Analytica Chimica Acta 1287 (2024) 342075

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Analytica Chimica Acta

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Humidity activated ultra-selective room temperature gas sensor based on W

doped MoS2/RGO composites for trace level ammonia detection
S.P. Linto Sibi a, M. Rajkumar a, *, Mathankumar Manoharan b, J. Mobika c, V. Nithya Priya a,
R.T. Rajendra Kumar b
a
Department of Physics, PSG College of Arts and Science, Coimbatore, 641014, Tamil Nadu, India
b
Advanced Materials and Devices Laboratory (AMDL), Department of Nanoscience and Technology, Bharathiar University, Coimbatore, 641046, Tamil Nadu, India
c
Department of Physics, Nandha Engineering College, Erode, Tamil Nadu, 638052, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• An in-situ hydrothermal method was

employed for the synthesis of W doped
MoS2/RGO composite.
• 5 % W doped MoS2/RGO exhibited 42-
fold increase in response relative to its
pristine counterparts under a RH of 70
%.
• Surplus amount of active edge sites
triggered humidity activated solvation
effect of ammonia gas analytes.
• Humidity activated high selectivity and
sensitivity of W5 gas sensor possess the
potential for breathomics application.

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

Handling Editor: Rebecca Lai The lack of highly efficient, cost effective and stable ammonia gas sensors functionable at room temperature even
in extreme humid environments poses significant challenge for the future generation gas sensors. The prime
Keywords: factors that impede the development of such next generation gas sensors are the strong interference of humidity
Room temperature gas sensor and sluggish selectivity. Herein, we fabricated tungsten doped molybdenum disulphide/reduced graphene oxide
Tungsten doped MoS2/RGO
composite by an in-situ hydrothermal method to exploit the adsorption, dissolution (solubility), ionization and
Humidity activated gas sensor
transmission process of ammonia and thereby to effectuate its trace level detection even in indispensable humid
Proton conductive Highly selective ammonia
gas sensor environments. The protype based on 5 at.% Tungsten doped MoS2/RGO (W5) gas sensor exhibited 3.8-fold
Edge site enrichment increment in its response to 50 ppm of ammonia when the relative humidity varied from 20 % to 70 % with
VOC ultra-high selectivity at room temperature. The as prepared gas sensor revealed a practical detection limit down
to 1 ppm with a substantial response and rapid recovery time. Furthermore, W5 gas sensor exhibited a 42-fold
increment in response to 50 ppm of ammonia relative to its pristine (MoS2/RGO) MG composite with a RH of 70

* Corresponding author.
E-mail address: [email protected] (M. Rajkumar).

https://doi.org/10.1016/j.aca.2023.342075
Received 25 August 2023; Received in revised form 24 November 2023; Accepted 25 November 2023
Available online 30 November 2023
0003-2670/© 2023 Elsevier B.V. All rights reserved.
S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

%. The proton hopping mechanism accountable for such an enormous enhancement in ammonia sensing and its
potential for breath sensor are briefly annotated.

1. Introduction characteristics of MoS2 based gas sensors have been attributed to the
edge sites with higher density of “d” electrons which helps in effective
Owing to the rapid developments and advancements of science and adsorption of gas analyte [5]. Besides, the lower intrinsic electronic
technology, a plethora of advances in therapeutic interventions and conductivity of the basal planes of MoS2 hinders the charge transfer
diagnostic measures were observed among which exhaled breath anal­ across the layers which in turn affects the adsorption and desorption
ysis as a point of care diagnostics has gathered significant attention. Due characteristics of target gas analytes. Hence, in order to overcome such
to its non-invasive, cost-effective nature for accurately detecting issues much efforts have been laid among which heteroatom doping
epidemic diseases like diabetes, obesity, and cancer in their early stages, proves out to be a most useful technique with pronounced outcomes for
developments in breath analysis brought about by science and tech­ gas sensors. Based on the current reports of Junmeng Zhang et al. doping
nology have made a significant contribution to human society [1]. In of MoS2 lattice tailored the electronic structure of the host lattice which
general, the exhaled human breath released by a healthy human com­ entailed in the reduction of potential barrier for the adsorption/de­
prises of a complex mixture of gases and volatile organic compounds sorption of the adions [6]. Also, the finding of the Ruichun Luo et al.
(VOC’s) that exist in wide range of concentrations from ppb to ppm reveals that the substitutional doping of nickel in the molybdenum sites
levels wherein excess concentration of VOC’s expired by an unhealthy of pristine MoS2 actuated a strong interaction of Ni with S that stimu­
patient than their threshold value serves as breath biomarkers for lated intense lattice distortion and local variations in the electronic
various acute diseases. Among such variety of biomarkers, ammonia structure which resulted in higher proton adsorption and reduction
that serve as a biomarker for kidney and liver disorders has drawn sig­ capability. Moreover, the enhanced charge transfer induced by the
nificant research attention due to its wide spread prevalence in human dopants were likely to boost up the catalytic activity of the surrounding
society. Due to the kidney malfunction of chronic kidney disease pa­ Mo and S sites in MoS2 [7]. Apart from these, the inert basal planes of
tients, the urea produced by the catabolism of protein in liver get MoS2 were reported to be activated by the integration of doping and
accumulated in the blood that can penetrate the blood lung barrier and sulphur vacancy which were responsible for room temperature gas
pop up in exhaled breath [2]. According to the recent reports on the sensing performance of MoS2 with a lowest detection limit of 8.1 ppb
ammonia breath sensor, the concentration of ammonia in the exhaled [8]. Notably, Mohapatra Prakash Kumar Sahoo et al. through their
breath of chronic kidney disorder (CKD) patients escalates to 4.8 ppm in density functional calculations proved that doping induced strain and
the final stage of renal disease [3]. Hence, the development of a defects in the MoS2 lattice could create an upswing in the rate of
non-invasive, cost-effective analysis technique with trace level detection adsorption of ammonia gas molecules onto the surface of MoS2 which
limit demands utmost attention for the early-stage diagnosis of such were further proved experimentally [9]. Hence, doping proves to be a
acute disease. vital technique to enhance the gas sensing attributes of MoS2. Never­
To analyse and detect the compositional variations of VOC’s present theless, high van der Waals forces between the neighbouring MoS2
in the exhaled breath of human beings several spectroscopic techniques layers made them vulnerable to severe restacking, which decreased the
such as proton transfer reaction-mass spectrometry (PTR-MS), gas amount of active sites for gas molecule adsorption and hampered the
chromatography-mass spectrometry (GC–MS), laser photoacoustic sensing capabilities of pristine MoS2. Sukhwinder Singh et al. developed
spectroscopy (LPAS) and selected mass flow tube mass spectrometry a TMDC based highly selective, room temperature ammonia gas sensor
(SIFT-MS) were used for a few decades which helps in early-stage that exhibited a substantial response and recovery time of 15 s and 135 s
diagnosis of the disease and deliver rapid customized interventions respectively which was attributed to the reduced stacking along with
and treatments. However, such analytical techniques demand pre- enriched edge sites of MoSe2 nanosheets [10]. Moreover, through their
treatment of exhaled breath along with trained operators and costly other works, they highlighted that the effective formation of hetero­
equipment with complex dimensions which impedes its usage in point of junctions formed at the interface of two materials could drastically
care medical diagnostics. Hence, in the search of a potential alternate for enhance the adsorption/desorption traits of MoS2 based gas sensor
such non-invasive human exhaled breath analysis techniques, chemir­ which led to the development of MoS2/SnO2 based room temperature
esistive gas sensors have grabbed the attention of the scientific com­ ammonia gas sensor that could effectively sense 0.4 ppm of ammonia [
munity due to its simple structure, ease of miniaturization and [11,12]. Many efforts have been made over the past few decades to
integration, low cost, user friendly and portability. Although, gas sen­ decrease the stacking nature of MoS2 and increase the density of the
sors based on metal oxide, polymers, MXenes, carbon, metal organic active sites. Of these efforts, van der Walls heterostructures of MoS2
frameworks (MOF) possess substantial gas sensing traits such as ultra- composited with RGO appear to be the most feasible approach because
sensitivity and enhanced stability they were prone to limitations such of the increased conductivity and larger surface area of the reduced
as low selectivity and deteriorated performance in extreme humid graphene oxide. Moreover, the electronic properties of the active sites of
environment [4]. Furthermore, in extremely humid conditions, the MoS2 were reported to be enhanced upon its integration with highly
lowest detection limit of these sensor materials was severely limited, conductive RGO [13].
making it unable to detect trace level of ammonia in exhaled air. Since, Inspired by the above context, we propose a unique strategy to un­
exhaled breath comprises of highly humidified mixture of thousands of wrap the ultra-selective and sensitive ammonia sensing traits of MoS2
gas analytes, gas sensors that could selectively sense ammonia gas activated by humidity through the synergetic effect brought by tungsten
molecules even under extreme humid environments with a potential for dopants and effective formation of MoS2/RGO heterojunctions. Instead
trace level detection were of utmost demand in ammonia breath sensors. of using the traditional strategies to avoid the anti-humidity effects on
Hence, in order to exceed the interference of foreign gas analytes and ammonia sensing, we employ a proton conductive strategy accom­
humidity, molybdenum disulphide (MoS2) as pioneer member of tran­ plished by adsorbed water molecules on the sensor surface that could
sition metal dichalcogenides (TDMC’s) family were employed due to its effectively enhance the diffusion, adsorption and desorption traits which
robust and versatile layer dependent properties such as surplus active in turn ameliorates the gas sensing characteristics of the proposed gas
sites, enhanced surface to volume ratio, variable bandgap that renders sensor. Also, the conductive channel established by the adsorbed water
them to be an ideal candidate for breath sensor application. molecules through hydrogen bonding could boost up the migration of
According to the recent research, the enhanced gas sensing ionized ammonia gas molecules which in turn increases the reactivity of

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

the target gas with host material. Herein, a cost effective, one step in-situ 40.18 mg, 56.25 mg of sodium tungstate dihydrate dissolved in 10 mL of
hydrothermal method was employed for the synthesis of pristine and D.I water was added followed by sonication of 10 min. The as obtained
tungsten doped MoS2/RGO hybrid composites. The mechanism for their brown colloidal solution was transferred to a 100 mL Teflon lined
corresponding enhancements in the selectivity and sensitivity of the autoclave at 200◦ C for 24 h. After the completion of the reaction, the
hybrid sensor induced by the dopants and heterojunction in combina­ obtained black precipitates were washed thoroughly and dried in vac­
tion with the proton conductive layer instigated by the humid envi­ uum oven at 60 ◦ C overnight. The as obtained black powder with
ronment were discussed briefly. The proposed combinational effect of different concentration (24.10 mg, 40.18 mg, 56.25 mg) of sodium
doping together with heterojunction in humidity activation of highly tungstate were designated as W3, W5 and W7 respectively.
conductive MoS2 were envisaged to sheds light on the future de­
velopments of transition metal dichalcogens (TMDC) based composites
for ammonia breath sensor and environmental applications. 2.4. Sensor fabrication and ammonia sensing measurement

A homemade gas sensing detection system was employed to inves­

2. Materials and methods
tigate the ammonia sensing performance of the prepared composites
which consist of a computer-controlled gas distribution unit interfaced
2.1. Chemicals
with data acquisition system. The detailed description of the gas sensing
system was previously reported by our group [15]. Briefly, 1 mL of
Hydrochloric acid (HCl, 36.46 %), Sulphuric acid (H2SO4, 98 %),
distilled water was used to sonicate 5 mg of the prepared composites
Potassium permanganate (KMnO4, 99 %), Natural graphite, Hydrogen
until they were evenly distributed. Following the full dispersion of the
peroxide (H2O2, 30 %), Ammonium molybdate ((NH4)6Mo7O24.4H2O,
nanocomposite, 10 μL of the prepared solution was dropped onto the
99 %) Thiourea (CH4N2S, 99 %), Sodium Tungstate dihydrate (Na2WO4.
gold interdigitated electrode surface and dried for 2 h at 60 ◦ C in a hot
2H2O, 99 %), Sodium nitrate (NaNO3, 99 %) were purchased from
air oven. Thereafter, the inter digitated electrode was positioned above
Merck, India. All the chemicals used were of analytical grade and was
the microheater whose temperature could be controlled with higher
used as such without any prior purification.
precision using Agilent B3649 temperature controller. Initially, syn­
thetic gas was passed onto the surface of the electrodes with a flow rate
2.2. Synthesis of MoS2/RGO composite of 200 sccm (standard cubic centimetres per minute). Once when a
stable resistance had been observed, target has been passed into the gas
A cost effective, one step, in-situ hydrothermal method was employed chamber. The ratio between the flow of ammonia and synthetic air was
for the synthesis of pristine MoS2/RGO (MG) and its corresponding controlled employing mass flow controllers to obtain the desired con­
tungsten doped hybrid composites. The graphene oxide (GO) used in the centration of NH3 gas wherein the total flow rate was regulated to 200
preparation of MoS2/RGO was derived from the modified hummers sccm. The corresponding dynamic resistance variation data were
method [14]. The as obtained GO powders was dried in a hot air oven at recorded employing Keysight B2912A source meter interfaced with a
60◦ C for 24 h. Initially, the GO solution was prepared by adding 14.6 mg data logger. Added, the cross selectivity of the prepared gas sensor
of GO into 30 mL of distilled water under continuous stirring followed by prototypes was investigated using the same strategy wherein different
ultrasonication for a period of 30 min until a well dispersed brown so­ concentration of target gases were used. By passing the carrier gas
lution was formed. Meanwhile, 0.5 g of ammonium molybdate tetra­ through deionized water, a humidity atmosphere was created, and a
hydrate and 1.2 g of thiourea was added into another 30 mL of D.I water high-precision commercial humidity sensor was used to periodically
followed by stirring for 10 min to obtain a translucent solution. The as measure the impact of the humidity. All the gas sensing trials were
procured clear solution of ammonium molybdate and thiourea was executed at room temperature (25 ◦ C) with 20 % relative humidity. The
added dropwise into the GO solution assisted by vigorous stirring observed response values of the gas sensor prototypes were calculated
accompanied by sonication aimed for the effective distribution of pre­ using the formula

( )
Rair − Rgas
R (%) = 100……………………………………………….……………….…. (1)
Rgas

cursors over the GO surface. The prepared colloidal solution was then Where Rair and Rgas attribute to the corresponding resistance of the gas
transferred into a 100 mL Teflon lined autoclave and kept inside a hot air sensors in air and target gas respectively. After the exposure of the target
oven at 200◦ C for 24 h. Following the completion of the reaction, the gas, the time taken by the gas sensor to reach 90 % of its stabilised signal
autoclave was allowed to naturally cool. The resulting black precipitates was considered as the response time whereas the time required to ach­
were then cleaned with ethanol and deionized water before being dried ieve 90 % of its stable baseline was calculated as the recovery time.
for a whole night in a vacuum oven to create the MoS2/RGO composite.
2.5. Materials characterization
2.3. Synthesis of tungsten doped MoS2/RGO composites
The X-ray diffraction analysis was performed on Empyrean Malvern
To prepare tungsten doped composites, the same synthesis process Panalytical diffractometer with Cu Kα radiation (λ = 1.54 Å). Using a
used for the MG was also used, coupled with the stochiometric addition laser excitation at 532 nm, the WiTec alpha 300 confocal Raman spec­
of tungsten precursor. Briefly, 14.6 mg of GO powder was added into 30 trometer was utilized to obtain the Raman spectra of the prepared
mL of deionized water in conjunction with stirring and ultrasonication samples. The surface morphology of the composites was assessed using
for a period of 30 min. Afterwards, 0.5 g of ammonium molybdate and field emission scanning electron microscopy (FESEM) micrographs
1.2 g of thiourea dispersed in 20 mL of D.I water was also added into the recorded on SIGMA HV – Carl Zeiss with Bruker Quantax 200 at an
GO solution followed by under magnetic stirring accompanied with accelerating voltage of 5 kV. The functional groups of the prepared
ultrasonication for a period of 10 min to achieve homogeneous distri­ composites were determined employing FTIR - Schimadzu IR Affinity
bution of MoS2 precursor over GO. To the above suspension 24.10 mg, model 1s having a double beam spectrometer with the wavenumber

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 1. (a) X-ray diffraction spectra of MG, W3, W5 and W7 composites (b) Magnified view of the shift of (002) plane in MG, W3, W5 and W7 composite.

range of 4000 cm− 1 to 400 cm− 1 and resolution of 0.5 cm− 1. The
chemical states and elemental composition were obtained with XPS (X-
ray photoelectron spectroscopy) using PHI 5000 VERSAPROBE SCAN­
NING ESCA MICROPROBE spectrometer.

3. Results and discussion

3.1. Microstructural and chemical properties

The crystallographic and microstructural changes imputed by the

incorporation of tungsten dopants into the lattice of MoS2 composited
with RGO were investigated employing X-Ray diffraction analysis.
Fig. 1a portrays relative X-ray diffraction pattern of pristine MoS2/RGO
(MG) and its tungsten doped composites (W3, W5 & W7) wherein the
diffraction peaks of MG were positioned at 33.45◦ , 39.84◦ , 49.51◦ ,
58.97◦ , 69.57◦ with its most intense peak at 14.24◦ that corresponds to
(100), (103), (105), (110), (201) and (002) planes of 2H MoS2 (JCPDS
card no: 37–1492). Moreover, the absence of the tungsten peaks apart
from the aforementioned peaks signifies the phase purity of the prepared
samples. It is also obvious from Fig. 1a that the diffraction patterns of
W3, W5 and W7 were analogous with MG which indicates that crystal
structure of MG was retained even after the introduction of dopants. Fig. 2. Raman spectra of the prepared MG, W3, W5 and W7 composites.
Meanwhile, as the dopant concentration increased, (002) diffraction
plane shifted to lower angles as shown in Fig. 1b with a broad diffraction hybrids, a greater number of active sites would be exposed. Hence, it
feature which signifies the enlarged interlayer distance and lattice dis­ could be concluded from the above inferences that W5 nanocomposite
tortions induced by the substitution of tungsten dopants into MoS2 lat­ possess higher edge defects along with expanded interlayer which could
tice. Such expansion of the interlayer distance significantly enhances the results in enhanced diffusion, adsorption and diffusion characteristics.
conductivity and adsorption ability of the doped composites which The nature of defects instigated by the tungsten dopants in the host
could result in enhanced gas sensing traits. Moreover, the dopants were lattice and the corresponding change in the phases of the prepared
reported to weaken the interlayer coupling between S–Mo–S layers due composites was investigated utilizing Raman spectroscopic analysis.
to the charge redistribution that indeed affect the stacking structure Fig. 2 illustrates Raman spectra of MG, W3, W5 and W7 nanocomposites.
[16]. Added, the intensity of the (100) plane in W5 nanohybrid with a The figure shows that MG composites have two prominent vibrational
threshold tungsten doping of 5 at.% get enhanced relative to (100) plane modes at 375.80 cm− 1 and 407.46 cm− 1, which correspond to the
of MG, W3 and W7 composites which signifies the edge enrichment typical MoS2 vibrational modes of A1g and E2g. Here, E2g modes asso­
effect triggered by the optimal doping of tungsten into the MoS2 lattice ciates with the in-plane vibration of two S atoms with respect to Mo
[17]. Previous reports state that the difference in the atomic radii of the atom in opposite direction (along the basal plane) whereas A1g denotes
host and dopant atoms causes the bond length to expand or contract, the out of plane vibration of S atoms in opposite direction (perpendic­
distorting the pristine geometry’s local symmetry and increasing the ular to the basal plane). Besides, two additional characteristics vibra­
magnitude of edge sites [18,19]. Furthermore, the heteroatom dopants tional modes of RGO were also observed with bands positioned at
were reported to activate the in-plane S sites of MoS2 within the basal 1350.82 cm− 1 and 1590 cm− 1 which could be well indexed to the D and
plane with the aid of strain mediated defect engineering [20]. Due to the G bands of RGO respectively wherein G bands corresponds to stretching
intense edge defects in W5 composite eventuated from the lattice vibrations of sp2 sites present in the graphitic carbon and D band sym­
distortion via optimal doping, smaller domains were likely to be formed bolize the defects and disorders actuated during the formation of com­
within the basal plane of MoS2 which was well reflected from the posite. The presence of these abovementioned peak assignments in MG
augmented growth of (100) and (110) planes relative to (103) plane confirms the successful formation of MoS2/RGO composite.
[21]. Scherrer’s formula was employed to calculate the crystallite size of As observed from Fig. 2, the frequency difference between E2g and
the prepared composite whose values were 6.69 nm, 7.06 nm, 6.98 nm & A1g vibrational modes for MG was estimated to be Δω = 32 cm− 1
7.56 nm for MG, W3, W5 and W7 composites respectively. Owing to the whereas W3, W5 and W7 holds a value of Δω ≈ 27 cm− 1 which signifies
smaller crystallite size of W5 nanocomposite relative to the doped

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

that the successful doping of tungsten atoms into the MoS2 lattice from 3200 cm− 1 to 3600 cm− 1 corresponds to O–H stretching vibration
attenuated the Van der Waals force enacting between the adjacent whereas the stretching vibrations of carbonyl and C–H groups were
S–Mo–S layers that ultimately resulted in limited number of layers on observed around 1738.05 cm− 1 and 2919.98 cm− 1 respectively. The
comparison with its pristine counterpart. Hence, tungsten doped com­ absorption band positioned at 1629.10 cm− 1 signifies the formation of
posites were likely to exhibit superior electrical characteristics relative sp2-hybridized carbons (C=C) present in RGO meanwhile the weak
to MG [22]. Further, it is noteworthy that with the introduction of the bands located at 1221.62 cm− 1, & 1063.20 cm− 1 attributes to stretching
dopants, E2g peaks of W3 exhibits a red shift to 376.46 cm− 1 whereas A1g vibrations of C–OH & C–O groups. Furthermore, the Mo–S stretching
peak displays a blue shift to 404.96 cm− 1 relative to the corresponding vibrations was observed around 602.23 cm− 1 which deduce the for­
peak positions of MG. With further increase in the concentration of mation of MoS2. From the relative comparison of the O–H stretching
dopants (W5 and W7), the E2g vibrational modes get further shifted to vibrations among the prepared composites, it is found that W5 com­
376.16 cm− 1 and 377.72 cm− 1 whereas no significant changes in the A1g posite exhibits larger proportion of O–H stretching vibration than
peak position were observed. Such a substantial shift of A1g peak in others. Huadou Chai et al. have reported recently that OH groups are
doped composites signifies the enhanced electron phonon coupling adsorbed more preferentially to the edge surface of 2H MoS2 than to
brought about by the increased electron concentration through the other active sites [26]. As revealed from the XRD and Raman analysis,
successful doping of tungsten into MoS2 lattice [23]. Furthermore, the the W5 nanocomposite reflected larger number of edge exposed surfaces
substitutional doping of W atoms into the MoS2 lattice causes due to which it exhibits higher proportion of surface adsorbed hydroxyl
strain-mediated lattice distortions that were consistent with XRD anal­ groups The presence of the characteristic vibration band assignments of
ysis because of the different atomic radii and electronegativity of RGO and MoS2 in all the prepared samples confirms the successful
tungsten dopants relative to Mo and S atoms. Hence, the E2g vibrational coexistence of MoS2/RGO in all the prepared composites [27–29].
modes which get preferentially excited for strain gets red shifted for W3, The surface morphology of the prepared composites and the effect of
W5 and W7 relative to MG nanocomposite. tungsten dopants in morphological refinement were assessed employing
Moreover, the line width of E2g and A1g in W5 nanohybrid exhibits a Field Emission Scanning Electron Microscopy (FESEM) analysis. Fig. 4
well reflected peak broadening on comparison with W3 and W7 which (a,b,c,d,e,f,g,h) depicts the low and high magnified images of the hier­
manifest the pronounced defects in W5 eventuated from the threshold archical MoS2/RGO (MG) and its tungsten doped composites (W3, W5,
doping of tungsten atoms into the host lattice. Also, the intensity of A1g W7) wherein all the prepared composites exhibit flower shaped
is higher than E2g peak which denotes the larger exposure of edge morphology with varied amount of aggregation. The average diameter
terminated structure in the prepared composites among which, W5 ex­ of the flower shaped microsphere of MG, W3, W5 and W7 were assessed
hibits higher intensity E2g/A1g ratio of 0.9182 where MG, W3 and W7 to be 1.59 μm, 7.3 μm, 2.3 μm and 3.7 μm respectively. Initially, when
possess value of 0.5176, 0.8540 & 0.8577 respectively [24]. Hence, it the dopant concentration was increased to 3 at%, the small trace of
could be summarized from the above results that the optimal incorpo­ dopant precursors could potentially behave as pre-seed which results in
ration of tungsten dopants in W5 nanocomposites yielded in large reduced nucleation density [30,31]. Hence, W3 microspheres possess
exposure of edge sites with metallic nature mediated by the strain higher diameter relative to others. As obvious from Fig. 4a,b, the MoS2
induced lattice distortions. In addition to the enriched edge sites, the nanostructures were densely distributed over the RGO in all the pre­
tungsten dopants reduced stacking of MoS2 layers in W5 that entailed in pared samples which reveals the unique ability of the RGO to serve as
boosted charge transfer kinetics. The synergetic effect of such minimal growth platform thereby reducing the self-stacking nature of the MoS2
strain and defects were reported to activate the inert basal plane of MoS2 nanostructures. Upon keen observation of the heterostructures depicted
that indeed enhanced the number of active sites with a stable 2H phase in the figure, it is observed that MoS2 sheets were perpendicularly ori­
[25]. ented upon the surface of RGO which benefits in the exposure of large
The functional groups present in the prepared composites were number of edge sites.
analysed employing Fourier Transform Infrared Spectroscopy (FTIR) A closer examination of the enlarged pictures of the W3, W5, and W7
analysis. Fig. 3 demonstrates the FTIR spectra of MG, W3, W5 and W7 composites with MG suggests that the thickness of the MoS2 sheets was
composites wherein the characteristics absorption bands of both MoS2 significantly reduced with a threshold tungsten doping of 5 at% in W5,
and RGO were observed. As shown in Fig. 3, the broad band observed which does, in fact, lead to effective target gas diffusion and adsorption.
These results were in accordance with Raman analysis which signifies
the structure refinement capability of the tungsten dopants. Moreover,
the relative open space between the MoS2 nanosheets in W5 were larger
than that were in pristine and doped counterparts which further boost
up the effective circulation and intercalation of the gas analytes deeper
into the heterostructure. In case of MG, W3 and W7 nanohybrids, larger
aggregations were observed on the surface which hinders the enhanced
adsorption and desorption kinetics of the gas analytes. Hence, it could be
deduced from the aforementioned observations that with an optimal
incorporation of tungsten dopants (W5) into MoS2/RGO composites, the
inherent agglomeration of MoS2 were curtailed which led to the devel­
opment of well refined micro-spherical flower shaped structures with
thin pellets of MoS2 self-assembled over RGO surface that could promote
effective diffusion and adsorption of gas analytes.
X-ray photoelectron spectroscopy (XPS) was employed to examine
the chemical composition and detect the valence state of the elements
present in the prepared composites. Fig. 6a portrays full survey scan XPS
pattern of MG and W5 that indicates the coexistence of Mo, S, C, O and
W elements. As show in Fig. 5a, the high-resolution Mo 3d spectrum of
MG could be resolved into two characteristic peaks positioned at 228.85
eV and 232.47 eV that could be ascribed to Mo 3d5/2 and Mo 3d3/2 peaks
of Mo4+ in MoS2. The resolved peaks in the S 2p spectrum of MG located
Fig. 3. FTIR spectra of MG, W3, W5 and W7 composites. at 161.48 eV and 162.60 eV could be assigned to the S 2p3/2 and S 2p1/2

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 4. Low and high magnified FESEM images of (a,b) MG (c,d) W3 (e,f) W5 and (g,h) W7 heterostructures.

of S2− in MoS2 [32]. Moreover, the peak observed at 284.60 eV, 287.35 The as exhibited shift indicates the proliferation of the surface electron
eV & 289.30 eV in the C 1s spectrum of MG signifies the existence of density in MoS2/RGO heterostructure imparted by the successful doping
C=C, C=O, HO–C=O groups [33,34]. Here, the intense peak at 284.6 eV of tungsten dopants into the MoS2 lattice. Such a substantial increment
indicates the restoration of the sp2 carbon networks due to the reduction in the surface electron density by the tungsten dopants paves way for the
of graphene oxide to reduced graphene oxide. Meanwhile, the O 1s enrichment of active gas sensing sites with better adsorption and
spectrum of MG depicts three resolved peaks fitted at 530.43 eV, 531.60 desorption characteristics. Furthermore, the presence of tungsten dop­
eV & 532.91 eV as shown in Fig. 5d. The oxygen species adsorbed on the ants in W5 hybrid composite was further confirmed from the peaks
surface hydroxyls is indicated by the peak at 531.6 eV, whereas gra­ positioned at 32.55 eV, 34.65 eV & 34.65 eV which corresponds to W
phenic oxygens are represented by the other peaks [35,36]. The afore­ 4f7/2, W 4f5/2 and W 5p3/2 respectively as portrayed in Fig. 6f [37].
mentioned peak positions infer the successful formation of MoS2/RGO The inferences from the aforementioned analysis deduce that the
composite. MoS2/RGO composites have been electronically sensitized employing
Relative to the peak positions in the Mo 3d spectrum of MG, the Mo tungsten dopants which further resulted in proliferation of active edge
3d5/2 and Mo 3d3/2 peaks of W5 get shifted by 0.35 eV towards 228.50 sites which benefits the hybrid composites to exhibit superior gas
eV and 231.79 eV respectively. Moreover, the S 2p3/2 and S 2p1/2 peaks sensing traits.
of W5 deviates towards 160.99 eV and 161.89 eV respectively on
comparison with the corresponding peaks in the S 2p spectrum of MG.

6
S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 5. Core level XPS spectra of the (a) Mo 3d (b) S 2p (c) C 1s & (d) O 1s peaks of MG composite.

3.2. Ammonia gas sensing performance gas analytes.

As reflected form Fig. 8, W5 gas sensor reveals exceptional sensing
The charge transfer characteristics of the prepared gas sensors MG, performance to 50 ppm of ammonia at room temperature with a
W3, W5 and W7 at room temperature were evaluated from their I–V response value of 11.60 % which could be attributed from the synergetic
graph as illustrated in Fig. 7. The figure infers the establishment of effect of numerous exposed edge sites on the surface of the sensing
ohmic contact between nanocomposites and gold electrode with negli­ material and enhanced charge transfer characteristics across the MoS2/
gible contact resistance that have been signified from the linear increase RGO heterojunction. The lattice distortion triggered by the incorpora­
in the current with increase in voltage from -5 V to +5 V. As observed tion of tungsten atoms into MoS2 lattice results in surplus amount of
from Fig. 7, W5 nanocomposite exhibits enhanced electrical conduc­ edge terminated structure that possess highest d-orbital electron density
tivity relative to MG, W3 and W7 that manifest the establishment of full- for adsorption of gas analytes. Due to the smaller crystallite size of W5,
fledged conduction channels with the incorporation of 5 at.% of tung­ the W5 nanocomposites possess more grain boundaries with enormous
sten dopants into the host lattice. Among the prepared composites W5 catalytically active edge sites relative to MG, W3 and W7 nano­
possess larger magnitude of active exposed edge sites relative to other composites which is in accordance with the XRD and Raman analysis.
composites. According to previous reports, the tensile strain formed Moreover, W-5d electrons were reported to be highly active than Mo-4d
during the formation of edge sites significantly increases the supply of electrons due to which dopants sites could effectively trap large number
electrons to the edge sites, resulting in W5 having a higher current of oxygen species which indeed results in enhanced gas sensing char­
density than W7 and its pristine counterparts [38]. Such an augmented acteristics [40]. Hence, the incorporation of tungsten dopants into MoS2
charge transfer characteristics of W5 on comparison with its pristine and consequently produced the aforementioned effects, which improved the
doped counterpart aids in effective gas sensing traits. sensing response of W5 sensors towards ammonia gas molecules.
The relative response curves obtained for W3, W5 and W7 nano­ In addition to the elevated sensing response, W5 gas sensor also
composites after exposure to 50 ppm of ammonia gas at room temper­ portray an excellent response time and recovery time of 49 s and 65 s
ature is illustrated in Fig. 8. It is observed that the resistance of the respectively in 20 % RH as shown in Fig. 9 with complete recovery to the
composites decreases when exposed to ammonia gas, resembling the n- baseline. Such an exceptional traits could be ascribed to the large area
type nature of the prepared gas sensors. In parallel, the composite MG interlayer expanded flower shaped morphology composed of thin sheets
indicates no response to 50 ppm of ammonia at room temperature due to of MoS2 tailored by the tungsten dopants anchored on RGO which helps
limited number of adsorbed oxygen species. Besides, as the temperature in effective diffusion of the ammonia analytes. Furthermore, it was re­
is increased to 50 ◦ C, the MG composite exhibits a slight response as ported that molybdenum ions had a higher adsorption energy value than
illustrated in Fig. S1 that could be attributed to temperature triggered tungsten ions when it came to adsorption towards ammonia molecules
activation of the surface oxygen species with subsequent interaction [41]. Hence, the relative binding of ammonia gas analytes to molyb­
with ammonia gas analytes which results in variation in the depletion denum atoms would be higher than tungsten due to which the W5 sensor
layer [39]. Hence, it could be deduced from the above inference that the exhibit faster desorption characteristics. Furthermore, ameliorated
introduction of tungsten dopants into the MoS2 lattice lowered the conductivity of W5 gas sensor commenced by the threshold doping of
working temperature and enhanced the sensing response to ammonia tungsten dopants further paved way for faster adsorption/desorption of

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 6. (a) Full survey scan XPS spectra of MG and W5 composites. Core level XPS spectra of the (b) Mo 3d (c) S 2p (d) C 1s (e) O 1s & (f) W 4f peaks of W5 composite.

NH3 molecules. Hence, it could be easily deduced from the above stated
results that optimal doping of tungsten into the host lattice of W5
bolstered up the gas sensing traits and thereby all the further gas sensing
assessment is performed only for W5 gas sensor at room temperature
with 20 % RH.
Fig. 10a, b illustrates the dynamic response curves of W5 gas sensor
on exposure to lower and higher concentrations of ammonia from 1 ppm
to 10 ppm and 10 ppm–100 ppm at room temperature respectively. The
figure clearly depicts that response of the W5 sensor expands linearly for
both lower and higher concentration variations of ammonia gas mole­
cules that accounts to the flower shaped heterostructure wherein thin
sheets of MoS2 were vertically stacked on the surface of RGO which in
turn exposes surplus amount of edge sites and large surface area for the
adsorption of gas molecules. Additionally, the thin nature of MoS2 sheets
enhances W5 gas sensor’s electrical conductivity, which accelerates the
kinetics of adsorption and desorption [42,43]. Hence, as the concen­
tration of target gas increases, the response of W5 gas sensor gets
magnified without any saturation as observed from the figure. In addi­
tion, it is to be noted that W5 gas sensor could effectively sense con­
centration of ammonia gas analytes as low as 1 ppm that could be
ascribed to effective formation of enormous p-n heterojunctions at the
Fig. 7. I–V characteristics of MG, W3, W5 and W7 composites. interface of W doped MoS2 and RGO obtained through the in-situ

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

calculated using the formula, LOD = 3σ/s, where ‘σ’ correspond to

standard deviation whereas ‘s’ attributes to the slope calculated from the
response calibration graph as shown in Fig. S3 [46].
Selectivity plays a pivotal role for the utilization of gas sensors for
practical application especially for breath analysis since, the exhaled
breath consists of wide mixture of VOC’s. As a result, the cross sensitivity
of the W5 gas sensor was investigated by exposing it to a variety of
VOC’s at 1000 ppm concentrations, including ethanol, methanol,
formaldehyde, propanol, toluene, and xylene. As summarized in Fig. 11,
W5 gas sensor possess a 5-fold increment than its response to interfer­
ence gases whose concentrations were 20 times greater than the con­
centration of ammonia (50 ppm). Such a significant potential of W5
sensor to selectively sense ammonia gas analytes could be assigned to
the preferential interaction between functional groups such as hydroxy
groups that acts as the Bronsted acid sites on the surface of the W5 gas
sensor with the basic ammonia gas molecules. Besides this, the strong
electron donor ability of the ammonia gas further promotes the
adsorption affinity relative to most other cross interference gases [47,
48]. Hence, the synergetic effect of the aforementioned inference in
conjunction with enhanced adsorption brought by the tungsten doping
in W5 gas sensor aided in selective detection of ammonia gas molecules.
Fig. 8. Response of W3, W5 and W7 sensors to 50 ppm of ammonia at room For the employment of the gas sensor in field applications, the
temperature. repeatability of the sensor proves to be one of the figures of merit.
Hence, the repeatability of the W5 gas sensor was tested towards 50 ppm
of ammonia as illustrated in Fig. 12. The figure reveals that the W5
prototype gas sensor manifests stable response for 15 on/off cycles.
Hence, it could be inferred that combined effects of tungsten doping and
MoS2/RGO heterojunction results in excellent repeatability that further
adds up to the sensing traits of W5 gas sensor.
The relative humidity proves to be a prime figure of merit and
indispensable condition in real time application of gas sensor especially
for breath sensor application. So, in order to investigate the effect of
humidity on the ammonia sensing property of W5 gas sensor, W5 sensor
was exposed to 50 ppm of ammonia under a wide range of humidity
background from 20 % to 80 % at room temperature and their relative
response is illustrated in Fig. 13. As observed from Fig. S2, the baseline
resistance of W5 gas sensor get reduced from 63.70 MΩ to 7.46 MΩ as
the relative humidity varies from 20 % to 80 % RH. Furthermore, it is
clear that at relative humidity levels of 50 % and higher, a significant
shift in the resistance of the W5 nanohybrid was observed. Such a pro­
found shift in resistance could be ascribed to the wide coverage of water
molecules over the large surface area of W5 sensing material followed by
their ionization which ultimately results in the hopping of protons (H+)
over the surface of the material as illustrated in the schematic diagram
shown in Fig. 14 [49]. Briefly, the hydrophilic groups present over the
Fig. 9. Response time and Recovery time of W5 gas sensor to 50 ppm of surface of the W5 gas sensor as evident from the FTIR analysis such as
ammonia at room temperature. amino, amide, hydroxyl and carboxylic groups forms a network of
hydrogen bonds which results in physisorption of water molecules.
hydrothermal synthesis. Briefly, earlier research on the relationship When an external electric field is applied, the adsorbed water molecules
between heterojunctions and crystallite size highlights that a smaller split into H+ and OH− ions. Under low humidity level (below 50 % RH),
crystallite size leads to a higher number of bulk heterojunctions [44]. the as produced protons (H+) hope between neighbouring hydroxide
With an optimal doping of 5 at.% tungsten dopants, W5 gas sensor ions sites which results in smaller change in resistance. As the humidity
procured reduced crystallite size leading to the development of larger level get increased (above 50 % RH), a continuous water layer is formed
number of heterojunctions such that even a slight change initiated by over the surface of W5 gas sensor which dissociates into hydroxide and
adsorption of smaller concentration of gas molecules would drastically hydronium ion according to Eq. (2) and (3) [50]:
affect the thickness of the depletion layer [45]. Hence, W5 gas sensor
H2 O(ads) + H2 O(ads)⇌H3 O+
could effective sense even the lower trace of ammonia down to 1 ppm at
room temperature. Moreover, Fig. 10c, d ascertains that the W5 gas + OH − …………………………………………………. (2)
sensor yields an excellent correlation coefficient factor of 0.9966 and
0.9916 upon linear fitting of concentration vs response curve for lower NH3 (ads) + H2 O(ads)⇌NH4+
and higher concentration of ammonia gas molecules which discloses its + OH − ………………………………………………….. (3)
exceptional stability and reliability to be deployed as a breath sensor.
Furthermore, upon complete coverage of the surface of W5 gas
Besides, the smallest trace of an analyte that could be reliably detected
sensor with water molecules, the charge transfer occurs through the
with a given probability is expressed in terms of limit of detection (LOD)
exchange of proton between the as formed hydronium ion and adjacent
that was measured to be 1.32 ppm for W5 composite which was
H2O molecule which in turn produces another hydronium ion that

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 10. Transient response curve of W5 gas sensor exposed to (a) lower concentration (1–10 ppm) (b) higher concentration (10–100 ppm) of ammonia gas and their
corresponding linear fit (c,d) respectively.

Fig. 11. Selectivity of W5 gas sensor to various VOC’s at room temperature.

further reacts with neighbouring water molecule. As a result, under high Fig. 12. Repeatability of W5 gas sensor to 50 ppm of ammonia at room
humidity conditions, a continuous channel of conductive protons temperature.
mediated by H3O+ was formed, which led to a significant decrease in the
resistance of the W5 gas sensor. These results confirm the Grotthuss inhibits its diffusion deeper into the material. Hence, W5 composite
mechanism and were consistent with previous reports on humidity exhibits a higher response at 70 % RH beyond which it gets reduced
enhanced gas sensing [51,52]. The extremely humid conditions that led [56].
to the higher conductivity of the W5 gas sensor accelerates the adsorp­
tion rate of oxygen species. Furthermore, the activation of more OH− NH3 + H2 O ↔ NH4+
adions on the surface of the W5 gas sensor was reported to be boosted by + OH − ………………………………………………………………. (4)
the defects caused by the threshold doping of tungsten dopants in the
MoS2 lattice [53,54]. During the exposure of target gas analytes, the NH4+ + O−2 → NO + H2 O
co-adsorbed water molecules on the surface of the W5 gas sensor sol­ + e− …………………………………………………………….. (5)
vates ammonia gas molecules into a monovalent ion (NH+ 4 ) that were
reported to be highly reactive to the surface adsorbed oxygen species Hence, the synergetic effect of proton hopping and solvation of
according to Eq. (4) and (5) [55]: However, at 80 % RH, a large amount ammonia in an extreme humidity background of 70 % aided W5 gas
of water molecules gets adsorbed onto the surface of W5 composite sensor to be a potential room temperature ammonia sensor that exhibits
which further prevents the adsorption of ammonia molecules and a response of 42.30 %–50 ppm ammonia which was a 3.7-fold increment

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Fig. 13. Comparative response of W5 gas sensor to 50 ppm of ammonia at

different relative humidity conditions. Fig. 15. Transient response of W5 gas sensor to different concentration of
ammonia gas at 70 % RH.
over the corresponding response at 20 % RH. Additionally, as shown in
Fig. 15, transient responses of the W5 gas sensor were recorded under relatable response with our work, a humidity activated gas sensor based
70 % relative humidity for lower and higher concentration variations of on W doped MoS2/RGO were not reported to our knowledge. Notably,
ammonia from 1 ppm to 9 ppm and 10 ppm–50 ppm, respectively, in the W5 gas sensor performs better than the majority of other prototype
order to further assess the performance and reliability of the sensor at sensors, covering a broad range of materials like composites, organic
70 % RH. The figure ascertains that the adsorption of ammonia mole­ molecules, polymers, etc. Subsequently, the incorporation of tungsten
cules onto the surface of W5 gas sensors were greatly fostered by the dopants into MoS2 lattice composited with RGO proves to be a better
humid environment with a practical least detection limit of 1 ppm. Be­ platform for the development of ultra-selective and sensitive ammonia
sides, an excellent correlation factor of 0.9938 (lower concentration) gas sensors which could enhance its performance in intense humid
and 0.9992 (higher concentration) were obtained for the linear fitting of environment where majority of the top-notch sensors shows degraded
the concentration vs response curves as shown in Fig. 16a,b which sig­ performance.
nifies the reliability of W5 gas sensor to be deployed in extreme humid On the other hand, as reported in our previous work, Zn doped
conditions. Based on the above analysis, it could be inferred that hu­ MoS2/RGO gas sensor exhibited a relatively higher response of 32.40 %
midity played a pivotal role in the enhancement of the ammonia sensing towards 50 ppm of ammonia at 200 ◦ C along with response and recovery
characteristics of W5 gas sensor that renders a unique capability for the time of 21.30 s and 44.90 s respectively [27]. Hence, Zn doped
utilization of W5 sensors under intense humid application such as breath MoS2/RGO sensor requires additional provision such as microheaters
sensor. along with its sensing element which adds up to the cost of operation
A comparative analysis was performed to investigate the relative and also possess a threat during the detection of volatile and flammable
performance of W5 gas sensor with previously reported humidity gases due to the higher temperature. Moreover, according to the pre­
enhanced ammonia sensor prototypes that are summarized in Table .1. vious reports on high temperature gas sensors, the continuous operation
When the humidity was increased, most of the reported ammonia sen­ at elevated temperature could also lead to contact degradation and
sors functioning at room temperature exhibited sluggish response even sluggish adhesion properties which in turn degrades the selectivity and
at higher concentrations. Even though sporadic reports reflected a stability [57]. Additionally, when the gas sensing prototype is exposed

Fig. 14. Schematic representation of the proton hopping mechanism in the W5 gas sensor under extreme relative humidity.

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

to a humid atmosphere, water molecules are adsorbed on the active temperature, the oxygen molecules get chemisorbed on the surface as
sites, obstructing the target ammonia molecules’ ability to adsorb O−2 according to Eq. (6):

O2 (air) + e− →O−2 …………………………………………………………………………… (6)

effectively. Thus, in the presence of a humid atmosphere, zinc doped With the optimal dopant concentration of tungsten dopants in W5
MoS2/RGO showed poor sensing traits to ammonia. nanohybrid, surplus amount of exposed active edge sites gets enhanced
On contrary, W doped MoS2/RGO (W5) exhibits a 42-fold increment in conjunction with reduced crystallite size. The pronounced catalytic
in response with a response percentage of 42.30 % when the humidity activity of tungsten dopants and higher electron density of edge sites in
increased from 30 % to 70 % along with 50 ppm of ammonia. Moreover, W5 gas sensor aided in effective anchoring of large amount of chem­
the as prepared W5 sensor possess a substantial ability to selectively isorbed oxygen species relative to the MG, W3 and W7 which were in
sense ammonia from among a group of gases at room temperature. accordance with XRD, Raman and XPS analysis. Consequently, upon the
Furthermore, since they operate at room temperature, it would be exposure of W5 gas sensor to target gas analytes, the ammonia gas
simple to interface them as a wearable gas sensing system. Hence, the molecules due to its reducing nature react with the adsorbed oxygen
synergetic effect of humidity enhanced response & room temperature species O−2 followed by the release of the trapped electron to the con­
operation combined with high selectivity in W5 gas sensor equipped it duction band of W5 gas sensor thereby reducing the electrical resistance
with a potential to be employed in top notch gas sensor application such as shown in Eq. (7). The magnitude of the response displayed by the W5
as breath analysis. Hence, the as prepared W5 sensor transpires to be gas sensor is indicated by the change in resistance caused by the
reliable and robust room temperature ammonia sensor with humidity ammonia gas reaction. Besides, upon exposure to humid atmosphere,
enhanced outfits to be employed in lab to fab translation for breathomics the functional groups present over the surface of the W5 composite
and environmental applications. forms hydrogen bonds leading to physisorption of water molecules that
get ionized into H+ and OH− ions under the supply of the external
electric field. When the relative humidity is low (below 50 % RH), the
3.3. Proposed ammonia sensing mechanism protons (H+) that are created hop between nearby hydroxide ion sites,
causing a smaller change in resistance. However, a continuous water
The gas sensing characteristics of a chemiresistive gas sensors pri­ layer forms over the surface of the W5 gas sensor when the humidity
marily relies on the diffusion, adsorption and desorption kinetics of the level rises (over 50 % RH) which eventually breaks down into hydroxide
gas analytes with the surface of the sensing material which governs the and hydronium ions after which protons are exchanged with adjacent
nature of the change in electrical resistance of the sensor. Hence, based H3O+ ions. Hence, the resistance of the W5 composites get reduced to a
upon the changes attributed by the adsorption and desorption of target larger extent which drastically enhances the rate of adsorption of the
gas molecules in the heterojunction and surface depletion layers of oxygen species. In addition, higher magnitude of defects eventuated
tungsten doped MoS2/RGO nanohybrid, a plausible mechanism for W5 from the threshold doping in W5 further increases the activation of OH−
gas sensor has been proposed. In general, upon the exposure of W5 gas adions. Upon exposure of W5 composite with ammonia gas molecules
sensors to the ambient air, the oxygen molecules present in the air get under such dense humid atmosphere, solvation of ammonia gas mole­
adsorbed on the active exposed surface layers where they serve as cules takes places which reacts readily with the adsorbed oxygen spe­
electron acceptors. These adions on the surface captures the electrons cies. Hence, the electrons captured during the adsorption of oxygen
from the conduction band of W5 gas sensor to become ionized chem­ species were released to the conduction band of W5 composite upon its
isorbed oxygen species that results in increased electrical resistance. reaction with solvated ammonia ions due to which W5 composite ex­
Also, the temperature of the surface layers has a major impact on the hibits higher magnitude of response at extreme humid conditions.
type of oxygen species present. Since, W5 gas sensor operates at room

4NH3 + 5O−2 → 4NO + 6H2 O + 5e− ……………………………………………………… (7)

Fig. 16. Linear fitting of the response vs concentration of W5 gas sensor for (a) low concentration, (b) higher concentration of ammonia gas at 70 % back­
ground humidity.

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

Table 1
Comparison of the previous reported ammonia sensors with the current work.
S. Sensor Material Ammonia Concentration Response Temperature Selectivity Tres/Trec Relative Humidity Reference
No (ppm) (S) (◦ C) (%)

1 Ti3C2Tx MXene/SnO 200 2.8e RT Moderate 61 s/119 s 33 [58]

2 rGO/NiO 100 4.14e RT Moderate 290 s/166 – [59]
s
3 Napthelene Diimide 50 27.7e RT High 200 s/350 90 [60]
s
4 WO3 100 3.32a 350 Low 150 s/210 – [61]
s
b
5 WS2/TiO2 QD 250 43.72 RT High -/174 s 30 [62]
6 SnO2 QDs @ MoS2 100 8.6e RT Moderate 6 s/121 s – [63]
7 SnO2/RGO 100 5.16e RT Moderate 94 s/57 s – [64]
8 rGO/Co3O4 20 1.78e RT Not tested 351 s/ 55 [65]
1199 s
9 Poly-L-aspartic acid (PAA) and L- 50 9.2c RT High – 80 [66]
glutamic acid (GA)
e
10 NiO/ZnO 50 23 RT Moderate 27 s/150 s 40 [67]
11 AuNP/V2O5/CuWO4 5 2.7d 150 Not Tested 35 s/33 s – [68]
12 PANI/MoS2/SnO2 100 10.9d RT Moderate 21 s/130 s 20 [69]
13 PANI/Ti3C2Tx 50 5e RT Moderate 200 s/600 40 [70]
s
14 PANI/TiO2 100 5.4e RT Low 100 s/232 – [71]
s
e
15 W@MoS2/RGO 50 42.30 RT High 49 s/65 s 70 This Work
a
S=Rair/Rgas.
b
S=(Ia-Ig)/Ia × 100.
c
S = Za/Zg.
d
S=Rg/Ra.
e
S=(Ra-Rg)/Rg × 100.

Fig. 17. Energy band diagrams of W5 gas sensor (a) before the formation of heterojunction, (b) heterojunction exposed to air & (c) heterojunction exposed
to ammonia.

and RGO, RGO possess higher work function than MoS2 [74]. Hence,
The alteration within the p-n heterojunction before and after the during the formation of the W doped MoS2/RGO heterojunction, elec­
exposure of target gas was taken into account to acquire an in-depth trons flow from MoS2 to RGO and holes flows in the opposite direction
profile of the enhanced sensing performance of W5 gas sensor. Fig. 17 until the fermi levels of W doped MoS2 and RGO gets aligned. Due to the
depicts the schematic illustration of the energy band diagram of W5 gas exchange of the charge carriers, a change in carrier concentration across
sensor before and after exposure to ammonia gas molecules. As observed the junction has been observed which results in the generation of
from the XRD, Raman and XPS analysis of W5 nanohybrid, the incor­ depletion layer at the interface of p-n junction accompanied by a band
poration of W atoms with higher atomic radii and larger electronega­ bending as shown in Fig. 17. The potential charge barrier created at the
tivity into the MoS2 lattice generated enhanced strain coupled with interface inhibits further movement of charge carriers across the junc­
lattice distortion at a larger magnitude. Such doping induced strain were tion. Upon the disclosure of the W5 gas sensor to air, oxygen molecules
reported to introduce additional energy states closer to the fermi level capture electrons and get adsorbed as O−2 on the surface of the W5 gas
[72,73]. Hence, in the prepared composite W doped MoS2 reveals n-type sensors which results in reduced number of charge carrier that further
semiconductor behaviour with electron as the principal charge carrier causes widening of the depletion layer. After the exposure of ammonia,
while RGO exhibits p-type nature with holes as its majority charge the trapped electrons are released back conduction band of W doped
carrier. According to the previous reports on the work function of MoS2 MoS2 which consumes the holes in RGO. Thus, an increase in electrons

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S.P. Linto Sibi et al. Analytica Chimica Acta 1287 (2024) 342075

leads to a decrease in the depletion layer’s width, which lowers the W5 the work reported in this paper.
gas sensor’s resistance. It is noteworthy that RGO paved as a conductive
platform for the growth of W doped MoS2 with surplus number of Data availability
effective heterojunctions and played a secondary role that enabled the
room temperature sensing of ammonia. In addition, the interlayer Data will be made available on request.
expanded flower shaped morphology of W5 nanohybrids with vertically
oriented MoS2 sheets exposed significant amount of edge site and pro­ Appendix A. Supplementary data
vided large area for the diffusion and adsorption of ammonia gas mol­
ecules. Besides, the lattice distortions eventuated from optimal doping of Supplementary data to this article can be found online at https://doi.
W into the host lattice resulted in the formation of smaller domains org/10.1016/j.aca.2023.342075.
within the basal plane which produced large number of exposed edge
sites. Moreover, the reduced stacking and thin nature of MoS2 sheets in References
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