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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
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.

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ARTICLE

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
theory Investigation
DOI: 10.1039/x0xx00000x Dongzhi Zhang,*a Junfeng Wu, a Peng Li *b and Yuhua Cao a
www.rsc.org/ 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

Journal of Materials Chemistry A Accepted Manuscript

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, Fig.2 Schematic of experimental setup for SO2-sensing.
and charge parameters via density functional theory (DFT) based on
the first-principles. The underlying sensing mechanism of transition drying in a vacuum oven at 50 °C for 6 h. The resulting powder was
metal doped MoS2 toward SO2 was discussed in detail by combining annealed at 700 °C for 2 h under the protection of pure nitrogen. As
experiment with DFT calculation. 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
2. Experimental in DI water and ultrasonicated for 10 min. Then resulting dispersion
was drop-casted on a FR4 epoxy substrate with interdigital
2.1 Materials
electrode microstructure to form sensing film. Finally, the sensor
Reagents used in this work involving Na2MoO4·2H2O (>99 %), was dried in a vacuum oven at 50 °C for 6 h. Fig. 1 shows the
thioacetamide (>99 %), NiCl2·6H2O (>98 %), FeCl3·6H2O (>99 %), and fabrication process of SO2 sensors based on one-step hydrothermal
Co(NO3)2·6H2O (>98.5 %) were all obtained from Chinese Medicine and drop-casting method.
Group Chemical Reagent Co. Ltd (Shanghai, China), and they were
used without further purification.
2.3 Instrument and analysis
In this paper, a schematic of SO2 gas sensing experimental setup
2.2 Fabrication
is exhibits in Fig. 2. Air was used as background gas and all the
To synthesize Ni-doped, Fe-doped, Co-doped, and pristine MoS2, measurements were performed at room temperature. A data
a facile one-step hydrothermal method was used in this work. 5 logger (Agilent 34970A) linked to a computer via RS-232 interface
mmol of Na2MoO4·2H2O (1.21 g) and 25 mmol of thioacetamide was used to record the real-time resistance of sensors. The sensing
(1.90 g) were dissolved into 60 mL of mixed solvent consisting of 50 film was placed in a conical flask with desired gas concentration of
% deionized (DI) water and 50 % ethanol, which were used as Mo SO2, which was obtained via injecting a precomputed volume of SO2
32, 33
and S sources, respectively. Then, 0.55 mmol of NiCl2·6H2O (0.131 gas into the conical flask using a syringe. In our experiment, the
g), FeCl3·6H2O (0.148 g), and Co (NO3)2·6H2O (0.131 g) were added sensors were exposed to varying concentrations of SO2 in a wide
into the resulting solution separately to get the doping range of 0.25 ppm to 4000 ppm to investigate their sensing
concentration of experiment samples and guarantee the final properties. The normalized response (R), determined by R=|△R|/R0
product can be defined as Mo0.9M0.1S2 (M indicates metal doped). =|R0-Rg|/R0×100%, was used for evaluating the sensing
Next, the mixture was stirred and ultrasonicated for 15 min, performances of sensors. R0 and Rg were the electrical resistance of
respectively. The obtained mixture solution was hydrothermally sensor in dry air and the given concentration of SO2, respectively.
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 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
Fig. 1 Hydrothermal and drop-casting processes for fabricating SO2 sensor. (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.
Fig. 5 (a) TEM micrograph of metal-doped MoS2 sample. HRTEM micrographs of

and shifting of diffraction peaks, which are consistent with the (b) Ni-doped MoS2, (c) Fe-doped MoS2, (d) Co-doped MoS2 samples.
27,35,36
previous reports. The phenomenon of the absence of other
metal sulfide peaks is attributed to the low doping concentration shows the structure of MoS2 that consists of nanosheets with a size
and high solubility of Ni, Fe, and Co ions, which suggests that of 620 nm and clusters stacked by nanorods with a size of 250 nm.
crystalline structure of MoS2 is not obviously affected by the close The high-resolution TEM (HRTEM) images of Ni, Fe, and Co doped
combination of these metal ions and MoS2.
27,35
The element MoS2 were depicted in Fig. 5(b)–5(d), respectively. The lattice fringe
component of metal doped MoS2 samples was examined by Hitachi spacing of 0.62 nm is shown in the three TEM images, which
S-4800 equipped with an energy dispersive spectrometer (EDS). The correspond to the (002) plane of MoS2.37 The lattice fringe spacing
EDS spectra of Ni, Fe, and Co doped MoS2 samples are shown in Fig. of NiS2, FeS2, and CoS2 attributed to separate (200) plane are
3(b)-3(d), respectively, which clearly verifies the existence of Mo, S, labelled in Fig. 5(b)-5(d), which are 0.28 nm, 0.27 nm, and 0.28 nm,
and respective doping metal without impurity element. respectively.38-40
Field emission scanning electron microscopy (FESEM, Hitachi S- XPS analysis (Thermo Scientific Escalab 250Xi) was carried out to
4800) was used to observe the surface micromorphology of MoS2, investigate the elemental composition and chemical state of metal
Ni doped MoS2, Fe doped MoS2, and Co doped MoS2, as shown in doped MoS2. The XPS survey spectra of all samples were plotted in
Fig. 4(a)-4(d) respectively. Undoped and doped MoS2 samples show Fig. 6(a), which demonstrates that experimental samples are
the similar flower-nanosphere morphology, which is constituted by composed of Mo, S, and respective metal elements. As shown in Fig.
nanosheets and wormlike nanorods stacking together. However, 6(b) and 6(c), two predominant peaks at 232.38 eV, 229.18 eV are
metal doped MoS2 exhibits the larger surface clearance due to the attributed to the doublet Mo 3d3/2 and Mo 3d5/2, and two peaks at
decreasing stack degree of their component units. 163.18 eV, 161.98 eV can be assigned to S 2p1/2 and S 2p3/2, which
41
The microstructure of the metal doped MoS2 was inspected by are in agreement with the previous reported results. In the XPS
JEOL JEM 2100, and the TEM images are shown in Fig. 5. Fig. 5(a) 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
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. 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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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
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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
Fig. 7 (a) Responses and (b) function fitting curves of the Ni-doped MoS2, Fe- agreement with the continuous switching response of various
doped MoS2, Co-doped MoS2 and pristine MoS2 sensor toward varying
concentrations of SO2.
concentrations of SO2 (Fig. 7(a)). Fig. 9(b) illustrates the
repeatability of the Ni-doped MoS2 film sensor toward 1, 100, and
exposure time and recovery time is 90 s, respectively. We can find 1000 ppm of SO2. The measurement was performed for four
that Ni-doped MoS2 sensor exhibits the highest response among the exposure/recovery cycles under the same conditions. The
four sensors, Fe-doped MoS2 sensor is the second, Co-doped MoS2 measurement results suggest a good consistency and

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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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.
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
film sensor has a good long-term stability.
gas species, (d) Long term stability for 1, 100, and 1000 ppm SO2 of the Ni-doped
Table 1 lists the SO2 gas-sensing performances of the Ni-doped
MoS2 film sensor. 8, 46-53
MoS2 sensor compared with the previous works . The
reproducibility. Fig. 9(c) demonstrates the selectivity of the Ni- comparison is made with the similar state-of-the-art materials in
doped MoS2 film sensor exposed to 500 ppm of sulfur dioxide (SO2), terms of detection limit, operating temperature and response,
nitrogen dioxide (NO2), ammonia (NH3), carbonic oxide (CO), carbon which demonstrates that Ni-doped MoS2 exhibits higher response,
dioxide (CO2), and hydrogen (H2) at room temperature, lower detection limit and convenient work condition of room
respectively. The results indicate that the response to SO2 is temperature (RT). It can be obviously proved that Ni-doped MoS2
significantly higher than that of other tested gases. It may be sensor is qualified to be a distinctive candidate for detection of SO2
attributed to that the surface sulphur vacancies have much higher in multifarious application fields.
adsorption energies toward SO2 gas, and hence much more SO2 gas
－ 44, 45
molecules are readily adsorbed and further converted to SO2 . 3.3 Simulation and mechanism of SO2 gas-sensing properties.
Fig. 9(d) exhibits the long-term stability of the Ni-doped MoS2 film
In this work, Material Studio Software was used to discuss the
sensor toward 1, 100, and 1000 ppm of SO2. The response of the
sensing mechanism of metal-doped MoS2 toward SO2 gas. The first-
sensor was measured every five days for over a month. It can be
principles electronic structure calculation was conducted in the
clearly found that the response of the sensor did not vary 3
framework of spin-polarized calculations with the DMol
significantly with time passing, which confirms the Ni-doped MoS2

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 metal atom, pristine MoS2 with a Mo vacancy, and the metal-doped
relativistic effects, which substitute core electrons with a single MoS2, respectively. The calculated results are presented in Table 2.
effective potential.61, 62 The real-space global orbital cutoff radius And spin-polarized total DOSs for Ni-doped, Fe-doped, Co-doped
was chosen as high as 4.9 Å. The Brillouin zone was set as 5×5×1 k- and pristine MoS2 are shown in Fig. 11. The computed results of
points for all the structures in geometry optimization computation. band gap (Eg), Mo-S bond length and perpendicular length for
The convergence tolerance energy, the maximum force, and the monolayer MoS2 are 1. 789 eV, 2.41 Å and 3.176 Å, respectively,
maximum displacement were set as 1.0×10-5 Ha (1 Ha = 27.211 eV), which are approximately equal to the experiment values that are
0.002 Ha/Å, and 0.005 Å, respectively. The density of states (DOSs) 1.9 eV, 2.41 Å and 3.16 Å, respectively.
65, 66
Furthermore, the
was calculated with 20×20×1 k-points based on the optimized calculation results represent that after doping, although bond
structures. length changes little, the Ni-doped MoS2 shows the strongest
Fig. 10 shows the adsorption sites we used and relaxed geometry interaction with its neighboring Mo atoms due to the largest EB
structures of Ni-doped, Fe-doped, Co-doped and pristine MoS2. For value and the most change of electronic structure among the four
matching the composition of experimental samples used in this samples. According to the changes of band gap (Eg), spin changes
work, which could be defined as Mo0.9M0.1S2, MoS2 monolayer was (μB) and DOS near the Fermi level, Ni-doped MoS2 suggests the
established by a supercell that included 3×3 units (which consisted magnetic metal properties altered from nonmagnetic
of 9 Mo atoms and 18 S atoms), and a single Ni, Fe or Co atom was semiconductor. It means that the electrochemical activity of Ni-
used to replace one Mo atom of MoS2 in TM site. Furthermore, the doped MoS2 is stronger due to the overlap of the conduction band
monolayer was separated by a 15 Å vacuum region in the Z and valence band, which makes the electron of valence band
63
direction to avoid interactions between adjacent atomic layers. maximum (VBM) easier to flow to the conduction band.
64
The binding energies (EB) were calculated using the equation: In order to obtain the most stable adsorption geometry
EB= Emetal + EMoS2 - Emetal/MoS2 (1) structure, we considered four adsorption sites as shown in Fig. 9 (a).
Emetal, EMoS2 and Emetal/MoS2 are the energies of the isolated doped 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 peaks of S 2p (from SO2) and O 2p reduced. It means that electronic
29
equation: structure of systems have a little change via van der Waals acts. This
Ead = ESO /system – Esystem - ESO
2 2 (2) can be explained as that SO2 undergoes physisorption and little
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 pristine MoS2 sensors than Ni doped MoS2, which is consistent with
suggests that the adsorption process is exothermic. Furthermore, the calculation results in Table 4.
more detailed information of parameters after adsorption is shown The charge transfer mechanism at the metal-MoS2 interface is
in Table 3. The Muliken charge transfer calculated from DFT is explored to further discuss the sensing mechanism toward SO2. The
summarized in Table 4, negative value means that SO2 acts as an interaction of typical organic electron donor and acceptor
electron acceptor and accept electrons from the substrate. We can molecules has been investigated to understand non-covalent n/p-
58, 67
clearly find that Ni doped MoS2 system has the most change of doping effects. The typical n/p type doping of adsorption
bond length values of SO2 molecule and doped atoms, the shortest systems depend on the work function of metal-doped MoS2
perpendicular distance from SO2 molecule to the sensing system, nanoflower (Φ) as well as highest occupied molecular orbital
and the largest Ead as well as charge transfer values among the four (HOMO) and lowest unoccupied molecular orbital (LUMO) of the
adsorption systems. The result demonstrates that the Ni doped target gas. Chemisorption-induced energy is a significant factor to
MoS2 system is the most sensitive to SO2, the Fe doped MoS2 is the cause the noticeable overlap and rearrangement of electron
second, the Co doped MoS2 is the third and the last is the pristine distributions between the gas molecules and adsorption systems.
MoS2. Furthermore, the direction and value of charge transfer in
To better verify the effect of SO2 adsorption, Fig. 13 plots the adsorption system are controlled by chemical potentials, electron
total and projected DOSs, where (a), (b), (c) and (d) are the DOSs of affinity, and ionization potential values. With the charge transfer
all species atoms of substrates and SO2 molecules in Ni-doped, Fe- continuing, the final molecularly charged states, considered as the
doped, Co-doped and pristine MoS2 systems before and after derived states of HOMO or LUMO from the perspective of
adsorption, respectively. For Ni-doped MoS2, electronic structure molecular orbital aspects, will balance the electron distribution and
+ -
changes significantly with SO2 adsorbed. The band gaps of the spin- stop the charge transfer process. Thereinto E and E represent a
up and spin-down states around the Fermi energy are covered with positively charged donor and a negatively charged acceptor
electron dominated by the Mo 4d and S 2p states after adsorption, formation energy state for adsorption system, respectively.
and the spin-splitting states vanish. The phenomenon could be Table 5 presents the HOMO and LUMO of SO2, The absolute
interpreted as that all peaks of Ni 3d orbital from -10 eV to 4.5 eV, positions of orbital energy are aligned to the vacuum level. Fermi
O 2p at -1.6 eV and S 2p (from SO2) orbital at around 4 eV reduced, energies of Ni-, Fe-, Co-doped and pristine MoS2, and the absolute
respectively, which indicates charge mainly transferred by SO2 value of energy differences between LUMO and Fermi energy (Ef-L)
molecule and Ni atom. However, we can hardly found differences in and energy differences between HUMO and Fermi energy (Ef-H). It
DOSs plots of other three systems after adsorption except the 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
Fig. 14 Schematic diagram of charge transfer mechanism. Φ, Evac, Ef, ELUMO, and continuing, an induced dipole at the interface is generated by the
E- represent the work function of the substrate, the energy of vacuum level, confrontation of positively charged film and negatively charged gas
Fermi energy of the substrate, the energy of LUMO from gas, and the molecule, which downshifts the Fermi energy of the sensing
equilibrium state of the adsorption system, respectively. system; in another word, it increases the work function. The

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electron flow process will finally stop until reaching an equilibrium 12 D. Z. Zhang, Y. E. Sun, C. X. Jiang, Y. Zhang, Sens. Actuators B
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Journal of Materials Chemistry A Accepted Manuscript

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29 K. N. Ding, Y. H. Lin, M. Y. Huang, Vacuum 2016, 130, 146-153.
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the Fundamental Research Funds for the Central Universities 26, 7445-7451.
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