gas

8 9 10
1. Introduction sensors, such as SnO2, WO3, and TiO2. However, most of
reported SO2 sensors based on semiconductor, especially metal
Sulfur dioxide (SO2), which is one of significantly hazardous
oxide, displayed good sensitivity over an operating temperature of
environmental pollutant gases and greenhouse gases (GHGs), is
200-600 °C, which lead to harsh operating condition and higher
discharged mainly from the coal combustion of fossil fuels in the 11,12
1,2 power consumption. Therefore, the fabrication of
process of industrial production. With the concentrations of SO2
semiconductor gas sensor working at room temperature is a
in atmosphere increasing, it contributes to acid rain as well as
3-5 beneficial and significant work for the detection of SO2.
severe damage to the human health. Therefore, an accurate and
Nowadays, two-dimensional (2D) layered nanomaterials, with
rapid method to detect sulfur dioxide is extremely important and
6 atomically ultrathin structure and remarkable electrical
necessary in various fields. Although, various approaches, such as
performances, have been investigated as an emerging building
chromatography and multiple spectroscopic techniques, to monitor 13-16
block for sensors fabrication. Among the family of inorganic 2D
the concentration of sulfur dioxide in atmosphere have been
layered nanomaterials, molybdenum disfulfide (MoS2) has attracted
developed, they are hard to use extensively owing to the problems
7 significant attention in various fields, especially fabrication of gas
of high cost, complicated operation, and bulky instrument. 17 18 19 20
sensors. Varieties of gas molecules, such as NO2, H2, NH3,
Fortunately, nanosized semiconductors gas sensor has attracted 21 22
water vapor, and volatile organic compounds, have been
increasing attentions due to the advantages of
measured at room temperature by gas sensors based on MoS2 due
microminiaturization, low cost, remarkable sensing characteristics, 23
to its large surface-to-volume ratio, distinctive electronic
and excellent physical-chemical stability. Therefore, late-model 24 25
properties, considerable band gap of 1.8 eV, and high carrier
nanosized semiconductors -based gas sensors, meeting the above- 26
mobility. Transition metal doping can increase the activity of MoS2
mentioned requirements, have been investigated.
by changing the original crystal structure to form new active sites,
Recently, a lot of research groups devote to employ various
and create capture trap of electron-hole to decrease the rate of
27
electron-hole recombination. Although, the theory study of gas
adsorption of metal-doped MoS2 has been investigated by many
25,28-31
researchers, the experiment has been rarely reported.

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In this paper, we prepared four SO2 gas sensors based on Ni-
doped, Fe-doped, Co-doped, and pristine MoS2 respectively via a
facile one-step hydrothermal route. To testify the as-prepared
samples, their morphologies, microstructures and compositions
were fully characterized via XRD, EDS, SEM, TEM, and XPS. The SO2-
sensing properties of the sensors were investigated at room
temperature, and Ni doped MoS2 was screened out as the optimal
SO2 sensor among the four sensors. To further verify that Ni-doped
MoS2 sensor is qualified to detect SO2, its extra sensing properties
including concentration measurement characteristics, repeatability,
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selectivity, and long-term stability were investigated. Moreover,
Materials Studio Software was used to construct the molecular
models of adsorption systems and calculate the geometry, energy,
and charge parameters via density functional theory (DFT) based on
the first-principles. The underlying sensing mechanism of transition
metal doped MoS2 toward SO2 was discussed in detail by combining
experiment with DFT calculation.
2. Experimental
2.1 Materials
Reagents used in this work involving Na2MoO4·2H2O (>99 %),
thioacetamide (>99 %), NiCl2·6H2O (>98 %), FeCl3·6H2O (>99 %), and
Co(NO3)2·6H2O (>98.5 %) were all obtained from Chinese Medicine
Group Chemical Reagent Co. Ltd (Shanghai, China), and they were
used without further purification.
2.2 Fabrication
To synthesize Ni-doped, Fe-doped, Co-doped, and pristine MoS2,
a facile one-step hydrothermal method was used in this work. 5
mmol of Na2MoO4·2H2O (1.21 g) and 25 mmol of thioacetamide
(1.90 g) were dissolved into 60 mL of mixed solvent consisting of 50
% deionized (DI) water and 50 % ethanol, which were used as Mo
and S sources, respectively. Then, 0.55 mmol of NiCl2·6H2O (0.131
g), FeCl3·6H2O (0.148 g), and Co (NO3)2·6H2O (0.131 g) were added
into the resulting solution separately to get the doping
concentration of experiment samples and guarantee the final
product can be defined as Mo0.9M0.1S2 (M indicates metal doped).
Next, the mixture was stirred and ultrasonicated for 15 min,
respectively. The obtained mixture solution was hydrothermally
treated in a 100 mL stainless-steel autoclave with a Teflon liner at
200 °C for 48 h. After cooling to room temperature naturally, the
product was obtained by washing with DI water multi-times and
Fig. 1 Hydrothermal and drop-casting processes for fabricating SO2 sensor.
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Fig.2 Schematic of experimental setup for SO2-sensing.
drying in a vacuum oven at 50 °C for 6 h. The resulting powder was
annealed at 700 °C for 2 h under the protection of pure nitrogen. As
a benchmarked sample, pristine MoS2 was prepared with the same
method as the transition metal doped MoS2 in the absence of the
doped transition metal source. The obtained powder was dispersed
in DI water and ultrasonicated for 10 min. Then resulting dispersion
was drop-casted on a FR4 epoxy substrate with interdigital
electrode microstructure to form sensing film. Finally, the sensor
was dried in a vacuum oven at 50 °C for 6 h. Fig. 1 shows the
fabrication process of SO2 sensors based on one-step hydrothermal
and drop-casting method.
2.3 Instrument and analysis
In this paper, a schematic of SO2 gas sensing experimental setup
is exhibits in Fig. 2. Air was used as background gas and all the
measurements were performed at room temperature. A data
logger (Agilent 34970A) linked to a computer via RS-232 interface
was used to record the real-time resistance of sensors. The sensing
film was placed in a conical flask with desired gas concentration of
SO2, which was obtained via injecting a precomputed volume of SO2
32, 33
gas into the conical flask using a syringe. In our experiment, the
sensors were exposed to varying concentrations of SO2 in a wide
range of 0.25 ppm to 4000 ppm to investigate their sensing
properties. The normalized response (R), determined by R=|△R|/R0
=|R0-Rg|/R0×100%, was used for evaluating the sensing
performances of sensors. R0 and Rg were the electrical resistance of
sensor in dry air and the given concentration of SO2, respectively.
3. Results and discussion
3.1 Materials characterizations
The X-ray diffractograms (XRD) measurement for the
experimental samples was performed by an X-ray diffractometer
(Rigaku D/Max2500PC, Japan) using Cu Kα radiation with a
wavelength of 1.5418 Å. The diffraction angle was set in the range
of 10°-80°. Fig. 3(a) shows the XRD spectra of MoS2, Ni-doped
MoS2, Fe-doped MoS2 and Co-doped MoS2 samples. No impurity
crystal phases are observed in the XRD patterns of all experimental
samples. The diffraction peaks of MoS2 are located at 2θ of 14.4°,
33.1°, 39.7°, and 58.5°, which are accorded with the (002), (100),
34
(103) and (110) planes, respectively. The patterns of metal doped
MoS2 samples only show slight changes from MoS2 in the widening
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Fig. 3 (a) XRD spectra of pristine MoS2 and metal-doped MoS2 samples. EDS
spectra of (b) Ni-doped MoS2, (c) Fe-doped MoS2, and (d) Co-doped MoS2.
and shifting of diffraction peaks, which are consistent with the
27,35,36
previous reports. The phenomenon of the absence of other
metal sulfide peaks is attributed to the low doping concentration
and high solubility of Ni, Fe, and Co ions, which suggests that
crystalline structure of MoS2 is not obviously affected by the close
combination of these metal ions and MoS2.
27,35
The element
component of metal doped MoS2 samples was examined by Hitachi
S-4800 equipped with an energy dispersive spectrometer (EDS). The
EDS spectra of Ni, Fe, and Co doped MoS2 samples are shown in Fig.
3(b)-3(d), respectively, which clearly verifies the existence of Mo, S,
and respective doping metal without impurity element.
Field emission scanning electron microscopy (FESEM, Hitachi S-
4800) was used to observe the surface micromorphology of MoS2,
Ni doped MoS2, Fe doped MoS2, and Co doped MoS2, as shown in
Fig. 4(a)-4(d) respectively. Undoped and doped MoS2 samples show
the similar flower-nanosphere morphology, which is constituted by
nanosheets and wormlike nanorods stacking together. However,
metal doped MoS2 exhibits the larger surface clearance due to the
decreasing stack degree of their component units.
The microstructure of the metal doped MoS2 was inspected by
JEOL JEM 2100, and the TEM images are shown in Fig. 5. Fig. 5(a)
Fig. 4 SEM images of (a) MoS2, (b) Ni-doped MoS2, (c) Fe-doped MoS2, (d) Co-
doped MoS2 samples.
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Fig. 5 (a) TEM micrograph of metal-doped MoS2 sample. HRTEM micrographs of
(b) Ni-doped MoS2, (c) Fe-doped MoS2, (d) Co-doped MoS2 samples.
shows the structure of MoS2 that consists of nanosheets with a size
of 620 nm and clusters stacked by nanorods with a size of 250 nm.
The high-resolution TEM (HRTEM) images of Ni, Fe, and Co doped
MoS2 were depicted in Fig. 5(b)–5(d), respectively. The lattice fringe
spacing of 0.62 nm is shown in the three TEM images, which
correspond to the (002) plane of MoS2.37 The lattice fringe spacing
of NiS2, FeS2, and CoS2 attributed to separate (200) plane are
labelled in Fig. 5(b)-5(d), which are 0.28 nm, 0.27 nm, and 0.28 nm,
respectively.38-40
XPS analysis (Thermo Scientific Escalab 250Xi) was carried out to
investigate the elemental composition and chemical state of metal
doped MoS2. The XPS survey spectra of all samples were plotted in
Fig. 6(a), which demonstrates that experimental samples are
composed of Mo, S, and respective metal elements. As shown in Fig.
6(b) and 6(c), two predominant peaks at 232.38 eV, 229.18 eV are
attributed to the doublet Mo 3d3/2 and Mo 3d5/2, and two peaks at
163.18 eV, 161.98 eV can be assigned to S 2p1/2 and S 2p3/2, which
41
are in agreement with the previous reported results. In the XPS
spectrum of Ni element in Fig. 6(d), two strong peaks are located at
873.78 eV and 856.18 eV, which are corresponding to the Ni 2p1/2
42
and Ni 2p3/2. And two weak peaks by the side of the strong peaks
are satelite peaks. Fig. 6(e) obviously shows two peaks at 720.48 eV
43
and 707.99 eV, which are indexed to the Fe 2p1/2 and Fe 2p3/2. As
shown in Fig. 6(f), two major peaks at 873.78 eV and 856.18 eV are
42
assigned to Co 2p1/2 and Co 2p3/2.
3.2 SO2 sensing properties
The sensing properties of the Ni-doped MoS2, Fe-doped MoS2,
Co-doped MoS2 and pristine MoS2 sensors were investigated at
room temperature. The measurement was performed by exposing
the sensors to various concentrations of SO2 from 0.25 ppm to
4000 ppm. Fig. 7(a) shows the time-dependent gas-sensing
response-recovery curves of the four sensors, which measured by
switching between different concentrations of SO2 and air, and the
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Fig. 6 XPS spectra of metal doped MoS2: (a) survey spectrum, (b) Mo 3d, (c) S 2p, (d) Ni 2p, (e) Fe 2p, and (f) Co 2p.

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Fig. 7 (a) Responses and (b) function fitting curves of the Ni-doped MoS2, Fe-
doped MoS2, Co-doped MoS2 and pristine MoS2 sensor toward varying
concentrations of SO2.
exposure time and recovery time is 90 s, respectively. We can find
that Ni-doped MoS2 sensor exhibits the highest response among the
four sensors, Fe-doped MoS2 sensor is the second, Co-doped MoS2
Fig. 8 The responses and recovery characteristics of (a) Ni-doped MoS2, (b) Fe-doped MoS2, (c) Co-doped MoS2 and (d) pristine MoS2 film sensors exposed to 5 ppm
and 500 ppm SO2.
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sensor is the third, and the last is pristine MoS2 sensor. Fig. 7(b)
plots the responses of the four sensors as a function of SO2 gas
concentration. The fitting equations of the sensor response Y and
gas concentration X are represented as Y = 5.251 + 3.965 lg X, Y =
Journal of Materials Chemistry A Accepted Manuscript
3.046 + 1.726 lg X, Y = 1.108 + 2.089 lg X, and Y = 0.073 + 0.318 lg X
for Ni-doped, Fe-doped, Co-doped, and pristine MoS2 film sensors
respectively, and the regression coefficient is 0.95766, 0.83171,
0.86804, and 0.58437 respectively. The result indicates that Ni-
doped MoS2 film sensor exhibits the highest sensitivity and linearity
with the common logarithm of SO2 gas concentration among the
four sensors.
Fig. 8 shows the resistance variations and response/recovery
times of Ni-doped, Fe-doped, Co-doped and pristine MoS2 film
sensors exposed to 5 ppm and 500 ppm SO2. With the gas
concentration increasing, the resistances of the four sensors
decrease monotonically. The response/recovery time is defined as
the time taken by a sensor to achieve 90% of the total resistance
change in the response/recovery stage. The Ni-doped MoS2 sensor
exhibits the highest response value and fairly fast response/
recovery time among the four sensors.
In conclusion, Ni-doped MoS2 film sensor exhibits the best sensing
properties for SO2 among the four samples. To further investigate
the advantages of the Ni-doped MoS2 film sensor, its properties in
terms of response-recovery characteristics, repeatability, selectivity
and long-term stability towards SO2 gas were measured. Fig. 9(a)
shows the response-recovery curves of single concentration
measurement, which were operated by switching the Ni-doped
MoS2 film sensor toward desired concentrations of SO2 and air. The
sensor exhibits stable response and recovery behaviours in
agreement with the continuous switching response of various
concentrations of SO2 (Fig. 7(a)). Fig. 9(b) illustrates the
repeatability of the Ni-doped MoS2 film sensor toward 1, 100, and
1000 ppm of SO2. The measurement was performed for four
exposure/recovery cycles under the same conditions. The
measurement results suggest a good consistency and
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Fig. 9 (a) Typical response-recovery curves for various concentrations of SO2, (b)
Repeatability for 1, 100, and 1000 ppm SO2, (c) Selectivity for 500 ppm of various
gas species, (d) Long term stability for 1, 100, and 1000 ppm SO2 of the Ni-doped
MoS2 film sensor.
reproducibility. Fig. 9(c) demonstrates the selectivity of the Ni-
doped MoS2 film sensor exposed to 500 ppm of sulfur dioxide (SO2),
nitrogen dioxide (NO2), ammonia (NH3), carbonic oxide (CO), carbon
dioxide (CO2), and hydrogen (H2) at room temperature,
respectively. The results indicate that the response to SO2 is
significantly higher than that of other tested gases. It may be
attributed to that the surface sulphur vacancies have much higher
adsorption energies toward SO2 gas, and hence much more SO2 gas
－ 44, 45
molecules are readily adsorbed and further converted to SO2 .
Fig. 9(d) exhibits the long-term stability of the Ni-doped MoS2 film
sensor toward 1, 100, and 1000 ppm of SO2. The response of the
sensor was measured every five days for over a month. It can be
clearly found that the response of the sensor did not vary
significantly with time passing, which confirms the Ni-doped MoS2
Fig. 10 (a) Top view of the pristine MoS2, the marked pink balls represent for the
adsorption site of H, B, TM, and TS, and side view of (b) Ni-doped, (c) Fe-doped,
and (d) Co-doped MoS2 in TM site.
film sensor has a good long-term stability.
Table 1 lists the SO2 gas-sensing performances of the Ni-doped
8, 46-53
MoS2 sensor compared with the previous works . The
comparison is made with the similar state-of-the-art materials in
terms of detection limit, operating temperature and response,
which demonstrates that Ni-doped MoS2 exhibits higher response,
lower detection limit and convenient work condition of room
temperature (RT). It can be obviously proved that Ni-doped MoS2
sensor is qualified to be a distinctive candidate for detection of SO2
in multifarious application fields.
3.3 Simulation and mechanism of SO2 gas-sensing properties.
In this work, Material Studio Software was used to discuss the
sensing mechanism of metal-doped MoS2 toward SO2 gas. The first-
principles electronic structure calculation was conducted in the
3
framework of spin-polarized calculations with the DMol

Table 1. Sensing performance of the SO2 sensor presented in this work compared with previous works.
Sensing material Limit of detection Operating temperature (°C) Response (%) Reference
Ni-MoS2 250 ppb RT 7.4 (5 ppm) This paper
NiO-SnO2 5 ppm 180 8.3 (50 ppm) 8
PANI 10 ppm RT 4.2 (10 ppm) 44
GO 5 ppm RT 6 (5 ppm) 45
ZnO 100 ppm RT 0.2 (100 ppm) 46
SnO2-PANI 2 ppm RT 3.1 (4 ppm) 47
WO3-PANI 5 ppm RT 4.3 (5 ppm) 48
WO3 20 ppm 350 3 (20 ppm) 49
V2O5/WO3/TiO2 20 ppm 400 5 (20 ppm) 50
Cu-SnO2 20 ppm 400 1.1 (20 ppm) 51

Table 2. Bond length, muliken charge, binding energy and band gap for the pristine and metal-doped MoS2.
Bond length (Å) Muliken charge (e)
System EB (eV) Eg (eV) Spin (μB)
Ma—S M S
Pristine MoS2 2.421 -0.024 0.012 — 1.789 0
Ni-doped MoS2 2.406 0.269 0.006 6.782 0 3.964
Fe-doped MoS2 2.318/2.251 -0.006 0.019/0.071 4.967 0.306 0
Co-doped MoS2 2.295/2.269 -0.036 0.035/0.056 5.609 0.104 0.997
a
M represents atom of TM site, i.e., Mo, Ni, Fe, Co atoms in pristine and metal-doped MoS2, respectively.

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Fig. 11 Spin-polarized total DOSs for Ni-doped MoS2 (red curve), Fe-doped MoS2
(pink curve) and Co-doped MoS2 (blue curve) compared with pristine MoS2
(black curve).

package,54,55 which included the Perdew-Burke-Ernzerh generalized

gradient approximation (GGA-PBE)56 for the exchange correlation
term, the double numerical plus polarization (DNP) basis set, and a
dispersion correction for an accurate description.57, 58 All adsorption Fig. 12 Top and side views of the most stable adsorption configurations of SO2 on

energies were obtained by using the Grimme’s empirically (a) Ni-doped MoS2, (b) Fe-doped MoS2, (c) Co-doped MoS2, and (d) pristine MoS2.

dispersion corrected density functional theory (DFT-D).59,60 The DFT The S, O atoms are yellow and red balls, respectively.

semi-core pseudopod core treatment was performed owing to its
relativistic effects, which substitute core electrons with a single
effective potential.61, 62 The real-space global orbital cutoff radius
was chosen as high as 4.9 Å. The Brillouin zone was set as 5×5×1 k-
points for all the structures in geometry optimization computation.
The convergence tolerance energy, the maximum force, and the
maximum displacement were set as 1.0×10-5 Ha (1 Ha = 27.211 eV),
0.002 Ha/Å, and 0.005 Å, respectively. The density of states (DOSs)
was calculated with 20×20×1 k-points based on the optimized
structures.
Fig. 10 shows the adsorption sites we used and relaxed geometry
structures of Ni-doped, Fe-doped, Co-doped and pristine MoS2. For
matching the composition of experimental samples used in this
work, which could be defined as Mo0.9M0.1S2, MoS2 monolayer was
established by a supercell that included 3×3 units (which consisted
of 9 Mo atoms and 18 S atoms), and a single Ni, Fe or Co atom was
used to replace one Mo atom of MoS2 in TM site. Furthermore, the
monolayer was separated by a 15 Å vacuum region in the Z
63
direction to avoid interactions between adjacent atomic layers.
64
The binding energies (EB) were calculated using the equation:
EB= Emetal + EMoS2 - Emetal/MoS2 (1)
Emetal, EMoS2 and Emetal/MoS2 are the energies of the isolated doped
metal atom, pristine MoS2 with a Mo vacancy, and the metal-doped
MoS2, respectively. The calculated results are presented in Table 2.
And spin-polarized total DOSs for Ni-doped, Fe-doped, Co-doped
and pristine MoS2 are shown in Fig. 11. The computed results of
band gap (Eg), Mo-S bond length and perpendicular length for
monolayer MoS2 are 1. 789 eV, 2.41 Å and 3.176 Å, respectively,
which are approximately equal to the experiment values that are
1.9 eV, 2.41 Å and 3.16 Å, respectively.
65, 66
Furthermore, the
calculation results represent that after doping, although bond
length changes little, the Ni-doped MoS2 shows the strongest
interaction with its neighboring Mo atoms due to the largest EB
value and the most change of electronic structure among the four
samples. According to the changes of band gap (Eg), spin changes
(μB) and DOS near the Fermi level, Ni-doped MoS2 suggests the
magnetic metal properties altered from nonmagnetic
semiconductor. It means that the electrochemical activity of Ni-
doped MoS2 is stronger due to the overlap of the conduction band
and valence band, which makes the electron of valence band
maximum (VBM) easier to flow to the conduction band.
In order to obtain the most stable adsorption geometry
structure, we considered four adsorption sites as shown in Fig. 9 (a).
We placed three different gas orientations at each site. SO2

Table 3. The bond length of SO2 molecule and doped atoms, perpendicular distance of SO2 to the substrate, the adsorption energy and the band gap of all systems.
Bond length (Å)
System Distance (Å) Ead (eV) Eg (eV)
M—S a S—O b
Pristine MoS2 2.422/2.421/2.420 1.466/1.465 3.103 -0.209 1.683
Ni-doped MoS2 2.248/3.246 1.470/1.468 2.775 -0.835 0.091
Fe-doped MoS2 2.321/2.252/2.302 1.466/1.466 3.023 -0.218 0.311
Co-doped MoS2 2.300/2.273/2.289 1.466/1.465 3.077 -0.213 0.105
SO2 — 1.465 — — —
a
M—S represents the bond length of Mo, Ni, Fe, Co atoms with neighboring S atoms from MoS2.
b
S—O represents the bond length of S and O atoms from SO2 gas molecule.

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Fig. 13 The total density of states (DOS) and projected density of states (PDOS) for the (a) Ni-doped, (b) Fe-doped, (c) Co-doped, and (d) pristine MoS2 before (left)
and after (right) adsorption of SO2.

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Table 4. Charge transfer of main atom and SO2 molecule in the doped and Table 5. Molecular frontier orbital energies and energy differences. Ef-L is the
pristine MoS2 systems before and after adsorption of SO2. absolute value calculated by Ef-substrate - ELUMO-gas. Ef-H is the absolute value
Charge transfer after adsorption (e) calculated by Ef-substrate - EHOMO-gas.
Systems
M S (from MoS2) S (from SO2) O SO2 Fermi energy HOMO LUMO Ef-H Ef-L
Systems

Journal of Materials Chemistry A Accepted Manuscript

MoS2 — 0.01/0.006/0 0.016 -0.011/-0.012 -0.006 (eV) (eV) (eV) (eV) (eV)
Ni-MoS2 -0.299 0.052/-0.106/0.069 -0.007 -0.035/-0.024 -0.065 Ni-MoS2 -5.525 — — 2.497 0.977
Fe-MoS2 0.001 0.006/-0.067/-0.004 0.013 -0.018/-0.012 -0.016 Fe-MoS2 -5.415 — — 2.607 0.867
Co-MoS2 0.007 0.015/-0.062/0.008 0.006 -0.014/-0.008 -0.015 Co-MoS2 -5.397 — — 2.625 0.849
MoS2 -5.355 — — 2.667 0.807
lied parallel to the monolayer and perpendicular to these sites SO2 — -8.022 -4.548 — —
with S or O atom pointed downward. The most stable geometry
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structures after adsorption are shown in Fig. 12. The doping

adsorption energies (Ead) were calculated using the following
29
equation:
Ead = ESO /system – Esystem - ESO
2 2 (2)
ESO /system is the total energy of the relaxed systems after adsorption,
2 charge transfer on Fe-, Co-doped and pristine MoS2 systems. The
and Esystem and ESO are total energies for the four monolayers and
2 result reveals a weaker sensitivity to SO2 for Fe-, Co-doped and
isolated SO2 molecule, respectively. The negative value of Ead
suggests that the adsorption process is exothermic. Furthermore,
more detailed information of parameters after adsorption is shown
in Table 3. The Muliken charge transfer calculated from DFT is
summarized in Table 4, negative value means that SO2 acts as an
electron acceptor and accept electrons from the substrate. We can
clearly find that Ni doped MoS2 system has the most change of
bond length values of SO2 molecule and doped atoms, the shortest
perpendicular distance from SO2 molecule to the sensing system,
and the largest Ead as well as charge transfer values among the four
adsorption systems. The result demonstrates that the Ni doped
MoS2 system is the most sensitive to SO2, the Fe doped MoS2 is the
second, the Co doped MoS2 is the third and the last is the pristine
MoS2.
To better verify the effect of SO2 adsorption, Fig. 13 plots the
total and projected DOSs, where (a), (b), (c) and (d) are the DOSs of
all species atoms of substrates and SO2 molecules in Ni-doped, Fe-
doped, Co-doped and pristine MoS2 systems before and after
adsorption, respectively. For Ni-doped MoS2, electronic structure
changes significantly with SO2 adsorbed. The band gaps of the spin-
up and spin-down states around the Fermi energy are covered with
electron dominated by the Mo 4d and S 2p states after adsorption,
and the spin-splitting states vanish. The phenomenon could be
interpreted as that all peaks of Ni 3d orbital from -10 eV to 4.5 eV,
O 2p at -1.6 eV and S 2p (from SO2) orbital at around 4 eV reduced,
respectively, which indicates charge mainly transferred by SO2
molecule and Ni atom. However, we can hardly found differences in
DOSs plots of other three systems after adsorption except the
Fig. 14 Schematic diagram of charge transfer mechanism. Φ, Evac, Ef, ELUMO, and
E- represent the work function of the substrate, the energy of vacuum level,
Fermi energy of the substrate, the energy of LUMO from gas, and the
equilibrium state of the adsorption system, respectively.
peaks of S 2p (from SO2) and O 2p reduced. It means that electronic
structure of systems have a little change via van der Waals acts. This
can be explained as that SO2 undergoes physisorption and little
pristine MoS2 sensors than Ni doped MoS2, which is consistent with
the calculation results in Table 4.
The charge transfer mechanism at the metal-MoS2 interface is
explored to further discuss the sensing mechanism toward SO2. The
interaction of typical organic electron donor and acceptor
molecules has been investigated to understand non-covalent n/p-
58, 67
doping effects. The typical n/p type doping of adsorption
systems depend on the work function of metal-doped MoS2
nanoflower (Φ) as well as highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) of the
target gas. Chemisorption-induced energy is a significant factor to
cause the noticeable overlap and rearrangement of electron
distributions between the gas molecules and adsorption systems.
Furthermore, the direction and value of charge transfer in
adsorption system are controlled by chemical potentials, electron
affinity, and ionization potential values. With the charge transfer
continuing, the final molecularly charged states, considered as the
derived states of HOMO or LUMO from the perspective of
molecular orbital aspects, will balance the electron distribution and
+ -
stop the charge transfer process. Thereinto E and E represent a
positively charged donor and a negatively charged acceptor
formation energy state for adsorption system, respectively.
Table 5 presents the HOMO and LUMO of SO2, The absolute
positions of orbital energy are aligned to the vacuum level. Fermi
energies of Ni-, Fe-, Co-doped and pristine MoS2, and the absolute
value of energy differences between LUMO and Fermi energy (Ef-L)
and energy differences between HUMO and Fermi energy (Ef-H). It
can be obviously found that the Ef-L are much lower than Ef-H in the
four adsorption systems, which means that the four systems exhibit
p-type doping property. A schematic diagram of the p-type doping
process is shown in Fig. 14. When the SO2 molecule makes contact
with the metal-doped MoS2 film, electrons from the film voluntarily
flows to the gas molecules via tunneling due to the smaller energy
gap from Fermi energy to LUMO than HOMO, so that electron is
more inclined to flow from the film to the LUMO of gas molecule
than from HOMO of gas to the film. With the electron flows
continuing, an induced dipole at the interface is generated by the
confrontation of positively charged film and negatively charged gas
molecule, which downshifts the Fermi energy of the sensing
system; in another word, it increases the work function. The

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electron flow process will finally stop until reaching an equilibrium
-
state, where Φ is equal to E , which means the Fermi level is pinned
to a negatively charged state. The energy Δ assigned to the
interface dipole is the absolute value of the difference between the
-
energy of E and Φ. Among the four sensors, Ni-doped MoS2 has the
most charge transfer due to the largest value of Ef-L, in other word,
the largest value Δ, and hence yields the largest response value.
4. Conclusions
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This paper reports the transition metal doped MoS2 film sensor
synthesized by an easy-operated single-step hydrothermal method.
The as-prepared samples were characterized by XRD, EDS, SEM,
TEM and XPS methods to find their micromorphology and
nanostructure. The gas-sensing properties of as-prepared sensors
were systematically investigated at room-temperature, and the Ni-
doped MoS2 film sensor was screened out as the optimal SO2 sensor
among the samples, which exhibits relatively high response value,
quick response/recovery time and outstanding stability for SO2 gas.
Furthermore, Material Studio Software was used to simulate
adsorption process of metal-doped MoS2 film and calculate the
geometry, energy, and charge parameters as an important basis to
explain the sensing mechanism. In conclusion, Ni-doped MoS2 film
sensor is verified to be a qualified candidate to detect SO2 gas at
room temperature by a comprehensive research approach of
combining experiment with software simulation.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 51407200, 51777215, 51405257),
the Fundamental Research Funds for the Central Universities
of China (No. 15CX05041A), and the Science and Technology
Development Plan Project of Qingdao (No. 16-6-2-53-nsh).
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