Sensors & Actuators: B.

Chemical 403 (2024) 135215

Contents lists available at ScienceDirect

Sensors and Actuators: B. Chemical

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

One-pot hydrothermal synthesis of self-assembled MoS2/WS2 nanoflowers

for chemiresistive room-temperature NO2 sensors
Zhiping Liang a, 1, Mingyuan Wang b, 1, Siwei Liu a, Mobashar Hassan a, Xiangzhao Zhang a,
Shuangying Lei b, Guanjun Qiao a, Guiwu Liu a, *
a
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
b
SEU-FEI Nano-Pico Center, Key Laboratory of MEMS of Ministry of Education, School of Electrical Science and Engineering, Southeast University, 210096 Nanjing,
China

A R T I C L E I N F O A B S T R A C T

Key words: Transition metal dichalcogenides (TMDs) based heterostructures are becoming hotspots of gas-sensing applica­
Transition metal dichalcogenides tions due to the high electronic mobility, high surface-volume ratio, and abundant adsorption sites. However, the
Self-assembled nanoflowers preparation of TMDs-based heterostructures is usually required multiple steps or higher synthesis temperatures
Heterostructure
(≥ 500 ◦ C). Herein, the flower-like MoS2/WS2 composites were firstly prepared by a facile one-pot hydrothermal
Hydrothermal synthesis
method to effectively detect NO2 at room temperature. The WS2 molecules prefer to grow on the edge of as-
Gas sensing
nucleated MoS2 to form the MoS2/WS2 nanosheets, and then they can grow by layer-by-layer self-assembly to
form the MoS2/WS2 heterostructure. The optimized MoS2/WS2 heterostructured composite exhibits the very high
sensitivity to NO2 at room temperature, involving high response, good reproducibility, excellent selectivity and
long-term stability. Specially, the responses (ΔR/Rg) of MoS2/WS2-0.5 composite to 5 and 100 ppb NO2 are 6.1%
and 23.1%, respectively. Moreover, a plausible gas sensing mechanism was proposed from viewpoints of electron
transfer and gas adsorption by combining multiple experiments and DFT calculations. This work provides a facile
process for synthesis of TMDs-based heterostructures, but also a prospective gas sensing material for room-
temperature NO2 detection.

1. Introduction dichalcogenides (TMDs), are becoming hotspots of electronic, opto­

Due to growing concerns about the environment and human health,
there has been an increasing focus on monitoring hazardous gases in
modern society [1,2]. NO2 is one of the most common air pollutants that
can damage the ecosystem by triggering photochemical smog, acid rain
and ground-level O3 depletion [3]. Moreover, the NO2 concentration in
ambient environments was regulated by Japan government as the
threshold limit value (TLV) of ≤ 40–60 ppb because of its harm to
human health [4,5]. Generally, the metal oxide semiconductors (MOSs)
are used as the gas and humidity sensing materials. However, their
higher operating temperatures of 200–400 ◦ C limit their potential for the
energy-saving development of gas sensor in future [6,7]. Therefore, the
development of room-temperature-operated and highly sensitive gas
sensing materials is critical to creating efficient and reliable gas sensors
for toxic and harmful gases.
Recently, two-dimensional materials, such as transition metal
electronic, energy-saving and gas-sensing applications due to their
unique properties, involving thickness-dependent bandgap, high elec­
tronic mobility, high surface-volume ratio, and abundant adsorption
sites [8–11]. WS2 and MoS2 are two typical TMDs with good thermal
stability and room-temperature sensitivity to some harmful gases in
ambient environments, so they draw more attentions in the field of gas
sensing [12]. What’s more, the dangling bonds at the edges of TMDs
possess more active sites, which contribute to the adsorption of the gases
and the formation of heterostructures with other materials [13]. How­
ever, the disadvantages of pristine WS2 and MoS2 cannot be ignored,
including the low response and incomplete recovery to target gases at
room temperature [14,15]. To address these issues, some feasible stra­
tegies were proposed by constructing TMDs-based heterostructures to
improve the room-temperature gas sensing performance. For instance,
Ikram et al. fabricated a large-surface-area WS2/MoS2 heterojunction by
combining the exfoliation and hydrothermal processes, indicating that

* Corresponding author.
E-mail address: gwliu76@ujs.edu.cn (G. Liu).
1
The authors contribute equally to this paper.

https://doi.org/10.1016/j.snb.2023.135215
Received 30 August 2023; Received in revised form 21 December 2023; Accepted 21 December 2023
Available online 23 December 2023
0925-4005/© 2023 Elsevier B.V. All rights reserved.
Z. Liang et al. Sensors and Actuators: B. Chemical 403 (2024) 135215

the formation of WS2/MoS2 heterostructure can greatly enhance the After the stainless steel autoclaves were furnace-cooled to room tem­
room-temperature gas sensitivity to NO2, with the detection limit of 10 perature, the deposits were removed from the autoclaves, and the main
ppb [16]. Kim et al. fabricated the WS2/WSe2 and MoS2/WSe2 com­ powder products were obtained by repeatedly washing with ethanol and
posites by in-situ chemical vapor deposition (CVD) process, indicating centrifuging, and then dried in a vacuum drying oven at 50 ◦ C for 10 h.
that the TMDs-based heterostructures present the good Finally, the as-dried powders were calcined at 380 ◦ C for 5 h in pure N2
room-temperature gas sensing performance, providing a platform for to obtain highly crystalline composite powder samples. Here, the MoS2/
highly sensitive and selective gas sensor applications [17]. WS2 composites with Mo/W molar ratios of 0.25, 0.5 and 1 are labeled
Indeed, the CVD process was commonly used to prepare the TMDs- as MoS2/WS2-0.25, MoS2/WS2-0.5 and MoS2/WS2-1, respectively. The
based heterostructures [17–20]. Actually, some multi-step processes, preparation method of MoS2 was similar to that of WS2 [24], where only
involving combination of exfoliation and hydrothermal synthesis [21], the Na2WO4⋅2 H2O was replaced by Na2MoO4⋅2 H2O. Fig. 1 shows the
two-step hydrothermal processes [22], and combination of etching, schematic of fabrication of self-assembled MoS2/WS2 nanoflowers and
intercalation and hydrothermal synthesis [23] were adopted to fabricate gas sensor. The detailed characterization methods of materials are
TMD-based heterostructures. However, the preparation of TMDs-based available in Supporting Information.
heterostructures is usually required multiple steps or higher synthesis
temperatures (≥ 500 ◦ C), thereby increasing the complexity of fabrica­
2.2. Preparation and performance characterization of gas sensors
tion process and energy consumption to a certain extent. Therefore, a
facile preparation of TMDs-based heterostructures needs to be explored
The drop casting method was employed to fabricate pristine WS2,
for large-scale gas sensor applications.
MoS2 and MoS2/WS2 composites based gas sensors as follows: 3 mg
In this work, flower-like MoS2/WS2 composite with TMDs hetero­
pristine MoS2 or WS2 or composite powders were added in 0.01 mL
structure were fabricated by a facile one-pot hydrothermal method. We
ethanol and ultrasonically treated for 10 min to get homogeneous sus­
investigated comparatively the room-temperature sensing performance
pensions, then dropped on the sensor substrates consisting of interdigital
of pristine MoS2, WS2 and MoS2/WS2 composites to different concen­
Pt electrode, and finally dried in a vacuum drying oven. The SD101-type
trations of NO2, and subsequently emphasized the reproducibility,
dynamic gas sensor test system was used to record the response and
selectivity and long-term stability of the optimized MoS2/WS2 com­
recovery characteristics of pristine MoS2, WS2 and MoS2/WS2 compos­
posite. The optimized MoS2/WS2 composite exhibits superior room-
ites. This test system consists of the gas cylinder, Al-alloy gas test
temperature (25 ◦ C) gas sensitivity to different concentrations
chamber, four-channel gas mass flow control module and software for
(0.005–50 ppm) of NO2. In particular, the responses of MoS2/WS2-0.5
controlling and testing the gas [24]. Noted that the precision of gas
composite to 5 and 100 ppb NO2 arrive at 6.1% and 23.1%, respectively.
control is ~0.35%. The as-coated sensor substrates were exposed to
The formation and gas sensing mechanisms of the MoS2/WS2 hetero­
0.005–50 ppm NO2, 5 ppm SO2, NH3 and H2S, 100 ppm CO,
structure were elucidated through a combination of multiple experi­
200 ppm H2, or 50 ppb NO2 at various levels of relative humidity (RH),
ments and DFT calculations. This work offers a facile synthesis of dual-
and the real-time resistances (Ra and Rg) in air and target gases were
TMDs heterostructure, and highlights the outstanding room-
recorded. All the operating temperature is 25 ◦ C (room temperature).
temperature gas sensing performance.
The gas responses of sensors were calculated by (Ra-Rg)/Rg for SO2 and
NO2 gases, while those for CO, NH3, H2S, H2 gases, acetone, ethyl
2. Experimental and computational methods
alcohol and water vapor were calculated by (Rg-Ra)/Ra. The response
and recovery times were defined as the ones required for 90% change in
2.1. Synthesis of MoS2/WS2 composites
sensor resistances in the target gas and air, respectively. All sample gases
are dry and are custom-made from the Nanjing Special Gas Co., Ltd, and
MoS2/WS2 composites were prepared by a one-pot hydrothermal
the purities of all these gases are 99.9%. The whole detection process can
route. 0.8 g Na2WO4⋅2 H2O, 0.63 g C2H2O4, and 0.16, 0.33 or 0.66 g
be found in our previous work [24]. Some samples were repeatedly
Na2MoO4⋅2 H2O (with purities of ≥99.5%) were dissolved in deionized
tested 3–5 times to analyze the reproducibility of MoS2/WS2 composites
water (30 mL) in turn, and uninterruptedly stirred by a magnetic bar for
towards various concentrations of NO2. The arithmetical averages were
40 min to obtain homogeneous solutions. Next, the 0.1 M HCl solution
adopted to calculate the mean response & recovery times and responses,
dripped into the above solutions to control the PH value of 1.2–2.
and the deviations were determined by the standard deviation method.
Meanwhile, according to the added amounts of Na2MoO4⋅2 H2O, 0.83,
0.99 and 1.25 g CH4N2S (≥99%) were dissolved in the above solutions
by magnetically stirring for 30 min, respectively. Subsequently, the 2.3. Computational method
resulting solutions were put into 50 mL Teflon-lined stainless steel au­
toclaves, and maintained at 140–230 ◦ C for 4–24 h in a drying oven. In this work, the density functional theory (DFT) based on the Vienna
Ab initio Simulation Package (VASP) [25] was used for calculations of

Fig. 1. Schematic of fabrication of self-assembled MoS2/WS2 nanoflowers and gas sensor.

2
Z. Liang et al.
adsorption energy, electrons transfer and binding energy. The electron
correlation was described by generalized gradient approximation with
the Perdew-Burke-Ernzerhof functional [26]. The projector augmented
wave method was employed to treat the ion–electron interaction [27]. A
vacuum space of over 15 Å was adopted to avoid the interactions be­
tween two periodic layers. Moreover, the DFT-D3 was applied due to the
van der Waals (vdW) interactions [28]. The cut-off energy of 500 eV and
the Brillouin Zone of 3 × 3 × 1 grid were set to calculate the electronic
properties and total energies. The adsorption energy (ΔE) was calculated
from Eq. (1) [29,30]:
ΔE = Etotal − Esurface − Egas (1)
where Etotal is the total energy of surface with different adsorption sites,
Esurface is the energy of substrate slab, and the Egas is the energy of
adsorbent in vacuum. We considered different adsorption sites and gas
orientations (including transverse and longitudinal orientations, as well
as the positions of the atoms of different gas molecules relative to the
adsorption sites) during our calculations.
Fig. 2. SEM images of MoS2/WS2-0.5 composite after hydrothermal processes at: (a) 140 ◦ C× 12 h, (b) 170 ◦ C× 12 h, (c) 200 ◦ C× 12 h; (d) 230 ◦ C× 4 h, (e)
230 ◦ C× 12 h, and (f) 230 ◦ C× 24 h; SEM images of MoS2/WS2-0.25 MoS2/WS2-1 composites after hydrothermal process at 230 ◦ C× 24 h; XRD patterns of pristine
MoS2, WS2, and MoS2/WS2 composites.
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3. Results and discussion
3.1. The growth of MoS2/WS2 composite
To reveal the growth mechanism of the MoS2/WS2 composite, the
SEM and corresponding EDS can be used to analyze the microstructures
and chemical compositions of the related products under different hy­
drothermal temperatures and reaction time. When the molar ratio of Mo
to W is fixed to 0.5 in raw materials, the needle-like WO3 and agglom­
erated MoS2 nanoparticles can be observed under 140 ◦ C× 12 h condi­
tion (Fig. 2a and S1a). When the temperature rises to 170 ◦ C, the needle-
like WO3 crystals grow up and transform into rod-like WO3, and
meanwhile the MoS2 nanoparticles transform into pleated MoS2 nano­
sheets (Fig. 2b and S1c). Indeed, the WS2 still fails to nucleate under
170 ◦ C× 12 h condition and the partial WO3 can turn into WS2 as the
temperature climbs to 200 ◦ C (Fig. S1b). So, the MoS2/WS2 nanosheets
start to form with coexisting of a little WO3 while employing 200 ◦ C
(Figs. 2c and S1d). When the temperature increases further to 230 ◦ C,
the MoS2/WS2 nanosheets can form and develop gradually into MoS2/
WS2 nanoflowers with the increase of reaction time (Fig. 2d–e). Actu­
ally, a little WO3 still remains under 230 ◦ C× 4 h condition ((Fig. S1e).
Moreover, the petals of MoS2/WS2 nanoflowers gradually become small
with the molar ratio of Mo to W increasing from 0.25 to 1 (Fig. 2f–h),
Z. Liang et al.
and they are greatly smaller than those of pristine MoS2 and WS2
(Fig. S2a and b).
As shown in Fig. 2i, the characteristic peaks of WS2 (JCPDS 08–0237)
can be observed in XRD patterns, and the distinct peaks of MoS2 cor­
responding to the (006) and (201) planes (JCPDS 37–1492) can also be
observed [31], indicating successful synthesis of MoS2/WS2 composites
by one-pot hydrothermal process [32]. Moreover, the corresponding
EDS spectra indicate that the atomic ratios of Mo/W in the three
MoS2/WS2 composites are in good agreement with the normal molar
ratios, respectively (Fig. S2c and d).
According to the above results, the schematic of evolution of
morphology and phase in the MoS2/WS2 system with the hydrothermal
temperature can be roughly deduced (Fig. 3a). At 140 ◦ C, the needle-like
WO3 and MoS2 nanoparticles coexist, and then they turn into nanorods
and nanosheets with the temperature increasing to 170 ◦ C, respectively.
The self-assembled MoS2/WS2 nanosheets start to form when the tem­
perature is raised to 200 ◦ C, and then evolve into nanoflowers with the
temperature further increasing to 230 ◦ C.
To further understand the grow mechanism of MoS2/WS2 composite,
the binding energies of WS2 molecules deposited on the MoS2 and WS2
edges were calculated by DFT. When the temperature rises to 200 ◦ C
(while MoS2 has already nucleated), the WS2 molecules can be deposited
on the edge of MoS2 firstly due to too high relative binding energy on the
surface (8.47 eV) (Fig. S3), and then grow laterally to form the MoS2/
WS2 nanosheets due to the lower relative binding energy (− 1.2 eV)
(Fig. 3b). When the lateral growth of WS2 arrives at a certain point, the
WS2 molecules can be deposit on the surfaces of MoS2/WS2 nanosheets
via van der waals force due to over high specific surface energy at the
edge and insufficient driving force (Fig. 3c). As a result, the MoS2/WS2
nanosheets can grow by layer-by-layer self-assembly to form the flower-
like MoS2/WS2 heterostructured composite.
Fig. 3. (a) Schematic of growth of MoS2/WS2 composite at different temperatures; (b) The relative binding energies of WS2 molecules deposited on the MoS2 and
WS2 edges; (c) Schematic of layer-by-layer growth of WS2 on the MoS2 and WS2 surfaces via van der waals force.
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3.2. TEM and chemical analyses
Fig. 4a shows the typical TEM image of MoS2/WS2-0.5 composite
fabricated at 230 ◦ C × 24 h, indicating the nanoflower-like morphology
with diameter of 1 µm. Clear MoS2/WS2 interface and symbiotic struc­
ture are produced, which can be demonstrated by the HRETEM images
and the corresponding Fast Fourier Transform (FFT) images [33], indi­
cating the formation of MoS2/WS2 heterostructure (Fig. 4b and d–f).
Specifically, the lattice spacings of 6.18 nm, 0.273 nm, and 6.15 nm are
assigned to the (002), (100) planes of WS2, and (002) plane of MoS2,
respectively [34–36]. Moreover, the clear diffraction rings are observed
in the SAED pattern, corresponding to the (002), (100), (101), (103)
planes of WS2, and (100), (101), (103) and (201) planes of MoS2
(Fig. 4c). Actually, the WS2 is mainly distributed at the edge of petals
instead of the center of the petals, and excess WS2 may grow on the MoS2
surface [37,38]. The EDS elemental mappings of MoS2/WS2-0.5 com­
posite also demonstrate that the Mo element is mainly distributed at the
center of petals and the W element is uniformly distributed on the whole
flower (Fig. 4g), implying that MoS2 can act as the nucleation center of
WS2 to form the MoS2/WS2 heterostructure in the hydrothermal process.
Raman spectra can effectively characterize the molecular structure of
materials, especially the TMDs. The two vibrational bands at 351 and
417 cm− 1 can be observed in pristine WS2, and the other two at 384 and
408 cm− 1 are assigned to the pristine MoS2, corresponding to the similar
vibration modes: in-plane optical (E12g ) and out-of-plane vibration (A1g ),
respectively (Fig. 5a) [39–41]. The characteristic peaks of WS2 and MoS2
can be observed in the MoS2/WS2 composites, and they have a slight red
or blue shift compared with the pristine WS2 and MoS2, implying the
formation of heterostructure. Moreover, with the increase of Mo con­
centration in the MoS2/WS2 composites, the intensity of WS2 charac­
teristic peaks gradually decreases and the offset level of these peaks
Z. Liang et al.
Fig. 4. (a) TEM, (b) HRTEM, (c) SAED and (g) EDS elemental mapping of MoS2/WS2-0.5 composite; (d–f) HRTEM and FFT images of the select regions “d–f” in (b),
respectively.
increases, indicating the enhanced resonance between WS2 and MoS2. It
is worth noting that the slight red shift of A1g of MoS2 only appears in the
MoS2/WS2-1 composite, which may contribute to a small amount of
covering of WS2 on the surface of MoS2/WS2 nanosheets [40]. The blue
shift of A1g of MoS2 can be observed in the other two composites may be
due to the partial encapsulation of MoS2 by the WS2.
The photoluminescence (PL) emission spectra of pristine MoS2, WS2
and MoS2/WS2 composites were collected in the 450–800 nm wave­
length region at the excitation wavelength of 360 nm to study the sep­
aration rate of electron-hole pairs (Fig. 5b). It is clear that the relative
intensities of the emission spectra of the two composites with higher Mo
concentrations are greatly lower than those of pristine WS2 and MoS2,
indicating that the photoexcited holes and electrons in the two com­
posites are difficultly recombined [20,42]. The remarkable quenching
effect indicates that the unique MoS2/WS2 heterostructure can effec­
tively suppress the recombination of electrons and holes, which is
favorable to the efficient interfacial electrons transfer between WS2 and
MoS2. However, the relative intensity of MoS2/WS2-0.25 composite is
higher than those of pristine WS2 and MoS2, which may be attributed to
the narrower bandgap.
To further understand the chemical states and electrons transfer
between MoS2 and WS2, the XPS analysis was carried out. The survey
XPS spectrum of MoS2/WS2-0.5 composite demonstrates that it is
composed of Mo, S, and W elements (Fig. S4a). For the W 4 f, the two
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Sensors and Actuators: B. Chemical 403 (2024) 135215
characteristic peaks can be observed due to the presence of W-S bonds in
the WS2-containing materials (Fig. 5c) [43]. The peaks of W6+ can be
observed due to the oxidation of pristine WS2 and MoS2/WS2-0.5 com­
posite. Obviously, the two peaks of W4f in the MoS2/WS2-0.5 composite
slightly shift towards higher binding energy compared with the pristine
WS2, indicating that the electrons can flow away from the WS2. The two
characteristic peaks at 323.40 and 229.29 eV are observed in the
MoS2/WS2-0.5 composite, corresponding to Mo 3d3/2 and Mo 3d5/2,
respectively (Fig. 5d) [31,44]. The two peaks shift towards lower
binding energy compared with the pristine MoS2, indicating that the
electrons can flow to the MoS2. The marked deviation of binding en­
ergies of W 4 f and Mo 3d indicates strong interactions between MoS2
and WS2 in the MoS2/WS2-0.5 composite. In particular, the shifts to­
wards the higher and lower binding energy are originated from the
decrease and increase of the electron density, implying that WS2 and
MoS2 act as the electron donor and acceptor in the composite as a whole,
respectively [44,45]. In addition, the specific surface area of
MoS2/WS2-0.5 composite is calculated to be 11.59 m2/g based on the N2
adsorption-desorption isotherm curves (Fig. S4c), which is much larger
than that of WS2 nanosheets (<8.4 m2/g) [46]. The pore sizes of the
MoS2/WS2-0.5 composite are mainly between 2 to 30 nm (Fig. S4d),
showing the mesoporous characteristic.
Z. Liang et al.
Fig. 5. (a) Raman and (b) PL spectra of the MoS2/WS2 composites, pristine MoS2 and WS2; XPS spectra of (c) W4f and (d) Mo 3d of MoS2/WS2-0.5 composite and
pristine WS2 or MoS2.
3.3. Gas sensing performance
The room-temperature gas sensing performance of pristine MoS2,
WS2, and the three MoS2/WS2 composite samples were recorded by the
dynamic gas sensor test system (Fig. 6 and S5). From the response and
recovery curves, the resistances of pristine MoS2 and MoS2/WS2 com­
posites decrease at different levels when these gas sensors contact
various concentrations of NO2, showing the characteristic of p-type
semiconductor (Fig. 6a). The responses and response time of pristine
MoS2 and MoS2/WS2 composites increase and decrease with the increase
of NO2 concentration, respectively (Fig. 6a and b). Indeed, the room-
temperature responses of pristine MoS2 and WS2 are going to zero
when the NO2 concentration is less than 1 or 2 ppm (Fig. 6a and S5a).
The outstanding gas sensing performance is achieved in the MoS2/WS2-
0.5 composite, with responses of 31.4%, 140.1%, 185.1% and 368.2% to
1, 5, 10 and 50 ppm NO2, respectively. These responses are ~8–15 and
13–23 times higher than those of pristine MoS2 and WS2, respectively
(Fig. 6b). According to the Langmuir model [47,48], all the MoS2/WS2
composites show good linearity with R2 of over 0.98 (Fig. 6b). Moreover,
the MoS2/WS2-0.5 composite presents the shortest response and recov­
ery times to for 5 ppm NO2 (Fig. S5b and c), showing the higher sensi­
tivity than the other four materials.
Low-concentration detection of hazardous gases at room tempera­
ture contributes to human health protection and energy conservation, so
the room-temperature sensing performance of MoS2/WS2-0.5 composite
to ppb-level NO2 was deliberately investigated here. The response of
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Sensors and Actuators: B. Chemical 403 (2024) 135215
MoS2/WS2-0.5 composite increases almost linearly with the concentra­
tion of NO2 increasing from 5 to 100 ppb, with R2 of 0.987 (Fig. 6c and
d), indicating the good potential in practical applications. Specifically,
the average responses of MoS2/WS2-0.5 composite to 100, 50, 10 and 5
ppb are 23.1%, 16.1%, 7.3% and 6.1%, respectively.
We also investigated the responses of MoS2/WS2-0.5 at various RH
levels to 50 ppb NO2. The response of MoS2/WS2-0.5 composite de­
creases gradually from 16.1% to 13.2%, 10.3%, 6.7%, and 3.1% with the
RH increasing from 0, to 25%, 33%, 50% and 65% (Fig. 6e inset). Under
the RH of ≤ 33%, the MoS2/WS2-0.5 composite shows the good recov­
ery, with the response of over 60% initial value. When the RH is lower
(≤25%), a small quantity of H2O molecules are adsorbed on the MoS2/
WS2 composite surface and can react with the adsorbed oxygen species
via Eq. (2):
H2O-gas + O-ads → 2-OHads + 2e- (2)
which can provide the less electrons to the MoS2/WS2 composite,
resulting in the lower resistance of material and the shorter response/
recovery times [24,49,50]. When the NO2 molecules enter into the gas
chamber, the NO2 molecules are adsorbed on the MoS2/WS2 composite
surface, and draw electrons from the sensing material and react with
-OH via Eq. (3) [51,52]:
NO2 + -OHads + e- → HNO-3 (3)
When the RH increases, lots of H2O molecules are adsorbed on the
MoS2/WS2 composite surface and occupy more adsorption sites, and
Z. Liang et al. Sensors and Actuators: B. Chemical 403 (2024) 135215

Fig. 6. (a,c) Dynamic response and recovery curves, and (b,d) the corresponding fitting curves of pristine MoS2, WS2, and/or MoS2/WS2 composites to 1–50 ppm or
5–100 ppb NO2; (e) Humidity-dependence to 50 ppb NO2 (The inset is the fitting curves of the composite response and baseline resistance under various RH) and (f)
reproducibility of MoS2/WS2-0.5 composite; (g) long-term stability and (h) Selectivity of pristine MoS2, WS2 and MoS2/WS2-0.5 composite; (i) Comparison of room-
temperature responses of MoS2- and WS2-containing materials to ppb-level NO2.

meanwhile more NO2 can react with the -OH, as a result of that the
adsorption of NO2 on the composite surface is reduced and the in­
teractions between NO2 and MoS2/WS2-0.5 composite are weakened.
Hence, the response/recovery times increase, and the response de­
creases with incomplete recovery. Moreover, the standard deviation of
response of MoS2/WS2 composite at various levels of RH ranges from
0.6% to 3.1%, indicating good reproducibility (Fig. S5d).
Good reproducibility, long-term stability and selectivity are the basic
requirements for gas sensors in order to precisely monitor the target gas
and prevent the interference from other gases during the whole sensing
process. Figs. 6 f and S5d–f show the room-temperature reproducibility
of MoS2/WS2-0.5 composite to 5 ppb, 100 ppb and 5 ppm NO2 and of
pristine WS2 and MoS2 to 5 ppm NO2. Compared with the pristine WS2
and MoS2, no obvious variations are generated in the response and re­
covery process of MoS2/WS2-0.5 composite during 5 cycles
(Fig. S5d–f), with respective responses of 140.1% ± 0.57% (0.41%),
23.1% ± 0.09% (0.39%) and 6.1% ± 0.04% (0.65%) (Fig. 6 f), indi­
cating excellent reproducibility. After exposure in air for 30 days, the
responses of pristine WS2 and MoS2 present decrease by 31.8% and
38.5%, respectively (Fig. 6 g). However, no significant decrease can be
observed in the response of MoS2/WS2-0.5 composite to ppb-level NO2.
Under long-term exposure to air, O2 can oxidize slowly the WS2-con­
taining materials and partially occupy the sulfur vacancies [53], leading
to a certain decrease in the signal of EPR and the response of composite
(Fig. S5i). In particular, a little decrease of 3.4% in the response appears
to 5 ppm NO2, indicating that the MoS2/WS2-0.5 composite has excel­
lent long-term stability (Fig. 6 g).
The room-temperature responses of pristine MoS2, WS2 and MoS2/
WS2-0.5 composite to 5 ppm NO2 and other hazardous gases in same or
higher concentrations (5–100 ppm) were comparatively investigated to
identify the selectivity of the MoS2/WS2-0.5 composite. Obviously, a
higher response of 140.1% to 5 ppm NO2 can be obtained in the MoS2/
WS2-0.5 composite, which is 14 times higher than those of pristine MoS2
and WS2, and meanwhile the MoS2/WS2-0.5 composite presents much
lower responses to other gases (H2, Co, H2S, NH3, SO2, acetone, ethanol
and water vapor), indicating excellent selectivity (Fig. 6 h).
The responses of related WS2- and MoS2-containing materials are
collected in this work to compare their gas sensing properties to ppb-

7
Z. Liang et al. Sensors and Actuators: B. Chemical 403 (2024) 135215

Fig. 7. (a) The dynamic response change curves (d(Ra/Rg)/dt) of different materials (including MoS2/WS2 composites, pristine WS2 and MoS2) to 5 ppm NO2 at
25 ◦ C; (b) The dynamic response change curves (d(Ra/Rg)/dt) of MoS2/WS2-0.5 composite to 5–100 ppb NO2 at 25 ◦ C.

Fig. 8. (a) The dynamic curve of MoS2/WS2-0.5 composite baseline resistance in air around room temperature (20–40 ◦ C); (b) The fitting curves of MoS2/WS2-0.5
composite baseline resistance in air around room temperature (20–40 ◦ C) and of MoS2/WS2-0.5 composite resistance to 5–100 ppb NO2 at 25 ◦ C; (c) The dynamic
curve of MoS2/WS2-0.5 composite baseline resistance to the concentration of NO2 under 25% RH at 25 ◦ C; (d) The fitting curves of MoS2/WS2-0.5 composite baseline
resistance under various RH and of MoS2/WS2-0.5 composite resistance to ppb-level NO2 (20–100 ppb) under 25% RH at 25 ◦ C.

8
Z. Liang et al. Sensors and Actuators: B. Chemical 403 (2024) 135215

level NO2 (Fig. 6i) [22–24,54–60]. Obviously, the responses of can detect over 50 ppb NO2 in view of the changes of temperature
MoS2/WS2-0.5 composite are much higher than those of MoS2- and WS2- (variation of ~10 ◦ C in a day) and RH on practical application.
containing materials to same concentrations of NO2 at room tempera­
ture, respectively. Moreover, room-temperature responses of some WS2-
3.4. Gas sensing mechanism
and MoS2- containing materials to NO2 are also exhibited in Table S1,
indicating that the as-fabricated MoS2/WS2 composite has excellent NO2
For further reveal gas sensing mechanism of MoS2/WS2 composite,
sensing performance.
the DFT was used to calculate the related adsorption energies and
Obviously, the rate of response change (d(Ra/Rg)/dt, i.e., the relative
electrons transfer, and the related structure models are shown in Figs. S7
adsorption rate) sharply decreases firstly and then flattens out with the
and S8. The excellent room-temperature sensing performance of MoS2/
time increasing. The MoS2/WS2-0.5 composite has higher d(Ra/Rg)/dt
WS2-0.5 composite to NO2 can be mainly ascribed to the following:
than other MoS2/WS2 composites, pristine WS2 and MoS2 to 5 ppm NO2
at 25 ◦ C (Fig. 7a). Moreover, the d(Ra/Rg)/dt of MoS2/WS2-0.5 com­
(1) The special morphology and microstructure. Nanoflower-like
posite slightly climbs with the NO2 concentration increasing from 5 to
MoS2/WS2 composite provides more adsorption sites to the
100 ppb NO2 (Fig. 7b), and the d(Ra/Rg)/dt of MoS2/WS2-0.5 composite
target gas due to the relatively large specific surface area [63–65]
to 5 ppm NO2 is far higher than those to ppb-level NO2. Therefore, the
(Fig. S4c). From the EPR spectrum of MoS2/WS2-0.5 composite
relative adsorption rate is positively related to the number of active sites
(Fig. 9a), the clear paramagnetic transition at g= 2.003 is
and the target gas concentration, which is good agreement with the
observed due to the formation of unpaired electrons originated
previous reports [61,62].
from the sulfur vacancies [66]. The sulfur vacancies can be usu­
Considering the practical application of MoS2/WS2-0.5 composite to
ally produced on the WS2 or MoS2 in hydrothermal process [67,
ppb-level NO2 at room temperature, the effects of working temperature
68]. Compared with the pristine WS2, MoS2 and the air-aged
(around 25 ◦ C) and RH cannot be ignored. Obviously, the baseline
MoS2/WS2-0.5 composite for 30 days, the MoS2/WS2-0.5 com­
resistance of MoS2/WS2-0.5 composite in air decreases lineally with the
posite presents the larger peak area and higher peak intensity
increase of temperature, and the composite resistance to NO2 decreases
(Figs. S5i and S9a). Actually, the larger peak area and higher peak
almost lineally with the concentration of ppb-level NO2 at 25 ◦ C (Fig. 8a
intensity indicates higher sulfur vacancy concentration. The
and b). Moreover, the effect of temperature on the composite response is
presence of abundant sulfur vacancies can provide more multiple
calculated as 3.41 ppb/◦ C (Fig. 8b), namely that the change of 1 ◦ C
active sites to adsorb gas molecules and thus increase the
temperature on the response of MoS2/WS2-0.5 composite is equivalent
adsorption ability of MoS2/WS2 composites to NO2. According to
to that of the adsorption of 3.41 ppb NO2. Similarly, the baseline
the DFT calculations, the MoS2/WS2 composite with S vacancy
resistance of composite increases lineally with the increase of RH, and
has the highest surface adsorption energy (− 0.34 eV) to NO2
the composite resistance to NO2 decreases lineally with the concentra­
(Fig. 9e).
tion of ppb-level NO2 increasing under 25% RH (Figs. 6e, 8c and d). The
Actually, the edge of MoS2/WS2 composite also increases the
− 8.47 ppb/%RH is obtained from these data (Fig. 8d), indicating that
adsorption ability to gases. The MoS2/WS2-0.5 composite has
the effect of 1% RH change on the composite response is equivalent to
more active W sites at the edge due to the presence of more S
that of desorption of 8.47 ppb NO2. In short, the MoS2/WS2 composite
vacancies than pristine MoS2 and WS2 (Fig. S9a), and its W site

Fig. 9. (a) EPR spectrum of MoS2/WS2-0.5 composite and the corresponding structure model; (b) Energy banding diagram of WS2 and MoS2; (c) Schematic of band
structure model for MoS2/WS2 heterostructure in air and NO2; (d) Charge density difference and planar-average-charge density of MoS2/WS2 heterostructure with S
vacancy to NO2; (e) The charges transfer and the adsorption energies at the surfaces of MoS2, WS2, MoS2/WS2 and MoS2/WS2 with S vacancy; (f) Schematic of
electrons transfer models of MoS2/WS2 composite in air and NO2.

9
Z. Liang et al.
has the highest adsorption energy (− 3.93 eV) (Fig. S9b), result­
ing in the maximum adsorption energy at the edge. Moreover, the
NO2 can gain the more electrons (0.97 e) from the W site at the
edge of MoS2/WS2 composite to form the W-O bonds, and
meanwhile the dangling S atoms at the edge of MoS2/WS2 com­
posite can provide the more electrons (1.16 e) to NO2 to form S-O
bonds (Figs. S7 and S9b), indicating the higher electron transfer
ability at the edge. However, the edge area of MoS2/WS2
composite-0.5 is much smaller than its surface area, so the
adsorption ability and electrons transfer ability at the surface of
MoS2/WS2-0.5 composite mainly determine the NO2 sensing
performance.
(2) The effect of MoS2/WS2 heterostructure. Based on the UV-Vis
absorption spectra of pristine MoS2, WS2, and MoS2/WS2-0.5
composites, their bandgaps are calculated to be 1.30, 1.03 and
1.10 eV, respectively (Fig. S10a and S10b). The valence band
(VB) edges of pristine MoS2 and WS2 measured by valence-band
XPS (VB-XPS) spectra are determined to be 0.31 and 0.14 eV
below their Fermi levels, respectively (Fig. S10c) [69]. Moreover,
the work function (Φ) of MoS2 and WS2 can be determined to be
5.2 and 4.9 eV according to these reports [70,71]. So, the energy
band structure can be described in Fig. 9b.
The electrons can transfer from WS2 to MoS2 due to the lower work
function, resulting in the separation of holes and electrons, and the
formation of charge depletion and accumulation layers in air (Fig. 9c,
d and f). So, the built-in electrical fields are established [72], which can
provide higher potential barrier and then decrease the conductivity of
MoS2/WS2 composite (Fig. 9c). When in air, the O2 molecules are
absorbed on the composite surface, and then draw electron to form O-2.
The relevant reactions in air are described by Eqs. 4 and 5. When in NO2,
partial NO2 molecules can prefer to be adsorbed on the edges of
MoS2/WS2 nanoflowers due to the higher adsorption energy at the edge
(Fig. 9e), while most of the NO2 molecules are adsorbed on the
MoS2/WS2 composite surface due to the larger surface area. And the
small amount of NO2 can react with the O−2 on the composite surface to
form NO−2 or NO−3 . The relevant reactions in NO2 are described by Eqs.
(6)–(9). Moreover, the NO2 can draw the more electrons (0.2 e) from
WS2 or MoS2 in the MoS2/WS2 composite with S vacancy (Fig. 9e),
which can break the balance of build-in electrical field. The decrease of
electrons can narrow down the height of potential barrier, and increase
the free-moving holes in the p-type MoS2/WS2 composite, leading to the
enhancement of the conductivity of MoS2/WS2 composite. The
MoS2/WS2 composite with S vacancies can provide the most electrons to
NO2 whatever at the surface and at the edge (Fig. 9e and S9b), leading to
the biggest drop in resistance (Fig. 6a and c). Therefore, the
MoS2/WS2-0.5 composite exhibits the optimal NO2 sensing performance
at room temperature.
In air:
O2 (g)→O2 (ad) (4)
O2 (ad) + e− →O−2 (ad) (5)
In NO2:
NO2 (g)→NO2 (ad) (6)
NO2 (ad) + e− →NO−2 (ad) (7)
NO2 (ad) + O−2 →NO−2 (ad) + O2 (8)
2NO2 (ad) + O−2 + e− →2NO−3 (ad) (9)
For reducing gases (CO, H2S, NH3 and H2), the mechanism of gas
sensing can be mainly explained in terms of electron transfer and gas
adsorption. In a dry atmosphere, they can be adsorbed on the composite
surfaces and provide some electrons to the composite, resulting in the
10
Sensors and Actuators: B. Chemical 403 (2024) 135215
decrease of the conductivity of p-type MoS2/WS2 composite (i.e., the
increase of the resistance) [53,73]. However, the adsorption energies of
the reducing gases to WS2 or MoS2 are lower than that of the NO2 [74,
75], so the responses of MoS2/WS2 composite to other reducing gases
are lower than that to NO2.
4. Conclusion
Nanoflower-like MoS2/WS2 composites were synthesized by a facile
one-pot hydrothermal method. With increasing the hydrothermal tem­
perature from 140 to 230 ◦ C, the needle-like WO3 and MoS2 nano­
particles turn into nanorods and nanosheets firstly, respectively, then
they are self-assembled into MoS2/WS2 nanosheets, and finally evolve
into nanoflowers. The WS2 molecules prefer to grow on the edges of as-
nucleated MoS2 to form the MoS2/WS2 nanosheets, and then they can
grow by layer-by-layer self-assembly to form the MoS2/WS2 hetero­
structure. The MoS2/WS2-0.5 composite presents very high sensitivity to
different concentrations of NO2 at room temperature. Specifically, the
responses of MoS2/WS2-0.5 composite to 5 ppb, 100 ppb and 5 ppm NO2
are 6.1%, 23.1% and 140.1%, respectively. Moreover, the MoS2/WS2-
0.5 composite exhibits excellent reproducibility, selectivity, and long-
term stability to NO2. The excellent NO2 sensing performance of
MoS2/WS2-0.5 composite can be mainly attributed to the flower-like
morphology, abundant sulfur vacancies and self-assembled hetero­
structure. This work provides a feasible strategy to fabricate self-
assembled dual-TMDs heterostructures for high-performance gas
sensing materials.
CRediT authorship contribution statement
Zhiping Liang: Investigation, Methodology, Visualization, Writing
− original draft. Mingyuan Wang: Formal analysis, Software, Writing −
original draft, Visualization. Siwei Liu: Investigation. Mobashar Has­
san: Methodology, Funding acquisition. Xiangzhao Zhang: Conceptu­
alization, Visualization. Shuangying Lei： ：Visualization. Guanjun
Qiao: Resource, Funding acquisition. Guiwu Liu: Formal analysis,
Resource, Supervision, Writing − review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
This work was supported by National Natural Science Foundation
(51950410596) of China, and the Key Research and Development Plan
(BE2019094), Qing Lan Project ([2016]15), Innovation/Entrepreneur­
ship Program (JSSCTD202146) of Jiangsu Province. We thank the Hefei
Advanced Computing Center for the facility support on the calculation
in this paper.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.snb.2023.135215.
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Z. Liang et al. Sensors and Actuators: B. Chemical 403 (2024) 135215

Shuangying Lei is an associate Professor at the School of
Electrical Science and Engineering, Southeast University. Her
current research includes nano materials and devices based on
experiment and DFT calculation.
Guiwu Liu is a Professor of the School of Materials Science and
Engineering, Jiangsu University. His current research includes
wetting and joining of ceramics, inorganic materials and de­
vices, such as gas-sensing, thermoelectric, light absorbing
materials and sensors.

Guanjun Qiao is a Professor and Dean of the School of Mate­

rials Science and Engineering, Jiangsu University. His current
research interest involves inorganic materials and devices,
such as design and optimization of advanced ceramics, and gas
sensors.

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