chemosensors

Article
Flexible Low-Temperature Ammonia Gas Sensor Based on
Reduced Graphene Oxide and Molybdenum Disulfide
Zhe Ren 1 , Yunbo Shi 1, *, Tianming Song 1 , Tian Wang 1 , Bolun Tang 1 , Haodong Niu 1 and Xiaoyu Yu 2

1 The Higher Educational Key Laboratory for Measuring & Control Technology and Instrumentations of
Heilongjiang Province, Harbin University of Science and Technology, Harbin 150080, China;
[email protected] (Z.R.); [email protected] (T.S.); [email protected] (T.W.);
[email protected] (B.T.); [email protected] (H.N.)
2 School of Atmospheric Sciences, Sun Yat-sen University, Guangzhou 519000, China; [email protected]
* Correspondence: [email protected]

Abstract: Owing to harsh working environments and complex industrial requirements, traditional
gas sensors are prone to deformation damage, possess a limited detection range, require a high
working temperature, and display low reliability, thereby necessitating the development of flexible
and low-temperature gas sensors. In this study, we developed a low-temperature polyimide (PI)-
based flexible gas sensor comprising a reduced graphene oxide (rGO)/MoS2 composite. The micro-
electro-mechanical system technology was used to fabricate Au electrodes on a flexible PI sheet to
form a “sandwiched” sensor structure. The rGO/MoS2 composites were synthesized via a one-step
hydrothermal method. The gas-sensing response was the highest for the composite comprising 10%





 rGO. The structure of this material was characterized, and a PI-based flexible gas sensor comprising
rGO/MoS2 was fabricated. The optimal working temperature of the sensor was 141 ◦ C, and its
Citation: Ren, Z.; Shi, Y.; Song, T.;
Wang, T.; Tang, B.; Niu, H.; Yu, X.
response-recovery time was significantly short upon exposure to 50–1500 ppm NH3 . Thus, this
Flexible Low-Temperature Ammonia sensor exhibited high selectivity and a wide NH3 detection range. Furthermore, it possessed the
Gas Sensor Based on Reduced advantages of low power consumption, a short response-recovery time, a low working temperature,
Graphene Oxide and Molybdenum flexibility, and variability. Our findings provide a new framework for the development of pollutant
Disulfide. Chemosensors 2021, 9, 345. sensors that can be utilized in an industrial environment.
https://doi.org/10.3390/
chemosensors9120345 Keywords: flexible electronics; micro-electro-mechanical system; reduced graphene oxide; NH3 gas
sensor; molybdenum disulfide
Academic Editors: Shaolin Zhang and
Fang Xu

Received: 9 October 2021

1. Introduction
Accepted: 30 November 2021
Published: 7 December 2021
Ammonia is the second most produced chemical in the world and the most common
industrial pollutant because of illegal ammonia discharge owing to leakage during chemical
Publisher’s Note: MDPI stays neutral
processing. Moreover, as a green and clean source of energy, ammonia has been developed
with regard to jurisdictional claims in
for various applications, including use as rocket fuel [1] as well as in fuel cells [2], hydrogen-
published maps and institutional affil- storage materials [3], and new energy vehicles [4]. This widespread use has resulted in an
iations. increase in ammonia leakage during industrial production processes. Thus, it is important
to address the problem of ammonia leakage through the implementation of effective
ammonia sensors in industries [5]. Presently, the most commonly used gas sensors are
semiconductor gas sensors made of metal oxide or polymer materials; they are widely used
Copyright: © 2021 by the authors.
for detecting the leakage of toxic and harmful gases [6,7]. However, because of their slow
Licensee MDPI, Basel, Switzerland.
desorption characteristics, such sensors require a high working temperature. Furthermore,
This article is an open access article
traditional sensors suffer from problems such as low selectivity, a narrow gas detection
distributed under the terms and range, and high power consumption. Moreover, some sensors exhibit baseline drift and
conditions of the Creative Commons need to be recalibrated frequently [8].
Attribution (CC BY) license (https:// Most ammonia sensors contain silicon or ceramic substrates that are rigid, brittle, and
creativecommons.org/licenses/by/ fragile [9], which make the sensors prone to deformation and damage, because industrial
4.0/). environments are complex and industrial gas leakage is often accompanied by stress shock.

Chemosensors 2021, 9, 345. https://doi.org/10.3390/chemosensors9120345 https://www.mdpi.com/journal/chemosensors

Chemosensors 2021, 9, 345 2 of 16

These problems can be prevented by developing sensors with flexible substrates, which
are expandable, stable, and stretchable [10], making them functional after deformation
induced by the impact of external forces. Such sensors can meet the gas-detection require-
ments in complex and dynamic environments and can be used in the fields with high
ammonia concentration, such as industrial preparation of ammonia fuel and industrial
ammonia storage.
In recent years, two-dimensional materials such as transition metal dichalcogenides
(TMDCs) have gained considerable research attention because of their applicability as gas
sensors. TMDCs possess an MX2 structure, where M is a transition metal (molybdenum,
tungsten, or titanium) and X is a chalcogen atom (such as sulfur and selenium). The layered
structure of TMDCs, with strong in-plane bonding and weak van der Waals interplanar
bonding, enables its easy peeling off by mechanical means [11]. Furthermore, TMDCs are
notable for their high surface area-to-volume ratio, absence of dangling bonds, strong spin–
orbit-coupling interaction, and high gas-adsorption capability [12,13]. TMDC materials
possess remarkable layer-related electrical, optical [14], thermal [15], and mechanical
properties [16], which can be adjusted easily by various external treatments, such as strain
application [17] and size scaling [18]. Thus, TMDC materials have demonstrated potential
for applications in nanoelectronics [7], spintronics [19] and as photodetectors [20] and
active gas sensors. In addition, it has been reported that molybdenum disulfide (MoS2 )
sheets can be bent to a radius of 0.75 mm without affecting their electronic properties [21].
Furthermore, MoS2 films possess a high Young’s modulus of up to 300 GPa, continuous
crack deformity of up to 11%, and excellent transparency [22], rendering them a candidate
material for flexible devices [23–25].
MoS2 exhibits excellent sensitivity to ammonia and can detect ammonia efficiently.
However, after gas adsorption, the material cannot be completely restored, which affects
sensor performance [21]. In 2012, Li et al. studied the responsiveness of MoS2 materials
comprising different layers to NO gas and observed unstable sensor performance after
repeated cycle tests, indicating that the materials are not conducive to repeated use [26]. In
2015, Ricciardella et al. reported a graphene-based gas sensor fabricated via chemical vapor
deposition. The NH3 detection limits were up to 17 ppm. However, the recovery time was
20 min [27]. In 2016, Long et al. fabricated a MoS2 /graphene hybrid structure and devel-
oped an ultrasensitive NH3 sensor with a detection limit of 50 ppb. However, its recovery
was low [28]. Recently, several reports have been published on the fabrication of mixed
MoS2 heterostructures for the improvement of the charge transfer in MoS2 and, therefore,
shortening the recovery time. In 2018, Min et al. successfully fabricated a MoS2 /reduced
graphene oxide (rGO) gas sensor by an aqueous solution mixing method [29]. At 25 ◦ C,
the response of a MoS2 /rGO material to NO2 was 4-fold that of pure rGO, and the flexural
radius of the sensor was up to 14 mm. However, its responsiveness was low, and the defor-
mation curvature and stability need to be improved. In 2020, Sangeetha et al. prepared
a MoS2 –rGO-composite-based optical-fiber sensor via a coating-modification method to
detect formaldehyde gas and to determine its concentration [30]. However, the detection
attains saturation at ~500 ppm, which limits the detection of higher gas concentrations.
These findings indicate that the use of two-dimensional materials, such as graphene and
TMDCs, in gas sensors can enable their operation at low temperatures and improve their
gas-sensing performance, while increasing their gas-sensing response. However, problems
such as a long response-recovery time, low flexibility, incomplete sensor recovery, and a
narrow detection range remain to be solved.
In this study, we developed a low-temperature polyimide (PI)-based flexible gas sen-
sor comprising a MoS2 /rGO composite. A heating sensor and gas-sensing electrode were
fabricated on the front and back sides of flexible PI sheets via the micro-electro-mechanical-
system (MEMS) technology. Sensing materials MoS2 and rGO were synthesized via a
one-step hydrothermal method to achieve gas-sensing properties. The morphology of
the synthetic materials was characterized by field-emission scanning electron microscopy
(SEM), X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) surface area analy-
Chemosensors 2021, 9, 345 3 of 16

sis, Raman spectroscopy, and thermogravimetric analysis (TGA). Further, a gas-sensing test
platform was established to verify the flexibility, selectivity, optimal working conditions,
and gas-sensing response of the sensor. The mechanism of the sensor was also discussed.

2. Materials and Methods

2.1. Synthesis of Sensing Materials
A graphene oxide (GO) dispersion (2 mg/mL) was prepared via Hummers’ method us-
ing graphite powder purchased from XFNANO Materials Tech Co., Ltd. (Nanjing, China) [31].
Further, 5%, 10%, and 15% GO solutions were prepared by stirring GO in 50 mL deion-
ized water; they were used as the experimental precursors. Sodium molybdate dihydrate
(Na2 MoO4 ·2H2 O, analytical grade, 3.82 g), thiourea (CH4 N2 S, analytical grade, 3.42 g), and
oxalic acid (H2 C2 O4 , analytical grade, 0.5 g) were dissolved in 50 mL of the GO precursor
solution and stirred for 1 h at 25 ◦ C. Then, the mixture was sonicated for 1 h, transferred to a
60 mL Teflon-lined stainless-steel vessel, and maintained at 190 ◦ C for 24 h. After naturally
cooling the mixture to 25 ◦ C, the precipitate was separated by centrifugation at 2000 rpm for
10 min and washed several times using absolute ethanol and deionized water and then dried
by freeze-drying at −70 ◦ C. Subsequently, the nanocomposites were obtained in a powder
form. To obtain pure MoS2 , the process was repeated without using GO. Further, a control
comprising only rGO was prepared. A schematic of the synthesis process is shown in Figure 1.
The obtained material was characterized, and its gas-sensing performance was analyzed.

Figure 1. Schematic of the synthesis of rGO/MoS2 composite.

2.2. Fabrication of Flexible Gas Sensors

The structural design of the flexible gas sensor is shown in Figure 2. The sensor
chip included a Pt heating layer, a flexible PI insulating substrate, and a sensitive layer
comprising a Pt interdigital electrode, to form a sandwiched structure. The dimensions of
the sensor chip were 5 mm × 2.5 mm × 50 µm.
The flexible gas sensors were fabricated as follows: PI films (50 µm), employed as
the substrates, were cleaned three times via sequential ultrasonication in acetone and
isopropanol. Then, the substrates were heated at 100 ◦ C for 10 min and blow-dried with
N2 . Heating electrode coils and interdigital electrodes, both with a thickness of 20 µm,
were fabricated through photolithography. Pt was used to fabricate the electrodes on both
sides. To improve the mechanical properties, metal pads of the same size were prepared
on the rear side of each pair of electrode pads. The electrode pads and conductor were
Chemosensors 2021, 9, 345 4 of 16

connected using a conductive adhesive silver paste, and the electrical signal data were
collected through a data acquisition unit.

Figure 2. (a) Schematic of the structure of the flexible sensor, and (b) photograph of the flexible sensor.

2.3. Characterization of Sensing Materials

The sensing materials were analyzed via XRD analysis (Ultima IV, Rigaku, Tokyo, Japan)
by using a high-intensity Cu Kα source (λ = 0.154 nm) at a scan rate of 5◦ /min, across a 2θ
range of 5◦ –75◦ . The crystallization phase and crystallinity of the samples were identified
from the XRD patterns obtained. The surface morphologies of the samples were analyzed
via FE-SEM (JEOL JSM-7500F, Tokyo, Japan). Further, the samples were subjected to Raman
analysis (Renishaw inVia Raman spectrometer, Renishaw plc., Wotton-under-Edge, UK), and
the characteristic peaks of graphene contained in the sample were analyzed from the spectra
obtained. Furthermore, the sensing materials were placed in a vacuum tube, degassed at
120 ◦ C for 12 h, and the N2 adsorption–desorption curves of the samples were obtained
at 350 ◦ C by using a specific surface area and porosity analyzer (ASAP 2460 Version 3.01,
Micromeritics Instrument (Shanghai) Ltd., Shanghai, China). The gas-adsorption capacity of
the sensing materials was evaluated using the BET equation. A thermal image analyzer (Flir
C3, West Malling, Kent, UK) was used to evaluate the heat. The thermogravimetric analysis
(TGA) and differential thermal analysis (DTA) of the sensing materials were analyzed by
ZCT-B-type differential thermal gravimetric analysis.

2.4. Test Platform for Gas Sensing

An appropriate amount of terpineol was added to the as-prepared samples and
ground separately in a pestle and mortar for 1 h each to obtain 5%, 10%, 15%, pure rGO,
and pure MoS2 slurries. Then, for each sample, a small amount of the slurry was coated
onto the surface of the flexible interdigital electrode and dried at 80 ◦ C for 1 h. Further, to
improve the stability and repeatability of the sensors, they were aged at 60 ◦ C for a week
in air. The sensing measurements were carried out on an experimental platform that was
developed in our laboratory. The resistance of the MoS2 /rGO sensor was measured via
the two-wire resistance measurement method. The platform comprised a closed sensor
chamber (60 L), low-power circulating fan, data acquisition card, and computer-controlled
software system, as shown in Figure 3. The volume of the gas was calculated corresponding
to the concentration, and a calibrated gas sampler (e.g., syringe) was used to inject a certain
volume of gas into the test chamber. For example, 2 µL corresponded to 10 ppm, and 100 µL
corresponded to 500 ppm. Because the volume of the chamber was much larger than that
of the injected gas, the gas-sampling error was neglected. The gas was rapidly and evenly
distributed by using a fan. When the test gas was adsorbed onto the sensing material,
the resistance of the sensing material changed and the electrical signal was measured.
Simultaneously, the control software recorded the data by using a data-acquisition unit.
Chemosensors 2021, 9, 345 5 of 16

Figure 3. Schematic of the gas sensor test platform.

3. Results and Discussion

3.1. Sensor Flexibility Test
To verify the applicability of the rGO/MoS2 flexible gas sensor in wearable and
variable electronic equipment, the mechanical properties such as bending and fatigue
resistance of the device were evaluated. In this study, the change in device resistance
with the number of bends was investigated. A bending experiment was conducted using
a bending machine (Bending system, Custom-made setup), as shown in Figure 4a, and
the precision of this test was 0.9◦ . The results of the bending experiment showed that
continuous mechanical bending slightly increased the resistance. As shown in Figure 4b,
although a small increase in resistance is observed owing to the tensile effect, the resistance
of the device is maintained after 1000 bends. Furthermore, the response of the rGO/MoS2
sensor to the change in NH3 gas concentration at different bending angles (0◦ , 30◦ , 45◦ ,
and 90◦ ) was studied. The deviation owing to the inherent resistance of the substrate
was eliminated by calibration. As shown in Figure 4c, the sensor demonstrates excellent
gas-sensing performance at bending angles of 0◦ –90◦ . The fabricated device exhibited
relatively stable conductivity and high bending resistance. The experimental results show
that the fabricated rGO/MoS2 sensor possesses mechanical flexibility and can be applicable
in complex industrial environments.

3.2. Scanning Electron Microscopy (SEM)

The morphologies of the synthesized samples were studied via SEM; the images
are shown in Figure 5. The SEM images of pure MoS2 (Figure 5a,b) show high-density
flower-like nanospheres, which is the characteristic morphology of MoS2 [32]. The SEM
images of pure rGO (Figure 5c,d) show that the rGO sheet comprises wrinkles and curls,
indicating its considerably thin characteristic. The SEM images of the 10% rGO/MoS2
composite material (Figure 5e–h) confirm the good combination between rGO flakes and
flower-like MoS2 nanospheres. Curd-like MoS2 in the rGO/MoS2 composite is arranged in
a lamellar layer. Compared with that of pure MoS2 (700 nm), the diameter of the curd-like
structure (150 nm) is less, as shown in Figure 5a,e. Furthermore, the number of spherical
structures is significantly large, which indicates the effective participation of MoS2 . Thus,
the specific surface area of the material is higher, and the active material can be used more
effectively in the electron-transport process.
During the hydrothermal treatment, GO is reduced to rGO. Owing to a partial overlap
or combination, GO self-assembles into a flexible structure. MoS2 in the composite material
mainly comprises a finite-layer structure and is tightly coupled with the rGO sheets. In
Figure 5f, the connected network formed by the layered or stacked MoS2 attached to rGO
can be clearly observed; this structure is beneficial to the acceleration of resistance transmis-
sion in the sensor. The layered stack structure formed in the 10% rGO/MoS2 composite is
conducive to the improvement of the mechanical properties of the material. This structure
Chemosensors 2021, 9, 345 6 of 16

can considerably expand the interface contact area and improve the sensitivity of the
sensor. Figure 5h shows the discontinuity and irregularity of the layered structure, the
MoS2 curd-like particles are scattered in a disorderly manner, and the continuous running
line of rGO is distorted, forming multiple defects. These defects enable an increase in the
number of sites for the adsorption process and gas analysis, provide active energy sites,
and improve gas detection efficiency [33].

Figure 4. Flexibility test: (a) photograph of sensor bending, (b) variation in device resistance with bending times, and
(c) relationship between the response and NH3 gas concentration (100–600 ppm) at different bending angles.

Figure 5. SEM images at different magnifications: (a,b) MoS2 , (c,d) rGO, and (e–h) 10% rGO/MoS2.

Furthermore, we characterized the 10% rGO/MoS2 composite via energy dispersive

X-ray spectroscopy (EDXS); the elemental distribution maps are shown in Figure 6. In
Chemosensors 2021, 9, 345 7 of 16

addition to Mo and S, C was detected. The composite contains a large amount of C and O,
indicating the existence and even distribution of rGO in the composite.

Figure 6. Energy dispersive X-ray spectroscopy (EDXS) maps of 10% rGO/MoS2 .

3.3. Powder XRD Analysis

In the XRD patterns of MoS2 and the 10% rGO/MoS2 composite material, no peaks
corresponding to other elements are observed (Figure 7), indicating the high purity of the
composite material. In the diffraction pattern of MoS2 , the main peaks at 14.15◦ , 33.77◦ ,
and 58.49◦ can be attributed to the (002), (100), and (110) planes of MoS2 , respectively
(JCPDS card No. 37-1492). We calculated the lattice spacing (d = 6.26 nm) from the (002)
peak at 2θ = 14.15◦ using the Bragg equation, 2dsinθ = nλ (d is the interplanar spacing, half
of the diffraction angle (2θ), n = 1, λ = 0.154 nm). In contrast, the rGO/MoS2 composite
material exhibits two different peaks at 2θ 1 = 9.38◦ and 2θ 2 = 18.78◦ , and correspond to
d1 = 9.42 nm and d2 = 4.82 nm, respectively. The relationship between d1 and d2 indicates
that the composite forms a layered structure with a wider interlayer spacing than that of
pure MoS2 . This may be attributed to the effect of the hydrothermal treatment that caused
GO reduction and the disappearance of most of the oxygen-containing functional groups,
resulting in the formation of numerous defects in the composite structure. Some of these
defect positions combine with MoS2 to form a new interlayer structure [34]. This new type
of defect location provides active energy sites for the adsorption of various gas molecules,
which is beneficial for the improvement of gas sensitivity.

3.4. Raman Spectroscopy

The Raman spectrum of pure MoS2 (Figure 8) features the characteristic peaks of MoS2
at 372 and 403 cm−1 , which are E1 2g and A2g peaks, respectively, thereby confirming that
the material is MoS2 . The E1 2g peak is owing to the internal molecular vibration of the
sulfur atoms relative to the atomic layer of MoS2 , and the vibration of the A2g peak is
attributed to the out-of-layer movement of the sulfur atoms in the MoS2 relative to the axis
of the non-MoS2 layer. In the 10% rGO/MoS2 composite, the E1 2g and A2g peaks of MoS2
are evident, and the characteristic peaks ascribed to the D and G bands of rGO are present
at 1349 and 1585 cm−1 , respectively, which proves that rGO has been successfully added to
the mixture. The intensity ratio ID/IG of peaks D and G serves as an important parameter
to evaluate the degree of order and defects of carbon materials. Generally, the smaller the
ID/IG value, the higher the degree of order of carbon materials [35]. After calculation, the
ID/IG value of the 10% rGO/MoS2 composite was approximately 1.39, which was higher
than those of rGO (~1.03) and GO (~0.91), indicating that the size of GO decreased after
reduction, resulting in the increase in the D peak intensity [36]. In addition, studies have
Chemosensors 2021, 9, 345 8 of 16

shown that the increase in the ID/IG value indicates the improvement of the electrical
properties of GO [37], which is beneficial to improve the gas-sensing response speed of
the composite.

Figure 7. X-ray diffraction (XRD) patterns of MoS2 and the 10% rGO/MoS2 composite.

Figure 8. Raman spectra of MoS2 and the 10% rGO/MoS2 composite.

3.5. Specific Surface Area and Porosity Analysis

The specific surface area is one of the most important parameters in the evaluation
of gas-sensing materials. To explore the influence of rGO addition on the specific surface
area of MoS2 , we conducted a N2 adsorption–desorption test on pure rGO, pure MoS2 and
the 10% rGO/MoS2 composite. The relevant results are shown in Figure 9. The specific
surface areas (Table 1) of pure rGO, pure MoS2 and the 10% rGO/MoS2 composite were
17.4157, 2.2204 and 23.2786 m2 /g, respectively, which showed an approximately ten-fold
increase for the as-prepared composite. Thus, rGO addition significantly increased the
specific surface area of MoS2 , enhancing its ability to adsorb and desorb gases.
Chemosensors 2021, 9, 345 9 of 16

Figure 9. N2 adsorption and desorption isotherms of (a) pure rGO, (b) pure MoS2 and the (c) 10% rGO/MoS2 composite.

Table 1. Specific surface area (SBET) and average pore diameter of MoS2 and the 10% rGO/MoS2 composite.

Parameters rGO MoS2 10% rGO/MoS2

SBET (m2 /g) 17.4157 2.2204 23.2786
Average pore size (nm) 5.4186 11.2850 7.7910

3.6. TGA
We conducted TGA on the prepared 10% rGO/MoS2 composite; the results are shown
in Figure 10. Within the test temperature range of 30–900 ◦ C, the mass loss of the com-
posite occurs in four stages. The small mass loss of 10% rGO/MoS2 in the first stage
(30–300 ◦ C) can be attributed to dehydration during physical adsorption. In the second
stage (300–400 ◦ C), the mass loss can be attributed to the thermal decomposition of the
remaining oxygen-containing functional groups on rGO. In this stage, there is an obvi-
ous endothermic peak in the differential thermal analysis (DTA) curve at 400 ◦ C. In the
third stage (400–780 ◦ C), the DTA and TG remains in a steady state. In the fourth stage
(780–900 ◦ C), the mass loss of the composite is due to the oxidation and pyrolysis of the
carbon in rGO. This indicates that the material can maintain stable physical and chemical
properties over 30–300 ◦ C, and the heating temperature of the material should not be higher
than 300 ◦ C. This result is in line with that reported in another paper [38].

Figure 10. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) curves of the
10% rGO/MoS2 composite.

3.7. Heating Electrode Test

Temperature has an important influence on the response-recovery time and sensitivity
of the sensor. To optimize the working conditions of the sensor, the relationship between
Chemosensors 2021, 9, 345 10 of 16

the heating temperature and the input power of the heating electrode was studied. The
sensor temperature (T0 ) before heating was 22 ◦ C, and the heater used different power
levels to obtain the temperature (T). Figure 11 shows the linear relationship between the
heating power and the temperature change.

Figure 11. Relationship between the heating power and temperature.

3.8. Gas-Sensing Response Parameters

Figure 12 shows a representative response curve obtained for 10% rGO/MoS2 upon
exposure to 100 ppm NH3 at 141 ◦ C. As shown in the figure, the resistance increased from
2983 Ω (in air) to 3080 Ω (in NH3 atmosphere). When the NH3 gas enters the gas-sensing
test chamber, the test resistance increases. Because of the electron-donating property of
NH3 molecules, the composite exhibits the p-type behavior of a semiconductor channel.
In Figure 12, the relative response is defined as Response = Rg /Ra , where Ra is the basic
resistance in air, and Rg is the test resistance. Response time (tresponse ) is defined as the time
required for the sensor to attain 90% of the maximum resistance value. Similarly, recovery
time (trecovery ) is defined as the time required for the maximum value to decrease to 10% of
the maximum value.

Figure 12. Representative response obtained upon exposing the gas-sensing material to 100 ppm of
NH3 gas. Ra represents the basic resistance in air, Rg represents the test resistance value, tresponse
represents the response time, and trecovery represents the recovery time.
Chemosensors 2021, 9, 345 11 of 16

The response parameters of the 10% rGO/MoS2 sensor to 100 ppm NH3 at 141 ◦ C
were tresponse = 17 s, trecovery = 56 s, and Response = 1.26. The limit of detection (LoD) of
the sensor was 10 ppm.

3.9. Optimization of Working Temperature and Mixing Ratio

The working temperature of the sensor has a significant impact on its performance;
therefore, it is critical to determine the optimal working temperature for analyzing sensor
performance. To identify the optimal working temperature of the sensor, we obtained
the response curves of the gas sensors made of composites containing different rGO con-
tent upon exposure to 100 ppm NH3 in the temperature range of 25–200 ◦ C, as shown in
Figure 13. Figure 13 shows that the response value of the sensor changes with temperature.
The response value of pure MoS2 to 100 ppm NH3 gas increases with an increase in the
temperature, reaches the peak at 141 ◦ C, and gradually decreases when the temperature
continues to increase. With an increase in the temperature, the sensor response demon-
strates an “increase–peak–decrease” trend. Under the same concentration and temperature
conditions, the response values of pure rGO and pure MoS2 materials to NH3 were not
high. In contrast, the response values of the composites with rGO and MoS2 were signifi-
cantly higher. Among all composites, the performance of the 10%-rGO-doped composite
was the highest, and the response value to 100 ppm NH3 gas attained a peak value of
1.26 at 141 ◦ C. Although the sensor had a certain response at room temperature (25 ◦ C),
higher response was obtained upon heating. Therefore, we considered 141 ◦ C and the
10% rGO/MoS2 composite to be the optimal working temperature and sensing material,
respectively. Furthermore, we fabricated the gas sensor under the optimal conditions and
studied its performance.

Figure 13. Response of pure MoS2 , pure rGO, and rGO/MoS2 composites with different graphene
contents to 100 ppm of NH3 at different operating temperatures.

Figure 14 shows the continuous transient resistance–response–recovery curve of the

sensor comprising the 10% rGO/MoS2 composite upon exposure to NH3 gas at concen-
trations of 50–1750 ppm at the optimal operating temperature. It is evident that the
resistance of the sensor increases with an increase in the NH3 concentration, indicating
its NH3 -sensing ability. The change curve (Figure 15) of sensor resistance with the NH3
concentration in an NH3 -flushed environment reflects the relationship between the NH3
concentration and the sensor resistance value. The resistance of the sensor comprising the
10% rGO/MoS2 composite exhibits a linear relationship with the NH3 concentration in the
range of 50–1500 ppm. The sensitivity of the sensor is 0.06672, and the linearity is relatively
high (R2 = 0.948). When the gas concentration was higher than 1500 ppm, the resistance
Chemosensors 2021, 9, 345 12 of 16

value did not change significantly, indicating that the sensor became saturated at a high
concentration of NH3 .

Figure 14. Variation in the response of the 10% rGO/MoS2 sensor to different concentrations of NH3 .

Figure 15. 10% rGO/MoS2 sensor response–concentration curve.

Furthermore, selectivity is an important parameter of the NH3 sensor in practical

applications. Figure 16 shows the responses of the 10% rGO/MoS2 sensor to various
gases, including Cl2 , NO, NO2 , and a few typical volatile organic compounds (VOCs). The
different responses of the sensor are mainly owing to the inherent chemical properties
and reactivities of the gas molecules. It is evident that the response of the sensor to
NH3 is much higher than that toward other gases. In addition, the response of the 10%
rGO/MoS2 composite to 10 ppm NH3 is much higher than that to 100 ppm VOCs. All
these observations confirm the high selectivity of the rGO/MoS2 sensor for NH3 sensing.

3.10. Sensing Mechanism

Gas sensing involves the processes of adsorption and desorption of gas molecules
and the use of a sensitive platform. Recent theoretical studies have revealed the negative
surface adsorption energy (−250 MeV) of NH3 molecules on the surface of MoS2 [39]. In
addition, the first principles calculation reveals the partial charge (E) transfer from the
adsorbed NH3 to the potential MoS2 channels. NH3 acts as an electron donor, and electrons
are transferred from NH3 to MoS2 , resulting in the decrease in MoS2 hole density, weaken
of MoS2 conductivity, and increase in resistance [40]. Moreover, due to the existence
Chemosensors 2021, 9, 345 13 of 16

of oxygen-containing functional groups and structural defects on rGO, the addition of

rGO can provide more adsorption sites and is more conducive to the adsorption of gas,
compared with those of pure MoS2 .

Figure 16. Response of the 10% rGO/MoS2 sensor to various gases.

In the process of hydrothermal preparation of rGO/MoS2 composites, due to the exis-

tence of oxygen-containing functional groups on the surface of GO, Mo4+ is adsorbed on
the surface of graphene because of the electrostatic interaction, which provides nucleation
sites for the growth of MoS2 materials. Compared with that of pure MoS2 , the size of
MoS2 in the composite is smaller and the active edge is more exposed, thus increasing the
number of active sites for the gas-sensing reaction and, consequently, effectively improving
the gas-sensing response [41]. The Fermi level of MoS2 is higher than that of graphene, and
the addition of a small amount of rGO is beneficial. When the two are in contact, the het-
erostructure formed by the rGO/MoS2 composite separates the carriers into electrons and
holes under the action of the potential field. The electron transfer ability of the composite
is enhanced under the action of the potential barrier at the heterojunction interface to accel-
erate the electron transfer, therefore effectively improving the gas-sensing response time.
When the content of added rGO exceeds the threshold (20% rGO/MoS2 ), a large amount
of rGO is accumulated, which easily forms a network between the electrodes. Due to the
high conductivity of rGO, the resistance adjustment of the composite is weakened, which
reduces the sensitivity of the gas sensor. In addition, high content of rGO easily covers
the active site of MoS2 and hinders the interaction between NH3 and MoS2 . Therefore, the
sensing performance of 10% rGO/MoS2 is optimal.

4. Conclusions
rGO/MoS2 composites were synthesized via a one-step hydrothermal method. The
result showed that the NH3 detection performance of the rGO/MoS2 composites was the
highest when the content of rGO was 10%. It was found by structural analysis that there
were various defects on MoS2 and rGO, which served as the active sites for the adsorption
of gas molecules. The flower-like MoS2 nanospheres in the rGO/MoS2 composite formed
thin layers. Thus, when the diameter of the flower-ball structure decreased, the number
of spherical structures significantly increased and the specific surface area of the material
increased, thereby resulting in the enhancement of the electron-transport capacity of the
active material. The XRD analysis results confirmed that most oxygen-containing functional
groups in the rGO/MoS2 composites disappeared and their structures possessed numerous
defects, which enabled the formation of a new interlayer structure. This resulted in an
increase in the number of active energy sites, which was conducive to the improvement of
the gas-sensing properties. The TGA results indicated that the composites could maintain
Chemosensors 2021, 9, 345 14 of 16

stable physical and chemical properties at temperatures below 300 ◦ C. The optimal working
temperature of the sensor in this study was 141 ◦ C, and the properties of the sensing
materials were stable at this temperature.
In this study, we used the MEMS technology to fabricate a heating electrode and
gas-sensing electrode on a flexible PI sheet with Pt to form a “sandwiched” sensor structure.
We developed a gas-sensing test platform and measured the response parameters of the
10% rGO/MoS2 sensor to 100 ppm NH3 at 141 ◦ C. The response time, recovery time, and
response value were 17 s, 56 s, and 1.26, respectively, for a test range of 50–1500 ppm of
NH3 . The LoD of the sensor was 10 ppm. The flexible chip maintained stable gas-sensing
performance under deformation at 30◦ , 45◦ , and 90◦ bending angles, and its performance
was stable after 1000 bending tests. The fabricated sensor demonstrated stable conductivity
and high bending resistance.
This sensor possessed the ability to detect NH3 across a broad concentration range and
demonstrated high sensing performance, low power consumption, fast recovery response,
low-temperature operation, and substrate flexibility. Further, the sensor possesses the
advantages of having a small volume, high flexibility, and stable performance. It is suitable
for mass production and for remote and distributed measurement. It provides a new
approach for the detection of pollutants in industrial environments and the atmosphere.

Author Contributions: Conceptualization, Z.R. and Y.S.; methodology, T.S.; validation, T.W.; data
curation, B.T.; writing—original draft preparation, Z.R.; writing—review and editing, Y.S.; visualiza-
tion, H.N.; funding acquisition, X.Y. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the National Key Research and Development Project, grant number
2016YFA0602701,and National Science Foundation Program of China, grant number 61801149.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Written informed consent has been obtained from the patient(s) to
publish this paper.
Data Availability Statement: The data presented in this paper are available in this article.
Acknowledgments: The authors would like to thank the research staff for their contributions to
this project.
Conflicts of Interest: The authors declare no conflict of interest.

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