chemosensors

Review
Metal Oxide Semiconductor Nanostructure Gas Sensors with
Different Morphologies
Ali Mirzaei 1 , Hamid Reza Ansari 2 , Mehrdad Shahbaz 3 , Jin-Young Kim 4 , Hyoun Woo Kim 5,6
and Sang Sub Kim 4, *

1 Department of Materials Science and Engineering, Shiraz University of Technology, Shiraz 71557-13876, Iran;
mirzaei@[Link]
2 Department of Electrical and Electronics Engineering, Shiraz University of Technology,
Shiraz 71557-13876, Iran; [Link]@[Link]
3 Department of Materials Science and Engineering, Urmia University, Urmia 5766-151818, Iran;
[Link]@[Link]
4 Department of Materials Science and Engineering, Inha University, Incheon 22212, Korea; piadote@[Link]
5 Division of Materials Science and Engineering, Hanyang University, Seoul 04763, Korea;
hyounwoo@[Link]
6 The Research Institute of Industrial Science, Hanyang University, Seoul 04763, Korea
* Correspondence: sangsub@[Link]

Abstract: There is an increasing need for the development of low-cost and highly sensitive gas sensors
for environmental, commercial, and industrial applications in various areas, such as hazardous gas
monitoring, safety, and emission control in combustion processes. Considering this, resistive-based
gas sensors using metal oxide semiconductors (MOSs) have gained special attention owing to their
high sensing performance, high stability, and low cost of synthesis and fabrication. The relatively low
final costs of these gas sensors allow their commercialization; consequently, they are widely used
and available at low prices. This review focuses on the important MOSs with different morphologies,
Citation: Mirzaei, A.; Ansari, H.R.; including quantum dots, nanowires, nanofibers, nanotubes, hierarchical nanostructures, and other
Shahbaz, M.; Kim, J.-Y.; Kim, H.W.; structures for the fabrication of resistive gas sensors.
Kim, S.S. Metal Oxide Semiconductor
Nanostructure Gas Sensors with Keywords: semiconductor; metal oxide; morphology; gas sensor; sensing mechanism
Different Morphologies. Chemosensors
2022, 10, 289. [Link]
10.3390/chemosensors10070289

Academic Editors: Joana Rodrigues 1. Introduction

and Nuno Santos Although industrial modernization facilitates social, cultural, and economic devel-
Received: 8 June 2022
opment globally, it results in the consumption of enormous amounts of energy every day.
Accepted: 18 July 2022
Consequently, the toxic gas and vapor emissions released into the atmosphere cause air
Published: 21 July 2022
pollution, which has been identified as a major concern in most countries. Air pollution
adversely affects humans, animals, vegetation, and materials [1]. Air pollution is mainly
Publisher’s Note: MDPI stays neutral
caused by the presence of NO2 , SO2 , CO, and O3 gases, along with volatile organic com-
with regard to jurisdictional claims in
pounds (VOCs), lead, and particulate matter (PM2.5 and PM10 ) in the air [2–4]. Air pollution,
published maps and institutional affil-
owing to its fluidity and diffusion, has a more adverse impact on human behavior and
iations.
economic growth than soil and river pollution [4]. About 12% of deaths in 2019 were
related to air pollution. In addition, it has been reported that air pollution was responsible
for approximately 20% of deaths from cardiovascular diseases [5]. Globally, air pollution
Copyright: © 2022 by the authors.
is the fourth-highest cause of mortality [6]. For example, the World Health Organization
Licensee MDPI, Basel, Switzerland. (WHO) reports that approximately 200,000 people die every year from air pollution in
This article is an open access article Bangladesh [7]. According to a WHO report, 92% of the global population lives in cities
distributed under the terms and with air pollution exceeding the WHO limits, indicating the need for further monitoring
conditions of the Creative Commons and control of air pollutant gases and vapors [8].
Attribution (CC BY) license (https:// Toxic gases are harmful to human bodies whether at low (chronic exposure) or high
[Link]/licenses/by/ (acute exposure) concentrations. The threshold limit value (TLV) is reported as the maxi-
4.0/). mum concentration of gas exposure permitted for 8 h without serious health effects. The

Chemosensors 2022, 10, 289. [Link] [Link]

Chemosensors 2022, 10, x FOR PEER REVIEW 2 of 23

Chemosensors 2022, 10, 289 Toxic gases are harmful to human bodies whether at low (chronic exposure) or high 2 of 23
(acute exposure) concentrations. The threshold limit value (TLV) is reported as the
maximum concentration of gas exposure permitted for 8 h without serious health effects.
The
TLVsTLVs for CO,
for CO, H2 S, H 2S, NO
and and2 NO are10,
are 250, 50,and
10,3and
ppm, 3 ppm, respectively,
respectively, indicating
indicating the highthe high
toxicity
toxicity of these gases [9]. Thus, the development of sensitive sensors for detecting
of these gases [9]. Thus, the development of sensitive sensors for detecting these toxic gases these
toxic gases is vital.
is vital.
The
Thehuman
humanolfactory
olfactorysystem
systemisisvery
verysensitive
sensitiveandand complex,
complex,andand comprises
comprisesseveral
several
million
millionolfactory
olfactoryreceptor
receptorcells
cellsthat
thatcontain
containnearly
nearly900
900olfactory
olfactoryreceptor
receptorgenes
genes(Figure
(Figure1).1).
Thus,
Thus,ititcan
canalmost
almostinstantaneously
instantaneouslydetect detecteven
evenextremely
extremelylowlowconcentrations
concentrationsof ofodorant
odorant
molecules.
[Link]
detect11inin2.5
2.5billion
billionparts
partsofofthe
theair
aircontaining
containingethyl
ethylmercaptan,
mercaptan,usually
usually
added as an odorant to natural gas
added as an odorant to natural gas [10]. [10].

Figure
Figure 1.1. Schematic
Schematicofofthe
thehuman
humanolfactory
olfactorysystem.
[Link]
Reprintedwith
withpermission
permissionfrom
fromRef.
Ref.[11].
[11].
Copyright
Copyright2018,
2018,MDPI.
MDPI.

However,
However,some sometoxictoxicgases—such
gases—suchas asCO—lack
CO—lackodor. [Link],
Moreover,some somegases gasesatatvery
very
low
lowconcentrations
concentrationscannot cannotbe bedetected
detectedby bythe thehuman
humanolfactory
olfactorysystem.
[Link] Toprecisely
preciselydetect
detect
dangerous
dangerousgases gasesand andvapors,
vapors,sensitive
sensitiveand andhigh-performance
high-performancegas gassensors
sensorswith withthetheability
ability
to
to detect
detect lowlow amounts
amounts of of gases
gases with
with aa fast
fast response
response are are necessary. Furthermore,
Furthermore, such such
sensors
sensorsshould
shouldbe be highly
highly stable
stable and
and cost-effective.
cost-effective. Considering
Consideringthis, this,gasgassensors
sensorsusingusing
different
differentsensing
sensingmaterials
materialsand andworking
workingprinciples
principleshave have been
been introduced.
introduced. Even Eventhough
though
chromatography techniques can
chromatography canbe beused
usedforfor thethe
detection
detectionof gases, the equipment
of gases, the equipment is heavy,is
expensive,
heavy, and needs
expensive, and aneeds
skilled operator.
a skilled Thus, gas
operator. Thus,sensors are theare
gas sensors preferred devicesde-
the preferred for
gas-sensing
vices applications.
for gas-sensing applications.
Among
Among all all gas sensors,
sensors, resistive-based
resistive-basedgas gassensors
sensorscomprising
comprisingmetal metal oxide
oxidesemicon-
semi-
ductors (MOSs) meet almost all criteria for a good gas sensor,
conductors (MOSs) meet almost all criteria for a good gas sensor, although their selec- although their selectivity and
sensing temperatures need to be optimized. MOS sensors
tivity and sensing temperatures need to be optimized. MOS sensors are very popular and are very popular and widely
used inused
widely different areas toareas
in different detect up to 150
to detect up todifferent types of
150 different gases
types of and
gases vapors, including
and vapors, in-
oxidizing
cluding and reducing
oxidizing gases [12].
and reducing Bardeen
gases and Brattain
[12]. Bardeen were thewere
and Brattain first scientists to report
the first scientists
gas-sensitive
to effects on effects
report gas-sensitive germanium in 1952 [13].inTwo
on germanium 1952years
[13].later,
Twoinyears
1954,later,
Heiland notedHei-
in 1954, that
the change in the partial pressure of oxygen is influenced by the
land noted that the change in the partial pressure of oxygen is influenced by the semi- semiconducting properties
of ZnO [14].
conducting After one
properties ofdecade,
ZnO [14]. in After
1962, oneSeiyamadecade,et in
al. 1962,
[15] reported
Seiyama the et [Link]
[15]gas sensor
reported
based on ZnO, in which the adsorption and desorption of
the first gas sensor based on ZnO, in which the adsorption and desorption of gases gases changed its conductivity.
In 1967, Shaver
changed used Pt and
its conductivity. other Shaver
In 1967, noble metals
used Pt asand
dopants
otherinnoble
WO3metals
for theas first time [16].
dopants in
Several years later, Taguchi used SnO 2 as the first commercial sensor
WO3 for the first time [16]. Several years later, Taguchi used SnO2 as the first commercial [17]. Since then, many
gas sensors
sensor [17]. using
Since different
then, many materials with various
gas sensors morphologies
using different have with
materials been various
[Link]-
Different MOSs
phologies have been reported. can be employed to produce gas sensors. However, a large band gap
(Eg ) Different
along with a low activation energy of the centers is suitable
MOSs can be employed to produce gas sensors. However, a large band gap for use in MOS-based gas
sensors. Generally, for room-temperature gas sensors, a low-band
(Eg) along with a low activation energy of the centers is suitable for use in MOS-based gas gas is advantageous [18].
Other properties of a good MOS are high stability as well as the high mobility of the charge
carriers [19].
 Chemosensors 2022, 10, x FOR PEER REVIEW 3 of 23

Chemosensors 2022, 10, 289 3 of 23

sensors. Generally, for room-temperature gas sensors, a low-band gas is advantageous
[18]. Other properties of a good MOS are high stability as well as the high mobility of the
charge carriers [19].
Figure
Figure22schematically
schematicallyindicates
indicatesaaschematic
schematicof ofaagas-sensing
gas-sensingdevice
device[20].
[20].MOS-based
MOS-based
gas
gassensors
sensorsare aregenerally
generallydeposited
depositedas asthick
thickor orthin
thinfilms
filmson oninsulating
insulatingsubstrates
substrates(flat
(flator or
tubular),
tubular),such
suchas asSiO
SiO22or
orAlAl22OO33, equipped withwith interdigitated
interdigitated electrodes
electrodes (e.g.,
(e.g.,Au,
Au,Pt,Pt,and
and
Ag/Pd)
Ag/Pd) to readread out
out the
the sensor
sensor resistance.
resistance. Electrodes
Electrodes cancan be
be deposited
deposited on on the
thesubstrate
substrate
before
before and after depositing the sensing film. This provides significant flexibility in
and after depositing the sensing film. This provides significant flexibility in the
the
fabrication process because of the compatibility with the sensing material.
fabrication process because of the compatibility with the sensing material. Generally, in- Generally,
interdigitated electrodesare
terdigitated electrodes areused
usedto toread
read the
the sensor
sensor resistance,
resistance, and
and their
their length
length and
and gapgap
size
sizecan
canaffect
affectthe
thegas
gasresponse.
[Link] Anexcellent
excellentdiscussion
discussionon onthe
theinfluence
influenceof ofthe
theelectrode
electrode
parameters
parameterson onthe
thegas
gasresponse
response can bebe
can found
found in the study
in the by Korotcenkov
study by Korotcenkov [21].[21].
In addition,
In addi-
an integrated heater or external heater is employed to enable the sensor
tion, an integrated heater or external heater is employed to enable the sensor temperature temperature to
reach the final value. Generally, the sensing temperature of MOS-based
to reach the final value. Generally, the sensing temperature of MOS-based gas sensors is gas sensors is high,
and it is
high, often
and it isnecessary to heattothe
often necessary sensor
heat to the required
the sensor temperatures.
to the required temperatures.

[Link]
Figure Schematicillustration
illustration
of of
an an MOS-based
MOS-based gas gas sensor,
sensor, showing
showing the sensing
the sensing material,
material, elec-
electrodes,
trodes, and heater. Reprinted with permission from Ref. [20]. Copyright 2020, MDPI.
and heater. Reprinted with permission from Ref. [20]. Copyright 2020, MDPI.

Gas-sensing
Gas-sensingmeasurement
measurement systems are are
systems categorized
categorized intointo
twotwotypes: dynamic
types: dynamic andandstatic. In
static.
both cases, the system requires gas valves and gas flow controllers to inject
In both cases, the system requires gas valves and gas flow controllers to inject the target gas the target gas
intothe
into thechamber.
chamber. InIn addition,
addition, a system
a system for controlling
for controlling the sensing
the sensing temperature
temperature is re-
is required,
quired,
and and the
the output output
signal signal is continuously
is continuously recorded usingrecorded using aIn
a computer. computer.
a dynamic Insystem,
a dynamicthe
system,gas
desired theconcentrations
desired gas concentrations
are continuously are introduced
continuously introduced
to the gas chamberto the gas chamber
through tubes,
through
and tubes, and
the resistance ofthe
theresistance
sensor in an of the sensorgas
air target in an air target at
atmosphere gas atmosphere
various at various
temperatures is
temperatures is registered. In a static system, the target gas is introduced
registered. In a static system, the target gas is introduced into the chamber and evaporated into the cham-
ber and
upon evaporated
contact with theupon
[Link] withsize
The exact theofheater.
the gasThe exact should
chamber size ofbe the gas chamber
defined. Upon
should be defined.
stabilization Upon resistance,
of the sensor stabilization theofgas
thechamber
sensor resistance,
door or outletthe gas chamber
is opened, and door
freshor
outlet
air is opened,into
is introduced andthefresh air is introduced
chamber [9]. into the chamber [9].
To date, different MOSs have been used for sensing studies. They are either n-type
or p-type MOSs. In most cases, the n-type MOS is preferred, because most of the n-type
MOSs are thermally stable and can function at low oxygen partial pressures. Furthermore,
the resistance of n-type oxides decreases upon exposure to reducing gases, contributing to
facile compatibility with the measurement systems [18]. According to Kim et al. [22], SnO2
 To date, different MOSs have been used for sensing studies. They are either n-type
or p-type MOSs. In most cases, the n-type MOS is preferred, because most of the n-type
Chemosensors 2022, 10, 289 MOSs are thermally stable and can function at low oxygen partial pressures. Further- 4 of 23
more, the resistance of n-type oxides decreases upon exposure to reducing gases, con-
tributing to facile compatibility with the measurement systems [18]. According to Kim et
al. [22], SnO2 is the most popular MOS for gas-sensing applications, and ZnO is the sec-
is the most popular MOS for gas-sensing applications, and ZnO is the second-most-used
ond-most-used MOS for sensing studies.
MOS for sensing studies.
It is well accepted that the variation of the resistance in the presence of the target gas
It is well accepted that the variation of the resistance in the presence of the target gas
is the basic mechanism of gas detection by resistive gas sensors. A schematic of the
is the basic mechanism of gas detection by resistive gas sensors. A schematic of the sensing
sensing
mechanism mechanism
for n- and forp-type
n- andMOSp-type MOS in
sensors sensors in the presence
the presence of an oxidizing
of an oxidizing gas is showngas isin
shown
Figure 3. Because of the high electronegativity of oxygen and the extraction of electrons of
in Figure 3. Because of the high electronegativity of oxygen and the extraction by
electrons by oxygen
oxygen species on thespecies
surfaceon of
thethe
surface of the gas
gas sensor, sensor, an
an electron electronlayer
depletion depletion layeron
is formed is
formed on the
the surface surfacegas
of n-type of sensors,
n-type gasandsensors, and a hole accumulation
a hole accumulation layer is formed layer
on is
theformed
surfaceon of
the surface of p-type gas sensors, as shown in Figure 3a,c, respectively.
p-type gas sensors, as shown in Figure 3a,c, respectively. When an n-type sensor is exposed When an n-type
sensor is exposed
to an oxidizing to electrons
gas, an oxidizing gas, electrons
are further extracted,are further
leading extracted, leading
to an increase to an
in the in-
width
crease in the width of the electron depletion layer and an increase in the
of the electron depletion layer and an increase in the sensor resistance (Figure 3b). In a sensor resistance
(Figure
reducing 3b).
gasInatmosphere,
a reducing the gaswidth
atmosphere, the width
of the electron of the layer
depletion electron depletion
decreases, layer de-
resulting in a
creases,
decreaseresulting in a decrease
in the sensor [Link] Upon
the sensor resistance.
exposing p-type Upon
MOS gas exposing
sensors p-type
to an MOS gas
oxidizing
sensors
gas, more to an oxidizing
electrons are gas, more electrons
extracted, resulting in arethe
extracted,
expansionresulting in the
of the hole expansion oflayer
accumulation the
hole accumulation layer and a decrease in the sensor resistance (Figure 3d).
and a decrease in the sensor resistance (Figure 3d). For reducing gases, the inverse is true, For reducing
gases,
and the the inverse isincreases.
resistance true, and the resistance increases.

Figure 3.
Figure The general
3. The general gas-sensing
gas-sensingmechanism
mechanismofof(a,b)
(a,b)n-type
n-typeand
and(c,d) p-type
(c,d) MOS
p-type gasgas
MOS sensors in the
sensors in
presence
the of air
presence of and an oxidizing
air and [Link].
an oxidizing

In resistive-based gas sensors, morphology plays a vital role in the response of the gas
sensor. As gas molecules are adsorbed on the surface of the sensing layer, the resistance
changes, and this modulation of the resistance contributes to the appearance of a sensing
signal. Accordingly, a higher surface area provides more adsorption sites for incoming gas
molecules, leading to the enhancement of the gas response. In recent years, many attempts
have been made to develop sensing materials with a high surface area, such as nanowires
 In resistive-based gas sensors, morphology plays a vital role in the response of th
gas sensor. As gas molecules are adsorbed on the surface of the sensing layer, the r
sistance changes, and this modulation of the resistance contributes to the appearance of
Chemosensors 2022, 10, 289 5 of 23
sensing signal. Accordingly, a higher surface area provides more adsorption sites fo
incoming gas molecules, leading to the enhancement of the gas response. In recent year
many attempts have been made to develop sensing materials with a high surface are
and [Link] asreview
This nanowires and focuses
mainly nanofibers. Thismost
on the review mainly
widely focuses
used on the most
morphologies andwidely use
structures for morphologies and structuresInfor
gas-sensing applications. thegas-sensing
following applications.
sections, theInmain
the following
features ofsections, th
MOS-based gasmain features
sensors of MOS-based
are discussed gas sensors are discussed in detail.
in detail.

2. [Link]
MOS-Based Gas Sensors
Sensors with with
Different Different Morphologies
Morphologies
2.1. Quantum-Dot-Based Gas Sensors Using
2.1. Quantum-Dot-Based MOSs Using MOSs
Gas Sensors
Morphology engineering
Morphology isengineering
an important is anapproach
importantfor enhancing
approach for the gas-sensing
enhancing the gas-sensin
features of MOS-based
features of gas sensors, and
MOS-based gas MOS
sensors, materials
and MOS with different
materials with morphologies have
different morphologies hav
been explored been explored forpurposes.
for gas-sensing gas-sensing Thepurposes.
main goal Theofmain
using goal
novelof using novel morphologies
morphologies for fo
sensing studies sensing studies isthe
is to increase to increase
surface the area. surface
The area.
largerThethelarger
surface the area,
surfacethearea, the greater th
greater
the availabilityavailability
of adsorption of adsorption sites, resulting
sites, resulting in the adsorption
in the adsorption of moreofgas more gas molecules
molecules on on th
surface of the gas sensor, along with the appearance
the surface of the gas sensor, along with the appearance of a higher sensing signal. For of a higher sensing signal. Fo
sensing studies, zero-, one-, two-, and three-dimensional
sensing studies, zero-, one-, two-, and three-dimensional morphologies have been explored. morphologies have been e
plored. Quantum dots (QDs) are zero-dimensional
Quantum dots (QDs) are zero-dimensional (0D) semiconductor nanoparticles, where the (0D) semiconductor nanoparticle
motion of chargewhere the motion
carriers of charge
is confined carriers
in all is confined in
three directions. all three
Thus, directions.
the energy Thus, the energ
difference
difference between energy bands changes depending
between energy bands changes depending on the size of the particle, and it is possible on the size of the particle,
to and it
tune the band gap of QDs by changing their size. Accordingly, the electrical properties of electric
possible to tune the band gap of QDs by changing their size. Accordingly, the
propertiesbyofcontrolling
QDs can be engineered QDs can bethe engineered
dot size [23].by controlling
Owing to the the extremely
dot size [23]. Owing
small size to the ex
of QDs, when the QDs are exposed to air, they are depleted of electrons, and subsequent of ele
tremely small size of QDs, when the QDs are exposed to air, they are depleted
exposure to thetrons,
targetand
gas subsequent exposure
leads to extensive to the target
modulation gaselectrical
of the leads to resistance,
extensive modulation
leading of th
electrical resistance, leading to a high sensing signal.
to a high sensing signal. In addition, owing to their large resistance variation and good In addition, owing to their large r
sistance variation and good electrical properties, most QD-based gas sensors can work
electrical properties, most QD-based gas sensors can work at low temperatures. In [24],
low temperatures. In [24], different approaches to synthesized SnO2 QDs are reviewe
different approaches to synthesized SnO2 QDs are reviewed. Recently, QDs have been
Recently, QDs have been widely used for sensing studies [25,26]. For example, Zhu et a
widely used for sensing studies [25,26]. For example, Zhu et al. [27] used SnO2 QDs with
[27] used SnO2 QDs with a size of 5–10 nm for ethanol sensing at 200 °C at a fixed relativ
a size of 5–10 nm for ethanol sensing at 200 ◦ C at a fixed relative humidity (RH) of 40%.
humidity (RH) of 40%. The sensor exhibited a response to 220–300 ppm of ethanol ga
The sensor exhibited a response to 220–300 ppm of ethanol gas. For SnO2 with a size larger
For SnO2 with a size larger than the space-charge layer, EDLs form on the surface of NP
than the space-charge layer, EDLs form on the surface of NPs, and upon exposure to a
and upon exposure to a reducing gas, the modulation of resistance occurs, as shown
reducing gas, the modulation of resistance occurs, as shown in Figure 4a. However, for
Figure 4a. However, for SnO2 QDs with a size smaller than the space-charge layer, th
SnO2 QDs withQDs a size smaller
become than the
depleted from space-charge
electrons inlayer, the
the air. InQDs become
this case, a flatdepleted from and th
band is formed,
electrons in theenergetic
air. In this case, a flat band is formed, and the energetic difference
difference between the conduction band and the Fermi level increases (Figur between
the conduction4b).band andpresence
In the the Fermi of level
ethanol,increases (Figureare
the electrons 4b). In the back
released presence of ethanol,
into the SnO2 QDs. At th
the electrons are released back into the
point, the QDs become more conductive,SnO 2 QDs. At this point, the QDs become
resulting in a significant increase more
in the senso
conductive, resulting in
conductivity. a significant increase in the sensor conductivity.

Figure 4. The sensing mechanism of SnO2 NPs and SnO2 QDs. (a) when the particle size is larger
than space-charge layer of SnO2 (b) When the particle size is smaller than space-charge layer of SnO2 .
Reprinted with permission from Ref. [27]. Copyright 2016, Elsevier.

2.2. Nanowire-Based Nanomaterial Gas Sensors

Among different morphologies, nanowires (NWs) with aspect ratios greater than
20 [28] are highly popular for sensing applications, owing to their high surface area, straight-
forward preparation methods, ease of gas sensor fabrication, high and rapid response to the
target gas, long-term stability, and high crystallinity [29,30]. Accordingly, several studies
Chemosensors 2022, 10, 289 6 of 23

have realized the enhanced gas-sensing capacity of NW-based gas sensors [31,32]. In [33],
various methods to synthesize NWs are discussed in detail.
Among different MOSs with NW morphology, SnO2 NWs are very popular for sensing
purposes [34–37]. SnO2 has a band gap of 3–4 eV, depending on the synthesis method, size,
surface states, and impurities [38]. However, most studies have reported a band gap of
3.7 eV for this MOS [39]. SnO2 is the most stable n-type oxide, and is extensively used in
the preparation of semiconductor gas sensors. Its high electron mobility (~160 cm2 /V·s)
makes it a key choice for sensing applications [19,40]. In addition, SnO2 NWs exhibit good
optical transparency and conductivity [41]. Wang et al. [42] performed one of the first
studies on SnO2 NWs for the detection of H2 gas, and compared the results with those
of SnO2 nanorods (NRs). It was reported that owing to the higher surface area of NWs,
size effects when the diameter of the NWs was less than the Debye length of SnO2 , and
the small electrode gap of the SnO2 NW gas sensor, a larger response was observed for
the SnO2 NWs at 300 ◦ C than that for SnO2 NRs. Notably, not only SnO2 NWs, but also
other MOS NWs, have been employed as gas sensors [43,44]. The construction of n–n and
p–n junctions is a commonly employed strategy for improving the sensitivity of NW-based
gas sensors [45]. Owing to the generation of these heterojunctions, the resistance of gas
sensors is higher than that of the pure sensing material, and the subsequent modulation of
resistance in the presence of target gases generates a high sensing signal for heterojunction
gas sensors [46].
Branched NWs (e.g., nanoforests or nanotrees) are a special type of NWs that have
recently been used for sensing applications. Their 3D morphology and numerous homo- or
heterojunctions make the branching NWs highly popular for sensing studies. With high
surface area, branched NWs can detect extremely low amounts of gases. Branched NWs
also offer an increased number of carrier paths and improved conduction between the
NW branches and backbones [47–49]. Several studies have elaborated on the enhanced
gas-sensing properties of branched NWs [50,51]. Woo et al. [52] reported the p-xylene-
sensing characteristics of Ni-doped branched ZnO NWs. As an n-type MOS, ZnO has high
physical and chemical stability, a high electron mobility of up to 1000 cm2 /V, and a wide
band gap—all of which are extremely favorable for sensing applications [53]. At 400 ◦ C, it
showed a high response to 42.44–5 ppm of p-xylene. The enhanced p-xylene gas response
was related to the increased resistance modulation owing to the presence of numerous
Schottky barriers between the branches. Importantly, selectivity was found to be related
to the catalytic activity of Ni. Thus, by the combination of the high surface area of MOS
and the catalytic effect of metals, it is possible to achieve highly sensitive gas sensors for
practical applications. In another report, Bi2 O3 -branched SnO2 NWs with a large surface
area were prepared for NO2 -sensing studies [54]. Figure 5a–d show the relevant XRD and
SEM characterizations, which demonstrate the formation of Bi2 O3 -branched SnO2 NWs
with the expected phase and morphology. The sensor exhibited a high response of 56.92
in the presence of only 2 ppm of NO2 gas at 250 ◦ C; this response is very high relative
to that shown by other MOS-based gas sensors. This superiority was attributed to the
presence of the following resistance modulation sources: (i) resistance modulation of the
exposed surfaces of SnO2 NWs, (ii) resistance modulation of the exposed surfaces of Bi2 O3
NWs, (iii) resistance changes in the SnO2 –SnO2 and Bi2 O3 –Bi2 O3 homojunctions, and (iv)
resistance modulation in the SnO2 –Bi2 O3 heterojunctions. However, the contribution of
SnO2 –Bi2 O3 heterojunctions was the highest.
 Chemosensors 2022, 10, x FOR PEER REVIEW 7 of

Chemosensors 2022, 10, 289 7 of 23

Bi2O3 homojunctions, and (iv) resistance modulation in the SnO2–Bi2O3 heterojunction
However, the contribution of SnO2–Bi2O3 heterojunctions was the highest.

Figureof5.(a)
Figure 5. XRD spectra XRD spectra
SnO 2 NWsofand
(a) (b)
SnOBi
2 NWs and (b) BiSnO
2 O3 -branched 2O3-branched SnOimages
2 NWs. SEM 2 NWs. of
SEM(c) images
SnO2 of (c) Sn
NWs
NWs and (d) Bi2 O and (d) Bi
-branched 2O3-branched SnO2 NWs. Reprinted with permission from Ref. [54]. Copyright 20
SnO NWs. Reprinted with permission from Ref. [54]. Copyright 2018,
3 2
Elsevier.
Elsevier.

Overall, the highOverall,

surfacethearea
highalong
surface areanumerous
with along with numerousmodulation
resistance resistance modulation
sources sourc
between the stem and branches of the NWs makes them
between the stem and branches of the NWs makes them suitable for gas-sensing studies. suitable for gas-sensing studie
Furthermore,
Furthermore, careful carefulofengineering
engineering the branched of the
NWs branched
allowsNWs allows the of
the fabrication fabrication
highly of high
sensitive gas sensors based
sensitive gas sensors based on MOS materials. on MOS materials.
In addition to NWs and branched NWs, single NWs have recently been used f
In addition to NWs and branched NWs, single NWs have recently been used for
sensing various gases [55–57]. For instance, Tonezzer et al. [58] reported the use of a si
sensing various gases [55–57]. For instance, Tonezzer et al. [58] reported the use of a single
gle SnO2 NW for gas-sensing applications. By applying a thermal gradient to the sing
SnO2 NW for gas-sensing applications. By applying a thermal gradient to the single SnO2
SnO2 NW gas sensor and combining its responses at five various working temperatur
NW gas sensor and combining its responses at five various working temperatures from 200
◦ from 200 to 400 °C, the sensor was able to distinguish seven different gases—name
to 400 C, the sensor was able to distinguish seven different gases—namely, acetone, NH3 ,
acetone, NH3, CO, ethanol, H2, NO2, and toluene—and measure their concentration
CO, ethanol, H2 , NO2 , and toluene—and measure their concentrations. Even though it is
Even though it is possible to achieve single NW gas sensors with the present technolog
possible to achieve single NW gas sensors with the present technology, it should be noted
it should be noted that the growth and realization of a single NW are difficult relative
that the growthother
and realization
highly dense of aNWs.
single NW are difficult
Moreover, because relative to other
of the lack highly dense resistan
of heterojunctions,
NWs. Moreover, because of the lack of heterojunctions, resistance modulation
modulation is relatively limited, and a high response cannot be expected is relatively
from a sing
limited, and a high
NW. response cannot be expected from a single NW.
Core–shell (C–S) NWs are(C–S)
Core–shell another
NWscategory
are anotherof NWs,
categorywhere the core
of NWs, is coated
where the corewith
is coated wi
another metal oxide to form the C–S NWs [59]. In C–S nanostructures,
another metal oxide to form the C–S NWs [59]. In C–S nanostructures, the core andtheshell
core and sh
materials should be semiconductors.
materials A good way to synthesize
should be semiconductors. A good way C–Sto NWs is by synthesizing
synthesize C–S NWs is by synth
the core NWs and then
sizing thecoating
core NWs them
andwith
thena coating
shell using
thematomic
with a layer deposition
shell using atomic(ALD).
layer depositi
In this way, the(ALD).
shell thickness
In this way,canthe
beshell
easily adjusted
thickness canbybecontrolling the ALD
easily adjusted cycles [60].
by controlling the ALD c
Thus, ALD is one of the
cles [60]. most
Thus, ALDaccurate techniques
is one of to control
the most accurate the shelltothickness.
techniques control the The
shell thickne
shell permits the
Thediffusion of thethe
shell permits gasdiffusion
into deeper parts
of the gasofinto
thedeeper
sensor;parts
accordingly, porous
of the sensor; according
shells are moreporous
suitable for are
shells such applications.
more suitable for In
suchC–S systems, the
applications. heterointerfaces
In C–S are
systems, the heterointerfac
maximized, and heterojunctions are formed between the core and shell layers, resulting
in superior modulation of the resistance [61]. Several C–S NW systems can be found in
the literature for sensing studies [62–65]. However, it should be noted that there is an
optimal shell thickness, at which the maximum response is obtained. This shell thickness is
often close to the Debye length of the shell material [65]. The effect of shell thickness on
Chemosensors 2022, 10, x FOR PEER REVIEW 8 of 23

are maximized, and heterojunctions are formed between the core and shell layers, re-
sulting in superior modulation of the resistance [61]. Several C–S NW systems can be
Chemosensors 2022, 10, 289 8 of 23
found in the literature for sensing studies [62–65]. However, it should be noted that there
is an optimal shell thickness, at which the maximum response is obtained. This shell
thickness is often close to the Debye length of the shell material [65]. The effect of shell
C–S systems
thickness has been
on C–S extensively
systems has been discussed
extensively indiscussed
a review paper [66]. In
in a review addition,
paper the
[66]. In use
addi-
of noble metals as decoration on the surface of the shell layer is a widely used
tion, the use of noble metals as decoration on the surface of the shell layer is a widely technique
to enhance
used the sensitivity
technique to enhance and selectivityand
the sensitivity of gas sensors of
selectivity to gas
a particular
sensors togas. For example,
a particular gas.
Au functionalization on the surface of SnO
For example, Au functionalization on the surface 2 –ZnO C–S NWs led to the enhancement
of SnO2–ZnO C–S NWs led to the en- of
the sensing response to CO gas, as shown in Figure 6a,b [67]. The senor
hancement of the sensing response to CO gas, as shown in Figure 6a,b [67]. The senor showed a high
responseaof
showed 26.6response
high to only 100 ppbtoofonly
of 26.6 CO gas
100 at
ppb300of◦ CO
C. gas at 300 °C.

Figure 6. (a)
(a) Dynamic
Dynamicresistance
resistancecurve
curveofofa Au-functionalized
a Au-functionalized SnO
SnO 2–ZnO
2 –ZnO C–SC–S
NWNW gasgas sensor
sensor to
to low
low concentrations
concentrations of COof gas.
CO gas. (b) Comparison
(b) Comparison between
between the responses
the responses of different
of different gas sensors
gas sensors to ppb
to 100 100
ppb of gas.
of CO CO gas. Reprinted
Reprinted withwith permission
permission fromfromRef. Ref.
[67]. [67]. Copyright
Copyright 2017,2017, Elsevier.
Elsevier.

In addition to the formation of SnO22–ZnO

–ZnO heterojunctions,
heterojunctions, the
the formation
formation of Au–ZnO
Au–ZnO
Schottky
Schottky barriers
barriers can
can contribute
contribute to
to the sensing signal (Figure 7a,b). The
The presence
presence of
of Au
changes the EDL thickness inside the ZnO shell, and in the the presence
presence of COCO gas,
gas, variations
variations
in EDL width can enhance the sensing
sensing response
response (Figure
(Figure 7c).
7c). Finally,
Finally, Au with a catalytic
(chemical sensitization) effect toward CO gas can promote the oxidation of CO gas on the
surface of the gas sensor, leading to an enhanced response
response toto CO
CO gas
gas (Figure
(Figure 7d).
7d).
Careful design and engineering of the shell choice as well as of the shell thickness
enables the formation of an additional EDL near the C–S interfaces, owing to electron
trapping at the interfaces. Thus, the depletion of the entire shell layer from the charge
carriers can occur. Furthermore, the large variations in the resistance of the C–S NWs can
result in the generation of a high response. Moreover, potential barriers are formed, and
the modulation of their height can contribute to the sensing signal [68]. In conclusion, C–S
NW sensors are among the most promising novel nanostructures for gas-sensing studies.
When the shell thickness is close to the Debye length of the shell material, they exhibit the
highest gas-sensing performance. Additionally, a core with a larger or lower work function
can significantly affect the optimized shell thickness.
Chemosensors 2022,10,
Chemosensors2022, 10,289
x FOR PEER REVIEW 99 of
of 23
23

Figure7.7. (a)
Figure (a)Energy
Energylevels
levelsof
ofSnO
SnO22–ZnO
–ZnO and
and Au
Au in
in vacuum
vacuum andandair
airafter
aftercontact.
contact. (b)
(b)Modulation
Modulationof of
SnO22–ZnO
SnO –ZnO heterojunctions
heterojunctions in
in the
the presence
presence of
of CO
CO gas.
gas. (c)
(c) Modification
Modification of
of an
an EDL
EDL inside
inside ZnO
ZnO byby Au.
Au.
(d)Chemical
(d) Chemicalsensitization
sensitizationofofAu.
Au. Reprinted
Reprinted with
with permission
permission from
from [Link].
[67].[67]. Copyright
Copyright 2017,
2017, Else-
Elsevier.
vier.
Self-heated gas sensors are a new generation of MOS gas sensors in which an external
voltageCareful design
is applied to and engineering
the electrodes ofof
thethe
gasshell choiceleading
sensors, as welltoasthe
of generation
the shell thickness
of heat
enables the
through the Joule
formation
heating of mechanism
an additional EDLthe
inside near the C–S
sensing interfaces,
material owing to
[69]. Notably, theelectron
opera-
trapping
tion of theatgasthe interfaces.
sensor in thisThus,
mode the depletion
allows of the entire
for extremely shell consumption,
low power layer from thewithout
charge
carriers
the need can occur. Furthermore,
for external heaters [69].the large variations in the resistance of the C–S NWs can
result in the generation
Typically, thin-film gas of asensors
high response. Moreover,
with external heaters potential
consume barriers are formed,
approximately 1–5and
W
the modulation of their height can contribute to the sensing
of power, and MEMS-based sensors consume less than 30–50 mW of power. However, signal [68]. In conclusion, C–
S NW
for sensors are
a self-heated gasamong
sensor, the most promising
significantly novel (in
lesser power nanostructures
the range of for gas-sensing
microwatts) is
studies. When
consumed [70].the shell thickness
Among is close
the different to the Debye
morphologies, NWslength
are of
thethe
mostshell material,
efficient forthey
the
exhibit the highest
development gas-sensing
of self-heated performance. Additionally, a core with a larger or lower
gas sensors.
workOnefunction
NW incan thesignificantly
self-heatingaffect
modethe canoptimized shell thickness.
generate power densities 10,000 times higher
than aSelf-heated
heater [60]. gasThe lengthare
sensors of athe
newNWs directly affects
generation of MOSthe gasheat generated
sensors inside
in which an the
ex-
gas
ternal voltage is applied to the electrodes of the gas sensors, leading to the generation to
sensor, thus allowing Joule heating to warm the NWs and ensure a higher response of
the
heattarget
[Link]
Moreover, powermechanism
Joule heating is consumed at the
inside themicrowatt scale due
sensing material to the
[69]. minimal
Notably, the
thermal capacitance of the NWs [71]. Several studies have reported self-heating gas sensors
 than a heater [60]. The length of the NWs directly affects the heat generated inside the g
sensor, thus allowing Joule heating to warm the NWs and ensure a higher response to
target gas. Moreover, power is consumed at the microwatt scale due to the minim
thermal capacitance of the NWs [71]. Several studies have reported self-heating gas s
Chemosensors 2022, 10, 289 10 of 23
sors based on NWs [72–75]. For instance, Kim et al. [76] reported that CuO-decora
SnO2–ZnO C–S NWs with an optimized shell thickness of 80 nm exhibited a good
sponse to approximately 2–10 ppm of H2S gas at a voltage as low as 5 V. This was
based on NWs [72–75]. For instance, Kim et al. [76] reported that CuO-decorated SnO2 –
tributed
ZnO toC–StheNWsself-heating effect shell
with an optimized of the gas sensor,
thickness electrical
of 80 nm exhibitedcontacts between
a good response to the th
NWs,approximately
SnO2–ZnO2–10 interfaces,
ppm of H2and
S gas the presence
at a voltage ofasCuO.
as low Kim
5 V. This was et al. [77]
attributed fabricated
to the
self-heating effect of the gas sensor, electrical contacts between the
self-heated gas sensor based on Pd-decorated SnO2–ZnO C–S NWs. The2 correspond thick NWs, SnO –ZnO
interfaces,results
gas-sensing and the are
presence
shownof CuO. Kim et al.
in Figure 8.[77] fabricated
A good a self-heated
response gas sensor
to 1.75–50 based
ppm of C6H6
on Pd-decorated SnO2 –ZnO C–S NWs. The corresponding gas-sensing results are shown
was in
reported for the sensor, with a low applied voltage of 10 V and a low power c
Figure 8. A good response to 1.75–50 ppm of C6 H6 gas was reported for the sensor, with
sumption of 22.6voltage
a low applied μW, which wasa related
of 10 V and low power toconsumption
the presence of heterojunctions
of 22.6 µW, which was relatedas well as
catalytic
to theeffect of Pd.
presence of heterojunctions as well as the catalytic effect of Pd.

Figure 8. (a) Dynamic resistance curves of a Pd-functionalized SnO2 –ZnO C–S NW sensor at different
Figure 8. (a)
values Dynamic
of applied resistance
voltages, curves
and 0.1–50 ppm Cof a Pd-functionalized SnO2–ZnO C–S NW sensor at
6 H6 , at room temperature. (b) Corresponding calibration
ferentcurves
values of applied
at different voltages,
applied [Link] 0.1–50 ppm
(c) Comparison C6H6responses
between , at roomtotemperature.
50 ppm C6 H6 at(b) Correspond
different
calibration curves at different applied voltages. (c) Comparison between
applied voltages. Reprinted with permission from Ref. [77]. Copyright 2020, [Link] to 50 ppm C
at different applied voltages. Reprinted with permission from Ref. [77]. Copyright 2020, Elsevie
Although a self-heated single NW gas sensor has not yet been reported, a single NW
gas sensor can consume very low power if the sensor works in self-heating mode. Since
Although a self-heated single NW gas sensor has not yet been reported, a single N
there is only one NW, it can be heated very fast with extremely low power consumption.
gas sensor can gas
Self-heated consume
sensors very low power
with extremely lowifpower
the sensor works can
consumption in self-heating
be integrated mode.
in Sin
thereportable
is onlysmart
one NW, itsuch
devices can as
besmart
heated very
mobile fast with extremely low power consumpti
phones.
 Self-heated gas sensors with extremely low power consumption can be integrated in
portable smart devices such as smart mobile phones.

2.3. Nanofiber-Based MOS Gas Sensors

Chemosensors 2022, 10, 289 Nanofibers (NFs) are another type of 1D material used in MOS gas sensors. 11 of Similar
23
to NWs, NFs have an aspect ratio of more than 20. However, their surfaces have many
nanograins, which result in a further increase in the surface area [78]. There are various
2.3. Nanofiber-Based
methods to synthesize MOS Gas however,
NFs; Sensors NFs are commonly produced using the electro-
spinning (ES) technique.
Nanofibers (NFs) are The ES technique
another type of 1Dconsists
materialofused
a spinneret
in MOS gas section,
sensors.a high-voltage
Similar
to NWs,
power supply,NFs and
haveaan aspect
metal ratio of [79].
collector moreDuring
than [Link],
However, their surfacesNFs arehave many
formed from a
nanograins, which result in a further increase in the surface
liquid jet and subsequently elongated under a high voltage. The NF formation process area [78]. There are various
methods
consists of to synthesize
the following: NFs;(i)however,
onset of NFs are commonly
jetting produced using
and development of athe electrospin-
rectilinear jet, (ii)
ning (ES) technique. The ES technique consists of a spinneret section, a high-voltage power
bending deformation along with solvent evaporation to form solidified NFs, and (iii) NF
supply, and a metal collector [79]. During electrospinning, NFs are formed from a liquid jet
collection [80]. In a simplified view, a sol is initially prepared in this technique, and is
and subsequently elongated under a high voltage. The NF formation process consists of the
subsequently
following: (i)poured
onset ofinto
jettinga syringe. Upon applying
and development a high
of a rectilinear jet,voltage to the
(ii) bending sol with a de-
deformation
fined
along with solvent evaporation to form solidified NFs, and (iii) NF collection [80]. In placed
viscosity, it is possible to collect extremely fine and long NFs on the collector a
at asimplified
fixed distance from
view, a sol the syringe.
is initially prepared After calcination
in this technique, andof the synthesizedpoured
is subsequently NFs at intoan ap-
a syringe.
propriate Upon applying
temperature a high voltage
for sufficient time,tothethefinal
sol with a defined
diameter viscosity,
decreases it is
due topossible
evaporation
to collect extremely fine and
of the solvent and organic materials [79]. long NFs on the collector placed at a fixed distance from
theBysyringe. After calcination of the synthesized NFs at an
optimization of the ES technique parameters—such as the applied voltage,appropriate temperature for dis-
sufficient time, the final diameter decreases due to evaporation of the solvent and organic
tance between the needle tip and the collector, flow rate, and temperature—it is possible
materials [79].
to tuneBy theoptimization
diameter of the resulting NFs [81,82]. In particular, the viscosity of the solu-
of the ES technique parameters—such as the applied voltage, distance
tion can significantly
between the needle tip affect
and the formation
the collector, of rate,
flow longandNFs [83]. If the viscosity
temperature—it is possibleof the ES solu-
to tune
tion is not adjusted to the desired value, NFs with beads are formed
the diameter of the resulting NFs [81,82]. In particular, the viscosity of the solution can [83].
Furthermore,
significantly affectwith a special of
the formation type
longofNFs
ES technique, known of
[83]. If the viscosity asthe
coaxial ES, it is not
ES solution possible
adjusted to
to directly the desiredC–S
synthesize value,
NFs NFs with beads
[84,85]. ManyareMOSs formed [83].been successfully synthesized
have
using the Furthermore,
ES technique withfor a special type ofstudies
gas-sensing ES technique, known as
[86]. Similar to coaxial
C–S NWs, ES, itthe
is possible
thickness of
to directly synthesize C–S NFs [84,85]. Many MOSs have been
the shell layer should be adjusted to obtain the maximum response to the target gas. For successfully synthesized
using the ES technique for gas-sensing studies [86]. Similar to C–S NWs, the thickness of
example, Kim et al. [87] reported that in SnO2–Cu2O C–S NF gas sensors with different
the shell layer should be adjusted to obtain the maximum response to the target gas. For
shell thicknesses, the sensor with a shell thickness of 30 nm gave the highest response to
example, Kim et al. [87] reported that in SnO2 –Cu2 O C–S NF gas sensors with different
COshell
gas—it showedthe
thicknesses, a response
sensor with to 5–10
a shellppm of COofgas
thickness at 300
30 nm gave °C.
the highest response to
CO MOS-based
gas—it showed gas asensors
responsewith to 5–10 NFppmmorphology
of CO gas atpossess
300 C. a high surface area, which
◦
provides many adsorption
MOS-based gas sensors with sites NF formorphology
the incoming possessgas molecules.
a high surface area,Moreover,
which the
nanograins on the surface of the NFs act as a powerful source of resistance modulation
provides many adsorption sites for the incoming gas molecules. Moreover, the nanograins
on the9)surface
(Figure [88]. of the NFs act as a powerful source of resistance modulation (Figure 9) [88].

Figure 9. (a,b) TEM images of 0.5 SnO2 –0.5 Co3 O4 composite NFs. Reprinted with permission from
Ref. [88]. Copyright 2017, Elsevier.
Chemosensors 2022, 10, 289 12 of 23

To date, several types of NFs have been used for sensing applications. Pristine NFs [89],
composite NFs [90], and noble-metal-decorated NFs [91] have been used for sensing studies.
Other relevant morphologies include hollow NFs [92] and C–S NFs [93]. Hollow NFs, in
particular, can provide a larger surface area for target gas molecules; hence, they are among
the most popular types of NFs for sensing studies. A detailed discussion of the sensing
mechanism of NFs can be found in the study by Kim et al. [94].

2.4. Nanotube-Based MOS Gas Sensors

Metal oxide nanotubes (NTs) have been studied less compared to their NW and NF
counterparts [95]. This may be due to the difficulty in the synthesis of MOS NTs. Various
techniques can be used for synthesizing MOS NTs. However, the most common method is
the use of a hard or soft sacrificial template. Hard templates have been prepared using silica,
carbon, and polystyrene beads, while soft templates have been fabricated from bubbles,
polymer vesicles, emulsion droplets, and surfactant micelles. The core can be removed
by dissolving in a solvent or calcination to generate hollow structures [96]. The main
features of gas sensors based on hollow structures such as NTs are (i) wall permeability,
(ii) wall thickness, and (iii) wall chemistry [97]. Although thinner NTs are expected to
provide greater surface area and more adsorption sites for gas molecules [98], the presence
of defects can sometimes alter the sensing properties. Hazra et al. investigated the effects of
shell thickness on the sensing characteristics of TiO2 NTs. Interestingly, the sensor with the
thinnest wall and largest surface area did not show the highest response to the target gas,
due to the lower amount of oxygen vacancies. The device with a thicker wall and sufficient
oxygen vacancies exhibited the highest response [99]. In conclusion, MOS-based NTs for
gas-sensing studies offer a high surface area owing to the hollowness of their structure,
which can provide many adsorption sites for gas molecules.

2.5. Nanorod-Based MOS Gas Sensors

Nanorod-based gas sensors are another popular category of MOS materials for gas-
sensing studies, owing to their unique electrical properties and high surface area provided
by the NR morphology. The hydrothermal method provides a convenient, fast, versatile,
and low-cost route for constructing well-ordered nanorod arrays [100–103]. However, other
methods—such as chemical bath deposition (CBD), which is economical, straightforward,
and scalable—can also be used to prepare NRs from different materials [104]. Chemical
vapor deposition [105,106], metal–organic chemical vapor deposition [107,108], and pulsed
laser deposition [109] are other methods for obtaining NRs in MOSs. NR-based MOS
materials are popular for sensing studies because of their ease of production, high surface
area, and compositional versatility.

2.6. Nanosheet-Based MOS Gas Sensors

Two-dimensional MOS nanostructured materials with a sheet-like morphology are
popular for gas-sensing studies due to their high surface area. Only a few 2D MOS (MoO3 ,
WO3 , and SnO2 ) analogs of graphene are known. Two-dimensional (2D) layered MOSs have
strong in-plane bonds and weak van der Waals forces between layers, and gas molecules
can be adsorbed on these sites. Thus, 2D layered MOSs can be employed for the production
of gas sensors [110]. Apart from the naturally 2D layered MOSs, other MOSs can also be
synthesized in a nanosheet-like morphology. For instance, Choi et al. [111] synthesized
porous ZnO nanosheets using a solvothermal technique for NO2 detection. The sensor
exhibited a high response to 74.68–10 ppm of NO2 gas at 200 ◦ C. The width of the EDL
increased in the presence of NO2 gas, contributing to the sensing signal. Moreover, homo-
junctions were formed, and changes in the height of the homojunctions led to resistance
modulation in the presence of NO2 gas. Furthermore, the highly porous morphology and
high specific surface area (11.51 m2 /g) contributed to the increased availability of active
sites for NO2 gas molecules [111].
 led to resistance modulation in the presence of NO2 gas. Furthermore, the highly porous
morphology and high specific surface area (11.51 m2/g) contributed to the increased
Chemosensors 2022, 10, 289 13 of 23
availability of active sites for NO2 gas molecules [111].
In another study, Kim et al. [112] synthesized self-heated 2D pristine and
Au-functionalizedInWS 2–SnO
another 2 core–shell
study, NSs
Kim et al. [112] with different
synthesized self-heatedshell thicknesses
2D pristine of up to 60
and Au-functionalized
nm on polyamide substrates.
WS2–SnO 2 core–shellBare
NSsand withAu-decorated gas sensors
different shell thicknesses of upwith shell
to 60 nm onthicknesses
polyamide sub- of
strates. Bare and Au-decorated gas sensors with shell thicknesses
15 and 30 nm exhibited the highest CO-sensing performance at a low voltage of 3.4 V. of 15 and 30 nm exhibited the
highest CO-sensing performance at a low voltage of 3.4 V. Figure 10a shows dynamic resistance
Figure 10a shows dynamic resistance curves of Au-decorated WS2–SnO2 with different
curves of Au-decorated WS2–SnO2 with different shell thicknesses to 10 ppm CO at a fixed
shell thicknesses to 10
applied ppmofCO
voltage 3.4 [Link]
a fixed
10b applied
shows the voltage of 3.4plots
corresponding V. ofFigure 10b
response andshows the
resistance
correspondingversusplots theof response
shell thickness. and resistance
The sensor versus
with a shell theofshell
thickness 10 nmthickness. The
showed a high sensor
response to
with a shell thickness
12–10 ppmof of10
COnm [Link] a high response to 12–10 ppm of CO gas.

Figure 10. (a) Dynamic

Figure [Link]
(a) Dynamicplots of Au-decorated
resistance WS2–SnO
plots of Au-decorated 2 C–S
WS2 –SnO NSNS
2 C–S gasgassensors withdifferent
sensors with dif-
ferent shell thicknesses to 10 ppm
shell thicknesses of CO
to 10 ppm gasgas
of CO atat3.4
3.4V.
V. (b) Corresponding
(b) Corresponding response
response and
and base base re-
resistance versus
sistance versus the
theshell
shellthickness. Reprinted
thickness. with permission
Reprinted from Ref. from
with permission [112]. Ref.
Copyright
[112].2022, Elsevier. 2022,
Copyright
Elsevier.
As shown in Figure 11a,b, when the thickness of the shell is less, the entire shell is
depleted of electrons in the air, and subsequent exposure to CO gas results in a significant
As shownmodulation
in Figureof11a,b, when
the sensor the thickness
resistance. of the
Furthermore, shell isin less,
as shown Figurethe
11c,entire shell is
the formation
depleted of electrons in the air,
of heterojunctions andand subsequent
modulation in theexposure
air and CO to atmospheres
CO gas results in a signifi-
contributes to the
sensing signal. Figure 11d–f show the effects of Au and the shell thickness
cant modulation of the sensor resistance. Furthermore, as shown in Figure 11c, the for- on the sensing
performance. It can be concluded that the Au NPs have a positive catalytic effect on the
mation of heterojunctions and modulation in the air and CO atmospheres contributes to
gas-detection mechanism.
the sensing signal. Figure 11d–f show the effects of Au and the shell thickness on the
sensing performance. It can be concluded that the Au NPs have a positive catalytic effect
on the gas-detection mechanism.
Chemosensors 2022, 10,
Chemosensors 2022, 10, 289
x FOR PEER REVIEW 14 of
14 of 23
23

Figure 11.
11. Gas-sensing
Gas-sensing mechanism
mechanism ofof (a)
(a) thin-shell
thin-shell and
and (b)
(b) thick-shell
thick-shell pristine
pristineWS
WS2–SnO
–SnO2 core–shell
Figure 2 2 core–shell
NSs. (c) Energy bands of Au-functionalized WS2–SnO2 core–shell NSs before and after contact.
NSs. (c) Energy bands of Au-functionalized WS2 –SnO2 core–shell NSs before and after contact.
Gas-sensing mechanism of (d) thin-shell and (e) thick-shell Au-decorated WS2–SnO2 core–shell
Gas-sensing mechanism of (d) thin-shell and (e) thick-shell Au-decorated WS2 –SnO2 core–shell
NSs. (f) Resistance modulation of pristine and Au-decorated WS2–SNO2 core–shell NS gas sensors.
NSs. (f) Resistance
Reprinted modulation
with permission fromofRef.
pristine
[112].and Au-decorated
Copyright WS2 –SNO2 core–shell NS gas sensors.
2022, Elsevier.
Reprinted with permission from Ref. [112]. Copyright 2022, Elsevier.
2.7. Three-Dimensional MOS Gas Sensors
2.7. Three-Dimensional MOS Gas Sensors
Hierarchical nanostructures
Hierarchical nanostructures with with three-dimensional
three-dimensional (3D)
(3D) morphology
morphology are are composed
composed
of zero-,
of zero-, one-,
one-, two-,
two-, and
and three-dimensional
three-dimensional morphologies,
morphologies, suchsuch as nanorods, nanotubes,
as nanorods, nanotubes,
or nanosheets [22]. Hierarchical nanostructures with high surface area
or nanosheets [22]. Hierarchical nanostructures with high surface provide more
area provide more
adsorption sites for target gases. In addition, with pores or channels in their
adsorption sites for target gases. In addition, with pores or channels in their structure, structure, the
diffusion of gases is facilitated, resulting in better interaction of the target gas
the diffusion of gases is facilitated, resulting in better interaction of the target gas with with deep
parts parts
deep of theofsensing material
the sensing [113].[113].
material Vapor-phase growth
Vapor-phase and and
growth hydrothermal
hydrothermaltechniques are
techniques
the two most-used methods to synthesize hierarchical nanostructures
are the two most-used methods to synthesize hierarchical nanostructures [22]. Owing [22]. Owing to
these advantages, hierarchical morphologies of MOSs are widely used
to these advantages, hierarchical morphologies of MOSs are widely used for sensing for sensing studies
[114,115].
studies [114,115].
For instance, Guo et al. [116] used a 3D hierarchical hollow structure of CuO/WO3
for p-xylene-sensing studies (Figure 12). The sensor showed a good response to 6.36–50
Chemosensors 2022, 10, 289 15 of 23

Chemosensors 2022, 10, x FOR PEER REVIEW 15 of 23

For instance, Guo et al. [116] used a 3D hierarchical hollow structure of CuO/WO3
for p-xylene-sensing studies (Figure 12). The sensor showed a good response to 6.36–
50 ppm of xylene ◦ C. The sensing mechanism was related to the unique 3D
ppm of xylene gasgas at 260
at 260 °C. The sensing mechanism was related to the unique 3D hier-
hierarchical structure with a high surface area 2 ·g−1 , the formation of defects
archical structure with a high surface area of of 23.4962
23.4962 mm2·g−1 , the formation of defects in
in
thethe interfaces
interfaces between
between CuOand
CuO andWOWO , andthe
3,3and theformation
formationofofp–n
p–nheterojunctions
heterojunctions between
between
CuO
CuO and WO33. Recently, Yu et. al. [117] reviewed MOSs with hierarchical structures for
and WO . Recently, Yu et. al. [117] reviewed MOSs with hierarchical structures for
gas-sensing
gas-sensing studies.
studies.

Figure 12.
Figure 12. (a,b)
(a,b)SEM
SEMimages
imagesofofhierarchical
hierarchical CuO–WOnanostructures
CuO–WO 3 nanostructures at two different magnifica-
at two different magnifications.
3
tions. Reprinted with permission from Ref. [116]. Copyright 2022, Elsevier.
Reprinted with permission from Ref. [116]. Copyright 2022, Elsevier.

2.8. Noble-Metal-Decorated MOS Gas Sensors

Gas-sensing properties can be improved by loading MOSs with small amounts of
appropriately
appropriatelychosenchosennoble
noblemetals. Noble
metals. Noblemetals suchsuch
metals as Au,
as Pt,
Au,Pd,Pt,Ag,
Pd,and
Ag,Ruand
are Ru
widely
are
used
widelyforused
the decoration or functionalization
for the decoration of the MOS
or functionalization of thesurfaces to improve
MOS surfaces the overall
to improve the
performance of the resulting
overall performance gas sensors.
of the resulting The basic
gas sensors. Theproperties of the of
basic properties prominent noble
the prominent
metals (i.e., Pt, Au, Pd, and Ag) are listed in Table 1 [118]. In particular, the work
noble metals (i.e., Pt, Au, Pd, and Ag) are listed in Table 1 [118]. In particular, the work functions
of Pt, Pd, Au,
functions and
of Pt, Pd,Ag areand
Au, approximately 5.65, 5.3, 5.1,
Ag are approximately and
5.65, 4.35.1,
5.3, eV,and
respectively.
4.3 eV, respectively.

Table 1. Properties
Table 1. Propertiesof
ofsome
somenoble
noblemetals
metals[118].
[118].Reprinted
Reprintedwith
withpermission
permissionfrom Ref.
from [118].
Ref. Copyright
[118]. Copy-
right 2015,
2015, Elsevier.
Elsevier.

Property
Property Pt Pt Pd Pd AuAu Ag
Ag
Melting point
Melting point (°C)
(◦ C) 1769 1769 1552
1552 1064.4
1064.4 961.9
961.9
Atomic number 78 46 79 47
Atomic number 78 46 79 47
Atomic mass (g/mol) 195.09 160.4 196.97 107.86
Atomic mass (g/mol) 195.09 160.4 196.97 107.86
Density (g/cm3) 21.45 12.02 19.30 10.49
Density (g/cm3 ) 21.45 12.02 19.30 10.49
Work function (eV) ~5.65 ~5.3 ~5.1 ~4.3
Work function
Electron (eV)
negativity ~5.65 2.2 ~5.32.2 ~5.1
2.4 ~4.3
1.9
Electron negativity 2.2 2.2 2.4 1.9
It should be noted that the noble metals need to be dispersed as finely as possible on
the surface
It shouldof be
thenoted
MOSs. Agglomeration
that of noble
the noble metals need metals on the surface
to be dispersed as finelyof the sensing
as possible
layer
on thecan lead of
surface tothe
a poor
MOSs. response of the gas
Agglomeration of sensor. Generally,
noble metals on thenoble metals
surface of theaffect the
sensing
gas-sensing performance via two well-known mechanisms: The chemical
layer can lead to a poor response of the gas sensor. Generally, noble metals affect the sensitization
mechanism, performance
gas-sensing which occurs via via two
the spillover
well-knowneffect, is a commonly
mechanisms: Theknown
chemical phenomenon
sensitizationin
catalytic chemistry. In this case, the noble metal activates the target gas
mechanism, which occurs via the spillover effect, is a commonly known phenomenon in to facilitate cata-
lytic oxidation
catalytic of gas.
chemistry. Noble
In this metals
case, increase
the noble theactivates
metal gas sensitivity as they
the target gas toincrease the
facilitate rate of
catalytic
chemical processes
oxidation [119]. metals
of gas. Noble In electronic sensitization,
increase because noble
the gas sensitivity as theymetals generally
increase have
the rate of
a larger work function than MOSs, electrons are transferred from the MOS
chemical processes [119]. In electronic sensitization, because noble metals generally have to the noble
metals, leading to the formation of Schottky barriers and contraction of the EDL or HAL
inside the MOS. In the target gas atmosphere, the width of the EDL and the HAL
changes, leading to significant modulation of the sensor resistance. Among noble metals,
Chemosensors 2022, 10, 289 16 of 23

a larger work function than MOSs, electrons are transferred from the MOS to the noble
metals, leading to the formation of Schottky barriers and contraction of the EDL or HAL
inside the MOS. In the target gas atmosphere, the width of the EDL and the HAL changes,
leading to significant modulation of the sensor resistance. Among noble metals, Pd is
well known for H2 gas detection [120], owing to its excellent catalytic activation ability for
hydrogen through the hydrogen spillover effect [121]. When a sensor decorated with Pd
NPs is placed in an atmosphere containing H2 molecules, hydrogen can easily dissociate
into hydrogen atoms on the Pd surface; in the spillover effect, hydrogen atoms move to the
neighboring MOS surfaces, leading to additional reactions between atomic hydrogen and
adsorbed oxygen [122]. Other noble metals also exhibit good catalytic activities toward
different gases. For example, Ag is often used for H2 S detection because of the generation
of Ag2 S upon exposure to H2 S gas [123]. Pt and Pd also have good catalytic activities
toward C7 H8 and C6 H6 gases, respectively [124,125].

2.9. Hybrid MOS Gas Sensors

A good strategy to enhance the gas-sensing characteristics of MOS-based gas sensors
is using another material in combination with the MOS. Hybrid MOS nanocomposites
are either (i) composites of MOS and carbon materials such as graphene, graphene oxide
(GO), reduced graphene oxide (rGO), and carbon nanotubes, or (ii) composites of MOS
and conductive polymers (CPs). Graphene, which comprises sp2 carbon atoms, is utilized
in gas sensors due to its high charge carrier mobility (200,000 cm2 V−1 s−1 ) and large
surface area (2630 m2 g −1 ) [126]. The first ever graphene gas sensor was introduced in
2007 [127]. Owing to its single-layer or few-layer nature, graphene can even interact with a
single molecule. Pristine graphene can easily agglomerate owing to the surface interactions.
Furthermore, graphene has no band gap, hindering its gas-sensing usage [128]. Thus, rGO,
with its many functional groups—such as -OH and –O—as well as defects, is a better choice
for gas-sensing studies. Although GO can be used for sensing applications, it has a very
high resistance owing to the presence of oxygen-based functional groups, limiting its use in
sensing studies [129]. rGO can be synthesized from GO using chemical reduction, thermal
reduction, and UV light reduction methods [130,131]. Many papers on gas sensors with
hybrids of MOSs and carbon allotropes have been reported. However, for sensing studies,
rGO is the most effective allotrope of carbon in its hybrid form. This is because of its
large surface area, presence of many defects, and high concentrations of charge carriers
with high mobility—all of which are beneficial for sensing. Accordingly, several studies
have been reported on hybrid MOS–rGO composites with the ability to operate at room
temperature [132,133].
CPs have tunable conductivity and high flexibility in synthesis and processing. How-
ever, because of the high affinity of CPs for moisture, they are unstable, and generally
exhibit poor sensitivity and selectivity for different gases in their pristine form. The use
of hybrid nanocomposites with CPs and MOSs could result in the development of room-
temperature gas sensors [134]. Accordingly, hybrids of CPs and MOSs have been used to
enhance the sensitivity of nanostructured sensors at low or room temperature [135,136].
One application of hybrids of MOSs and CPs is the development of flexible and wearable
gas sensors. Flexible gas sensors are generally deposited on flexible substrates, and need to
work at low temperatures, e.g., room temperature. Since composites of MOs and CPs can
function at low temperatures, they are good candidates for such applications.

2.10. Comparison of Performance of Gas Sensors with Different Morphologies

Table 2 summarizes the performance of gas sensors with various morphologies. Dif-
ferent morphologies and compositions have been used for the detection of various gases at
different temperatures. Moreover, pristine gas sensors show lower responses and higher
sensing temperatures, while composite or decorated sensing materials show better perfor-
mance at lower temperatures.
Chemosensors 2022, 10, 289 17 of 23

Table 2. Gas-sensing properties of different sensors with various morphologies.

Sensing Response (Ra /Rg ) or

Morphology Gas Conc. (ppm) T ( ◦ C) Ref.
Material (Rg /Ra )
TiO2 /SnO2 QD NO2 1 300 2.62 [25]
SnO2 QD C4 H10 8219.2 25 8.09 [26]
SnO2 QD C2 H5 OH 300 N/A * 215 [27]
Pt-SnO2 NW C7 H8 100 300 55 [32]
In2 O3 /SnO2 NW NO2 5 300 25 [34]
In2 O3 NR CO 400 350 3.5 [35]
SnO2 NW NO2 5 200 180 [36]
SnO2 NW LPG 2000 350 21.8 [37]
SnO2 NW H2 1000 300 3.3 [42]
ZnO NW NO2 20 225 95 [43]
SnO2 NW C2 H5 OH 100 300 50.6 [48]
ZnO NW NO2 5 300 106 [49]
ZnO-SnO2 NR C2 H5 OH 100 275 18 [50]
Ni/ZnO NW p-xylene 5 400 42.44 [52]
Gr/ZnO NW C2 H5 OH 20 125 23 [53]
Bi2 O3 /SnO2 NW NO2 2 250 56.92 [54]
Pt/CeO2 NW CO 200 25 3 [56]
SnO2 NW NO2 500 300 17 [57]
SnO2 NW C2 H5 OH 50 350 6.7 [58]
NiO/NiFe2 O4 Nanotetrahedrons HCHO 50 240 19 [61]
ZnO/SnO2 NW C2 H5 OH 200 400 280 [62]
ZnGa2 O4 /ZnO NW NO2 10 250 23 [63]
ZnO/WO3 NW H2 1000 25 6.45 [64]
Ga2 O3 /SnO2 NW C2 H5 OH 1000 400 66 [65]
Au/SnO2 –ZnO NW CO 0.1 300 26.6 [67]
Pt/W18 O49 NW H2 1000 200 0.528 [70]
Ag/SnO2 NW H2 S 0.5 N/A * 21.2 [73]
Rh/SnO2 NF C3 H6 O 50 200 60.6 [78]
ZnO/In2 O3 NF C2 H5 OH 100 225 31.87 [85]
SnO2 /Cu2 O NF NO2 10 300 5 [87]
In2 O3 NF CO 100 300 5.4 [89]
Pd/SnO2 NF HCHO 100 160 18.8 [92]
Co3 O4 /ZnO NF HCHO 100 220 5 [93]
TiO2 /ZnO Hemitube NO2 25 25 1.23 [98]
ZnO NR NO2 5 250 200 [100]
ZnO NR C2 H5 OH 250 400 7 [101]
α-Ag2 WO4 NR C3 H6 O 20 350 3.6 [103]
ZnO NR O3 2.5 575 850 [106]
ZnO NS NO2 10 200 74.68 [111]
* N/A: No available data.

3. Conclusions and Outlooks

MOS-based gas sensors are popular for different applications because of their high
sensing performance and low cost of synthesis and fabrication. Many MOSs can be utilized
for the production of gas sensors; however, most studies deal with n-type MOSs—especially
SnO2 and ZnO materials. There are many techniques to synthesize sensing materials
with different morphologies. One of the most popular techniques for the synthesis of
MOS NWs and branched NWs is the vapor–liquid–solid technique. In this technique, by
controlling the gas flow, furnace temperature, time, and catalyst, it is possible to achieve
extremely long MOS NWs. Electrospinning is mainly used for the synthesis of MOSs
with NF morphology. In this technique, by controlling the feeding rate, applied voltage,
solution viscosity, needle-to-collector distance, and temperature, it is possible to control the
morphology. In this way, the creation of very long and rough NFs is possible. The ALD
technique has been successfully used to deposit a shell over a core. In this technique, by
adjusting the ALD cycles, it is possible to control the thickness of the shell layer. MOS NTs
Chemosensors 2022, 10, 289 18 of 23

are mainly synthesized using a soft core; after synthesis, the core is removed, and a hollow
structure remains. In this technique, choosing an appropriate soft core and annealing
temperature to remove the core are key factors determining the hollowness of the structure.
Chemical methods such as hydrothermal and sol–gel methods are used for the fabrications
of NSs, NRs, and hierarchical structures. In these techniques, appropriate choices of the
concentration of the solution, annealing temperature, time, and pH are important to obtain
the best morphology.
Various morphologies of MOS-based gas sensors—such as QDs, NWs, NFs, NTs, NRs,
NS, and hierarchical structures—have been fabricated for sensing applications, with the
goal of increasing the active surface of the resulting gas sensor. Furthermore, C–S structures
with NW or NS morphology have been extensively investigated, wherein an optimal shell
with the highest sensing performance was employed. NSs with 2D morphology offer a
high surface area for incoming gas molecules. However, owing to the presence of surface
forces, they are generally bonded together, which may decrease their sensing performance.
Hierarchical nanostructures are also promising for sensor fabrication. With the ease of
synthesis and high response, they are among the best materials for sensing studies. The
effects of different noble metals—such as Au, Ag, Pt, and Pd—on MOS gas sensors have
also been extensively studied. Noble metals promote sensing performance through both
chemical and electronic sensitization effects. However, uniform dispersion on the surface
and optimization of the amounts are necessary to achieve optimal performance. A hybrid
MOS with carbon and polymer materials can remarkably reduce power consumption and
enable operation at low temperatures. Another strategy is the use of a sensor in self-heating
mode to reduce power consumption.
Future directions for this research can include the production of novel morphologies
and combinations of 1D, 2D, and 3D materials with high surface area and high porosity.
For example, there is limited literature on the synthesis of 1D/2D composite materials for
sensing studies. Moreover, the combination of two noble metals on the surface of an MOS
can be used to increase the sensor response and the dynamics of the sensor, such as the
response and recovery times. Finding optimal composites of MOSs, carbon nanomaterials,
or CPs could lead to high-performance gas sensors suitable for low-temperature operation.
Composites with novel sensing materials such as MXenes, transition metal dichalcogenides,
and metal–organic frameworks can provide many opportunities to decrease the sensing
temperature, increase the response to target gases, and improve the selectivity of MOS-
based gas sensors. The integration of gas sensors into low-power-consumption and portable
electronic devices such as smartphones needs further development of MOS-based gas
sensors in terms of reduction in sensing temperature, increase in response, and selectivity.

Author Contributions: Conceptualization, A.M., H.W.K. and S.S.K.; investigation, A.M., H.R.A. and
J.-Y.K.; writing—original draft preparation, A.M., H.W.K., M.S. and S.S.K.; writing—review and
editing, A.M., H.W.K. and S.S.K.; supervision, H.W.K. and S.S.K. All authors have read and agreed to
the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Acknowledgments: This research was supported by Inha University.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Kampa, M.; Castanas, E. Human health effects of air pollution. Environ. Pollut. 2008, 151, 362–367. [CrossRef] [PubMed]
2. Paralovo, S.L.; Barbosa, C.G.G.; Carneiro, I.P.S.; Kurzlop, P.; Borillo, G.C.; Schiochet, M.F.C.; Godoi, A.F.L.; Yamamoto, C.I.;
de Souza, R.A.F.; Andreoli, R.V. Observations of particulate matter, NO2 , SO2 , O3 , H2 S and selected VOCs at a semi-urban
environment in the Amazon region. Sci. Total Environ. 2019, 650, 996–1006. [CrossRef] [PubMed]
3. Jung, S.J.; Mehta, J.S.; Tong, L. Effects of environment pollution on the ocular surface. Ocul. Surf. 2018, 16, 198–205. [CrossRef]
Chemosensors 2022, 10, 289 19 of 23

4. Elizabeth, F.Y.; Kenneth, Z.; Naus, A.; Forbes, C.; Wu, X.; Dey, T. A review on the biological, epidemiological, and statistical
relevance of COVID-19 paired with air pollution. Environ. Adv. 2022, 8, 100250.
5. Li, X.; Li, Y. The impact of perceived air pollution on labour supply: Evidence from China. J. Environ. Manag. 2022, 306, 114455.
[CrossRef] [PubMed]
6. Brauer, M.; Casadei, B.; Harrington, R.A.; Kovacs, R.; Sliwa, K.; The WHF Air Pollution Expert Group. Taking a stand against
air pollution—The impact on cardiovascular disease: A joint opinion from the World Heart Federation, American College of
Cardiology, American Heart Association, and the European Society of Cardiology. Circulation 2021, 143, e800–e804. [CrossRef]
7. Khuda, K.E. Air Pollution in the Capital City of Bangladesh: Its Causes and Impacts on Human Health. Pollution 2020, 6, 737–750.
8. Ming, Y.; Deng, H.; Wu, X. The negative effect of air pollution on people’s pro-environmental behavior. J. Bus. Res. 2022, 142,
72–87. [CrossRef]
9. Mirzaei, A.; Lee, J.-H.; Majhi, S.M.; Weber, M.; Bechelany, M.; Kim, H.W.; Kim, S.S. Resistive gas sensors based on metal-oxide
nanowires. J. Appl. Phys. 2019, 126, 241102. [CrossRef]
10. Pifferi, S.; Menini, A. Odorant detection and discrimination in the olfactory system. Sens. Microsyst. 2011, 91, 3–18.
11. Kotecha, A.M.; Corrêa, A.D.C.; Fisher, K.M.; Rushworth, J.V. Olfactory dysfunction as a global biomarker for sniffing out
Alzheimer’s disease: A meta-analysis. Biosensors 2018, 8, 41. [CrossRef] [PubMed]
12. White, L.T. Hazardous Gas Monitoring: A Guide for Semiconductor and Other Hazardous Occupancies; William Andrew: New York, NY,
USA, 2001; ISBN 081551784X.
13. Brattain, W.H.; Bardeen, J. Surface properties of germanium. Bell Syst. Tech. J. 1953, 32, 1–41. [CrossRef]
14. Heiland, G. Zum Einfluß von adsorbiertem Sauerstoff auf die elektrische Leitfähigkeit von Zinkoxydkristallen. Z. Phys. 1954, 138,
459–464. [CrossRef]
15. Seiyama, T.; Kato, A.; Fujiishi, K.; Nagatani, M. A new detector for gaseous components using semiconductive thin films. Anal.
Chem. 1962, 34, 1502–1503. [CrossRef]
16. Shaver, P.J. Activated tungsten oxide gas detectors. Appl. Phys. Lett. 1967, 11, 255–257. [CrossRef]
17. Taguchi, N. Gas-Detecting Device. U.S. Patent 3,631,436, 28 December 1971.
18. Korotcenkov, G. Metal oxides for solid-state gas sensors: What determines our choice? Mater. Sci. Eng. B 2007, 139, 1–23. [CrossRef]
19. Yamazoe, N.; Sakai, G.; Shimanoe, K. Oxide semiconductor gas sensors. Catal. Surv. Asia 2003, 7, 63–75. [CrossRef]
20. Quan, W.; Hu, X.; Min, X.; Qiu, J.; Tian, R.; Ji, P.; Qin, W.; Wang, H.; Pan, T.; Cheng, S. A highly sensitive and selective ppb-level
acetone sensor based on a Pt-doped 3D porous SnO2 hierarchical structure. Sensors 2020, 20, 1150. [CrossRef]
21. Korotcenkov, G. The role of morphology and crystallographic structure of metal oxides in response of conductometric-type gas
sensors. Mater. Sci. Eng. R Rep. 2008, 61, 1–39. [CrossRef]
22. Kim, H.-J.; Lee, J.-H. Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview. Sens. Actuators B
Chem. 2014, 192, 607–627. [CrossRef]
23. Vardan, G. Quantum dots: Perspectives in next-generation chemical gas sensors—A review. Anal. Chim. Acta 2021, 1152, 238192.
24. Chen, D.; Huang, S.; Huang, R.; Zhang, Q.; Le, T.T.; Cheng, E.; Hu, Z.; Chen, Z. Highlights on advances in SnO2 quantum dots:
Insights into synthesis strategies, modifications and applications. Mat. Res. Lett. 2018, 6, 462–488. [CrossRef]
25. Lee, J.-H.; Mirzaei, A.; Kim, J.H.; Kim, J.-Y.; Nasriddinov, A.F.; Marina Rumyantseva, N.; Kim, H.W.; Kim, S.S. Gas-sensing
behaviors of TiO2 -layer-modified SnO2 quantum dots in self-heating mode and effects of the TiO2 layer. Sens. Actuators B-Chem.
2020, 310, 127870. [CrossRef]
26. Liu, J.; Lv, J.; Xiong, H.; Wang, Y.; Jin, G.; Zhai, Z.; Fu, C.; Zhang, Q. Size effect and comprehensive mathematical model for
gas-sensing mechanism of SnO2 thin film gas sensors. J. Alloys Compd. 2022, 898, 162875. [CrossRef]
27. Zhu, L.; Wang, M.; Lam, T.K.; Zhang, C.; Du, H.; Li, B.; Yao, Y. Fast microwave-assisted synthesis of gas-sensing SnO2 quantum
dots with high sensitivity. Sens. Actuators B-Chem. 2016, 236, 646–653. [CrossRef]
28. Murphy, C.J.; Jana, N.R. Controlling the aspect ratio of inorganic nanorods and nanowires. Adv. Mater. 2002, 14, 80–82. [CrossRef]
29. Comini, E.; Sberveglieri, G. Metal oxide nanowires as chemical sensors. Mater. Today 2010, 13, 36–44. [CrossRef]
30. Ramgir, N.; Datta, N.; Kaur, M.; Kailasaganapathi, S.; Debnath, A.K.; Aswal, D.K.; Gupta, S.K. Metal oxide nanowires for
chemiresistive gas sensors: Issues, challenges and prospects. Colloids Surf. A Physicochem. Eng. Asp. 2013, 439, 101–116. [CrossRef]
31. Yuan, K.; Wang, C.-Y.; Zhu, L.-Y.; Cao, Q.; Yang, J.-H.; Li, X.-X.; Huang, W.; Wang, Y.-Y.; Lu, H.-L.; Zhang, D.W. Fabrication of a
micro-electromechanical system-based acetone gas sensor using CeO2 nanodot-decorated WO3 nanowires. ACS Appl. Mater.
Interfaces 2020, 12, 14095–14104. [CrossRef]
32. Tonezzer, M.; Kim, J.-H.; Lee, J.-H.; Iannotta, S.; Kim, S.S. Predictive gas sensor based on thermal fingerprints from Pt-SnO2
nanowires. Sens. Actuators B Chem. 2019, 281, 670–678. [CrossRef]
33. Galstyan, V.; Moumen, A.; Kumarage, G.W.; Comini, E. Progress towards chemical gas sensors: Nanowires and 2D semiconductors.
Sens. Actuators B-Chem. 2022, 357, 131466. [CrossRef]
34. Park, S.; Jung, Y.W.; Ko, G.M.; Jeong, D.Y.; Lee, C. Enhanced NO2 gas sensing performance of the In2 O3 -decorated SnO2 nanowire
sensor. Appl. Phys. A 2021, 127, 898. [CrossRef]
35. Van Tong, P.; Minh, L.H.; Van Duy, N.; Hung, C.M. Porous In2 O3 nanorods fabricated by hydrothermal method for an effective
CO gas sensor. Mater. Res. Bull. 2021, 137, 111179. [CrossRef]
36. Choi, Y.-J.; Hwang, I.-S.; Park, J.-G.; Choi, K.J.; Park, J.-H.; Lee, J.-H. Novel fabrication of an SnO2 nanowire gas sensor with high
sensitivity. Nanotechnology 2008, 19, 95508. [CrossRef] [PubMed]
Chemosensors 2022, 10, 289 20 of 23

37. Hoa, N.D.; Le, D.T.T.; Tam, P.D.; Le, A.-T.; Van Hieu, N. On-chip fabrication of SnO2 -nanowire gas sensor: The effect of growth
time on sensor performance. Sens. Actuators B Chem. 2010, 146, 361–367.
38. Arlinghaus, F.J. Energy bands in stannic oxide (SnO2 ). J. Phys. Chem. Solids 1974, 35, 931–935. [CrossRef]
39. Yadav, K.K.; Guchhait, S.K.; Sood, K.; Mehta, S.K.; Ganguli, A.K.; Jha, M. Mechanistic insights of enhanced photocatalytic
efficiency of SnO2 -SnS2 heterostructures derived from partial sulphurization of SnO2 . Sep. Purif. Technol. 2020, 242, 116835.
40. Gondal, M.A.; Drmosh, Q.A.; Saleh, T.A. Preparation and characterization of SnO2 nanoparticles using high power pulsed laser.
Appl. Surf. Sci. 2010, 256, 7067–7070. [CrossRef]
41. Das, S.; Jayaraman, V. SnO2 : A comprehensive review on structures and gas sensors. Prog. Mater. Sci. 2014, 66, 112–255. [CrossRef]
42. Wang, B.; Zhu, L.F.; Yang, Y.H.; Xu, N.S.; Yang, G.W. Fabrication of a SnO2 nanowire gas sensor and sensor performance for
hydrogen. J. Phys. Chem. C 2008, 112, 6643–6647. [CrossRef]
43. Ahn, M.-W.; Park, K.-S.; Heo, J.-H.; Park, J.-G.; Kim, D.-W.; Choi, K.J.; Lee, J.-H.; Hong, S.-H. Gas sensing properties of
defect-controlled ZnO-nanowire gas sensor. Appl. Phys. Lett. 2008, 93, 263103. [CrossRef]
44. Yi, S.; Tian, S.; Zeng, D.; Xu, K.; Zhang, S.; Xie, C. An In2 O3 nanowire-like network fabricated on coplanar sensor surface by
sacrificial CNTs for enhanced gas sensing performance. Sens. Actuators B Chem. 2013, 185, 345–353. [CrossRef]
45. Kaur, N.; Zappa, D.; Maraloiu, V.; Comini, E. Novel Christmas Branched Like NiO/NiWO4 /WO3 (p–p–n) Nanowire Heterostruc-
tures for Chemical Sensing. Adv. Funct. Mater. 2021, 31, 2104416. [CrossRef]
46. Liu, H.; Wang, Z.; Cao, G.; Pan, G.; Yang, X.; Qiu, M.; Sun, C.; Shao, J.; Li, Z.; Zhang, H. Construction of hollow NiO/ZnO pn
heterostructure for ultrahigh performance toluene gas sensor. Mater. Sci. Semicond. Process. 2022, 141, 106435. [CrossRef]
47. Cheng, C.; Fan, H.J. Branched nanowires: Synthesis and energy applications. Nano Today 2012, 7, 327–343. [CrossRef]
48. Wan, Q.; Huang, J.; Xie, Z.; Wang, T.; Dattoli, E.N.; Lu, W. Branched SnO2 nanowires on metallic nanowire backbones for ethanol
sensors application. Appl. Phys. Lett. 2008, 92, 102101. [CrossRef]
49. An, S.; Park, S.; Ko, H.; Jin, C.; Lee, W.I.; Lee, C. Enhanced gas sensing properties of branched ZnO nanowires. Thin Solid Film.
2013, 547, 241–245. [CrossRef]
50. Yang, X.; Zhang, S.; Zhao, L.; Sun, P.; Wang, T.; Liu, F.; Yan, X.; Gao, Y.; Liang, X.; Zhang, S. One step synthesis of branched
SnO2 /ZnO heterostructures and their enhanced gas-sensing properties. Sens. Actuators B Chem. 2019, 281, 415–423. [CrossRef]
51. Wang, Y.; Zhou, Y.; Meng, C.; Gao, Z.; Cao, X.; Li, X.; Xu, L.; Zhu, W.; Peng, X.; Zhang, B. A high-response ethanol gas sensor
based on one-dimensional TiO2 /V2 O5 branched nanoheterostructures. Nanotechnology 2016, 27, 425503. [CrossRef]
52. Woo, H.-S.; Kwak, C.-H.; Chung, J.-H.; Lee, J.-H. Highly selective and sensitive xylene sensors using Ni-doped branched ZnO
nanowire networks. Sens. Actuators B Chem. 2015, 216, 358–366. [CrossRef]
53. Rafiee, Z.; Roshan, H.; Sheikhi, M.H. Low concentration ethanol sensor based on graphene/ZnO nanowires. Ceram. Int. 2021, 47,
5311–5317. [CrossRef]
54. Bang, J.H.; Choi, M.S.; Mirzaei, A.; Kwon, Y.J.; Kim, S.S.; Kim, T.W.; Kim, H.W. Selective NO2 sensor based on Bi2 O3 branched
SnO2 nanowires. Sens. Actuators B Chem. 2018, 274, 356–369. [CrossRef]
55. Afshar, M.; Preiß, E.M.; Sauerwald, T.; Rodner, M.; Feili, D.; Straub, M.; König, K.; Schütze, A.; Seidel, H. Indium-tin-oxide
single-nanowire gas sensor fabricated via laser writing and subsequent etching. Sens. Actuators B Chem. 2015, 215, 525–535.
[CrossRef]
56. Liao, L.; Mai, H.X.; Yuan, Q.; Lu, H.B.; Li, J.C.; Liu, C.; Yan, C.H.; Shen, Z.X.; Yu, T. Single CeO2 nanowire gas sensor supported
with Pt nanocrystals: Gas sensitivity, surface bond states, and chemical mechanism. J. Phys. Chem. C 2008, 112, 9061–9065.
[CrossRef]
57. Tonezzer, M.; Hieu, N.V. Size-dependent response of single-nanowire gas sensors. Sens. Actuators B Chem. 2012, 163, 146–152.
[CrossRef]
58. Tonezzer, M. Selective gas sensor based on one single SnO2 nanowire. Sens. Actuators B Chem. 2019, 288, 53–59. [CrossRef]
59. Czaban, J.A.; Thompson, D.A.; LaPierre, R.R. GaAs core−shell nanowires for photovoltaic applications. Nano Lett. 2009, 9,
148–154. [CrossRef]
60. Kim, J.H.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Variation of shell thickness in ZnO-SnO2 core-shell nanowires for optimizing sensing
behaviors to CO, C6 H6 , and C7 H8 gases. Sens. Actuators B-Chem. 2020, 302, 127150. [CrossRef]
61. Xu, Y.; Tian, X.; Fan, Y.; Sun, Y. A formaldehyde gas sensor with improved gas response and sub-ppm level detection limit based
on NiO/NiFe2 O4 composite nanotetrahedrons. Sens. Actuators B Chem. 2020, 309, 127719. [CrossRef]
62. Hwang, I.-S.; Kim, S.-J.; Choi, J.-K.; Choi, J.; Ji, H.; Kim, G.-T.; Cao, G.; Lee, J.-H. Synthesis and gas sensing characteristics of
highly crystalline ZnO–SnO2 core–shell nanowires. Sens. Actuators B Chem. 2010, 148, 595–600. [CrossRef]
63. Chen, I.; Lin, S.-S.; Lin, T.-J.; Hsu, C.-L.; Hsueh, T.J.; Shieh, T.-Y. The assessment for sensitivity of a NO2 gas sensor with
ZnGa2 O4 /ZnO core-shell nanowires—A novel approach. Sensors 2010, 10, 3057–3072. [CrossRef] [PubMed]
64. Park, S.; Hong, T.; Jung, J.; Lee, C. Room temperature hydrogen sensing of multiple networked ZnO/WO3 core–shell nanowire
sensors under UV illumination. Curr. Appl. Phys. 2014, 14, 1171–1175. [CrossRef]
65. Jang, Y.-G.; Kim, W.-S.; Kim, D.-H.; Hong, S.-H. Fabrication of Ga2 O3 /SnO2 core–shell nanowires and their ethanol gas sensing
properties. J. Mater. Res. 2011, 26, 2322–2327. [CrossRef]
66. Mirzaei, A.; Kim, J.-H.; Kim, H.W.; Kim, S.S. How shell thickness can affect the gas sensing properties of nanostructured materials:
Survey of literature. Sens. Actuators B Chem. 2018, 258, 270–294. [CrossRef]
Chemosensors 2022, 10, 289 21 of 23

67. Kim, J.H.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Extremely sensitive and selective sub-ppm CO detection by the synergistic effect of
Au nanoparticles and core–shell nanowires. Sens. Actuators B-Chem. 2017, 249, 177–188. [CrossRef]
68. Salehi, A. A highly sensitive self heated SnO2 carbon monoxide sensor. Sens. Actuators B Chem. 2003, 96, 88–93. [CrossRef]
69. Fàbrega, C.; Casals, O.; Hernández-Ramírez, F.; Prades, J.D. A review on efficient self-heating in nanowire sensors: Prospects for
very-low power devices. Sens. Actuators B Chem. 2018, 256, 797–811. [CrossRef]
70. Zhu, L.F.; She, J.C.; Luo, J.Y.; Deng, S.Z.; Chen, J.; Ji, X.W.; Xu, N.S. Self-heated hydrogen gas sensors based on Pt-coated W18 O49
nanowire networks with high sensitivity, good selectivity and low power consumption. Sens. Actuators B Chem. 2011, 153,
354–360. [CrossRef]
71. Majhi, S.M.; Mirzaei, A.; Kim, H.W.; Kim, S.S.; Kim, T.W. Recent advances in energy-saving chemiresistive gas sensors: A review.
Nano Energy 2021, 79, 105369. [CrossRef]
72. Ngoc, T.M.; Van Duy, N.; Hung, C.M.; Hoa, N.D.; Trung, N.N.; Nguyen, H.; Van Hieu, N. Ultralow power consumption gas
sensor based on a self-heated nanojunction of SnO2 nanowires. RSC Adv. 2018, 8, 36323–36330. [CrossRef]
73. Ngoc, T.M.; Van Duy, N.; Hoa, N.D.; Hung, C.M.; Nguyen, H.; Van Hieu, N. Effective design and fabrication of low-power-
consumption self-heated SnO2 nanowire sensors for reducing gases. Sens. Actuators B Chem. 2019, 295, 144–152. [CrossRef]
74. Ngoc, T.M.; Van Duy, N.; Hung, C.M.; Hoa, N.D.; Nguyen, H.; Tonezzer, M.; Van Hieu, N. Self-heated Ag-decorated SnO2
nanowires with low power consumption used as a predictive virtual multisensor for H2 S-selective sensing. Anal. Chim. Acta
2019, 1069, 108–116. [CrossRef] [PubMed]
75. Kim, J.-H.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Low-voltage-driven sensors based on ZnO nanowires for room-temperature detection
of NO2 and CO gases. ACS Appl. Mater. Interfaces 2019, 11, 24172–24183. [CrossRef] [PubMed]
76. Kim, J.-H.; Mirzaei, A.; Bang, J.H.; Kim, H.W.; Kim, S.S. Selective H2 S sensing without external heat by a synergy effect in
self-heated CuO-functionalized SnO2 -ZnO core-shell nanowires. Sens. Actuators B Chem. 2019, 300, 126981. [CrossRef]
77. Kim, J.-H.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Pd-functionalized core-shell composite nanowires for self-heating, sensitive, and
benzene-selective gas sensors. Sens. Actuators A Phys. 2020, 308, 112011. [CrossRef]
78. Kou, X.; Xie, N.; Chen, F.; Wang, T.; Guo, L.; Wang, C.; Wang, Q.; Ma, J.; Sun, Y.; Zhang, H. Superior acetone gas sensor based on
electrospun SnO2 nanofibers by Rh doping. Sens. Actuators B Chem. 2018, 256, 861–869. [CrossRef]
79. Li, Y.; Zhu, J.; Cheng, H.; Li, G.; Cho, H.; Jiang, M.; Gao, Q.; Zhang, X. Developments of advanced electrospinning techniques: A
critical review. Adv. Mater. Technol. 2021, 6, 2100410. [CrossRef]
80. Rodríguez-Tobías, H.; Morales, G.; Grande, D. Comprehensive review on electrospinning techniques as versatile approaches
toward antimicrobial biopolymeric composite fibers. Mater. Sci. Eng. C 2019, 101, 306–322. [CrossRef]
81. Abideen, Z.U.; Kim, J.-H.; Lee, J.-H.; Kim, J.-Y.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Electrospun metal oxide composite nanofibers
gas sensors: A review. J. Korean Ceram. Soc. 2017, 54, 366–379. [CrossRef]
82. Islam, M.S.; Ang, B.C.; Andriyana, A.; Afifi, A.M. A review on fabrication of nanofibers via electrospinning and their applications.
SN Appl. Sci. 2019, 1, 1–16. [CrossRef]
83. Haider, A.; Haider, S.; Kang, I.-K. A comprehensive review summarizing the effect of electrospinning parameters and potential
applications of nanofibers in biomedical and biotechnology. Arab. J. Chem. 2018, 11, 1165–1188. [CrossRef]
84. Tsai, P.; Chen, J.; Ercan, E.; Chueh, C.; Tung, S.; Chen, W. Uniform luminous perovskite nanofibers with color-tunability and
improved stability prepared by one-step core/shell electrospinning. Small 2018, 14, 1704379. [CrossRef]
85. Huang, B.; Zhang, Z.; Zhao, C.; Cairang, L.; Bai, J.; Zhang, Y.; Mu, X.; Du, J.; Wang, H.; Pan, X. Enhanced gas-sensing performance
of ZnO@ In2 O3 core@ shell nanofibers prepared by coaxial electrospinning. Sens. Actuators B Chem. 2018, 255, 2248–2257.
[CrossRef]
86. Ding, B.; Wang, M.; Yu, J.; Sun, G. Gas sensors based on electrospun nanofibers. Sensors 2009, 9, 1609–1624. [CrossRef] [PubMed]
87. Kim, J.H.; Lee, J.H.; Kim, J.Y.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Enhancement of CO and NO2 sensing in n-SnO2 -p-Cu2 O core-shell
nanofibers by shell optimization. J. Hazard. Mater. 2019, 376, 68–82. [CrossRef] [PubMed]
88. Kim, J.-H.; Lee, J.-H.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Optimization and gas sensing mechanism of n-SnO2 -p-Co3 O4 composite
nanofibers. Sens. Actuators B Chem. 2017, 248, 500–511. [CrossRef]
89. Lim, S.K.; Hwang, S.-H.; Chang, D.; Kim, S. Preparation of mesoporous In2 O3 nanofibers by electrospinning and their application
as a CO gas sensor. Sens. Actuators B Chem. 2010, 149, 28–33. [CrossRef]
90. Liu, L.; Zhang, Y.; Wang, G.; Li, S.; Wang, L.; Han, Y.; Jiang, X.; Wei, A. High toluene sensing properties of NiO–SnO2 composite
nanofiber sensors operating at 330 ◦ C. Sens. Actuators B Chem. 2011, 160, 448–454. [CrossRef]
91. Im, D.; Kim, D.; Jeong, D.; Park, W.I.; Chun, M.; Park, J.-S.; Kim, H.; Jung, H. Improved formaldehyde gas sensing properties of
well-controlled Au nanoparticle-decorated In2 O3 nanofibers integrated on low power MEMS platform. J. Mater. Sci. Technol. 2020,
38, 56–63. [CrossRef]
92. Lin, Y.; Wei, W.; Li, Y.; Li, F.; Zhou, J.; Sun, D.; Chen, Y.; Ruan, S. Preparation of Pd nanoparticle-decorated hollow SnO2 nanofibers
and their enhanced formaldehyde sensing properties. J. Alloys Compd. 2015, 651, 690–698. [CrossRef]
93. Gao, X.; Li, F.; Wang, R.; Zhang, T. A formaldehyde sensor: Significant role of pn heterojunction in gas-sensitive core-shell
nanofibers. Sens. Actuators B Chem. 2018, 258, 1230–1241. [CrossRef]
94. Majhi, S.M.; Mirzaei, A.; Kim, H.W.; Kim, S.S. Reduced graphene oxide (rGO)-loaded metal-oxide nanofiber gas sensors: An
overview. Sensors 2021, 21, 1352. [CrossRef]
Chemosensors 2022, 10, 289 22 of 23

95. Cho, I.; Kang, K.; Yang, D.; Yun, J.; Park, I. Localized liquid-phase synthesis of porous SnO2 nanotubes on MEMS platform for
low-power, high performance gas sensors. ACS Appl. Mater. Interfaces 2017, 9, 27111–27119. [CrossRef]
96. Jankiewicz, B.J.; Jamiola, D.; Choma, J.; Jaroniec, M. Silica–metal core–shell nanostructures. Adv. Colloid Interface Sci. 2012, 170,
28–47. [CrossRef]
97. Lee, J.-H. Gas sensors using hierarchical and hollow oxide nanostructures: Overview. Sens. Actuators B Chem. 2009, 140, 319–336.
[CrossRef]
98. Choi, H.-J.; Kwon, S.-H.; Lee, W.-S.; Im, K.-G.; Kim, T.-H.; Noh, B.-R.; Park, S.; Oh, S.; Kim, K.-K. Ultraviolet photoactivated room
temperature NO2 gas sensor of ZnO hemitubes and nanotubes covered with TiO2 nanoparticles. Nanomaterials 2020, 10, 462.
[CrossRef]
99. Hazra, A.; Bhowmik, B.; Dutta, K.; Chattopadhyay, P.P.; Bhattacharyya, P. Stoichiometry, length, and wall thickness optimization
of TiO2 nanotube array for efficient alcohol sensing. ACS Appl. Mater. Interfaces 2015, 7, 9336–9348. [CrossRef]
100. Liu, F.-T.; Gao, S.-F.; Pei, S.-K.; Tseng, S.-C.; Liu, C.-H.J. ZnO nanorod gas sensor for NO2 detection. J. Taiwan Inst. Chem. Eng.
2009, 40, 528–532. [CrossRef]
101. Rai, P.; Song, H.-M.; Kim, Y.-S.; Song, M.-K.; Oh, P.-R.; Yoon, J.-M.; Yu, Y.-T. Microwave assisted hydrothermal synthesis of single
crystalline ZnO nanorods for gas sensor application. Mater. Lett. 2012, 68, 90–93. [CrossRef]
102. Wei, Y.; Hu, M.; Yan, W.; Wang, D.; Yuan, L.; Qin, Y. Hydrothermal synthesis porous silicon/tungsten oxide nanorods composites
and their gas-sensing properties to NO2 at room temperature. Appl. Surf. Sci. 2015, 353, 79–86. [CrossRef]
103. Da Silva, L.F.; Catto, A.C.; Avansi, W., Jr.; Cavalcante, L.S.; Mastelaro, V.R.; Andres, J.; Aguir, K.; Longo, E. Acetone gas sensor
based on α-Ag2 WO4 nanorods obtained via a microwave-assisted hydrothermal route. J. Alloys Compd. 2016, 683, 186–190.
[CrossRef]
104. Zhang, H.; Feng, J.; Wang, J.; Zhang, M. Preparation of ZnO nanorods through wet chemical method. Mater. Lett. 2007, 61,
5202–5205. [CrossRef]
105. Liu, Y.; Liu, M. Ordered ZnO nanorods synthesized by combustion chemical vapor deposition. J. Nanosci. Nanotechnol. 2007, 7,
4529–4533. [CrossRef]
106. Chien, F.S.-S.; Wang, C.-R.; Chan, Y.-L.; Lin, H.-L.; Chen, M.-H.; Wu, R.-J. Fast-response ozone sensor with ZnO nanorods grown
by chemical vapor deposition. Sens. Actuators B Chem. 2010, 144, 120–125. [CrossRef]
107. Cha, H.G.; Kim, C.W.; Kim, Y.H.; Jung, M.H.; Ji, E.S.; Das, B.K.; Kim, J.C.; Kang, Y.S. Preparation and characterization of α-Fe2 O3
nanorod-thin film by metal–organic chemical vapor deposition. Thin Solid Film. 2009, 517, 1853–1856. [CrossRef]
108. Pradhan, S.K.; Reucroft, P.J.; Yang, F.; Dozier, A. Growth of TiO2 nanorods by metalorganic chemical vapor deposition. J. Cryst.
Growth 2003, 256, 83–88. [CrossRef]
109. Liu, B.; Hu, Z.; Che, Y.; Allenic, A.; Sun, K.; Pan, X. Growth of ZnO nanoparticles and nanorods with ultrafast pulsed laser
deposition. Appl. Phys. A 2008, 93, 813–818. [CrossRef]
110. Yang, T.; Yu, H.; Xiao, B.; Li, Z.; Zhang, M. Enhanced 1-butylamine gas sensing characteristics of flower-like V2 O5 hierarchical
architectures. J. Alloys Compd. 2017, 699, 921–927. [CrossRef]
111. Sik, C.M.; Young, K.M.; Mirzaei, A.; Kim, H.-S.; Kim, S.-I.; Baek, S.-H.; Won, C.D.; Jin, C.; Hyoung, L.K. Selective, sensitive, and
stable NO2 gas sensor based on porous ZnO nanosheets. Appl. Surf. Sci. 2021, 568, 150910.
112. Kim, J.-H.; Mirzaei, A.; Kim, J.-Y.; Yang, D.-H.; Kim, S.S.; Kim, H.W. Selective CO gas sensing by Au-decorated WS2 -SnO2
core-shell nanosheets on flexible substrates in self-heating mode. Sens. Actuators B Chem. 2022, 353, 131197. [CrossRef]
113. Xia, Y.; Wang, J.; Chen, R.; Zhou, D.; Xiang, L. A review on the fabrication of hierarchical ZnO nanostructures for photocatalysis
application. Crystals 2016, 6, 148. [CrossRef]
114. Liu, J.; Zhang, L.; Fan, J.; Zhu, B.; Yu, J. Triethylamine gas sensor based on Pt-functionalized hierarchical ZnO microspheres. Sens.
Actuators B-Chem. 2021, 331, 129425. [CrossRef]
115. Cheng, P.; Dang, F.; Wang, Y.; Gao, J.; Xu, L.; Wang, C.; Lv, L.; Li, X.; Zhang, B.; Liu, B. Gas sensor towards n-butanol at low
temperature detection: Hierarchical flower-like Ni-doped Co3 O4 based on solvent-dependent synthesis. Sens. Actuators B-Chem.
2021, 328, 129028. [CrossRef]
116. Guo, M.; Luo, N.; Chen, Y.; Fan, Y.; Wang, X.; Xu, J. Fast-response MEMS xylene gas sensor based on CuO/WO3 hierarchical
structure. J. Hazard. Mater. 2022, 429, 127471. [CrossRef]
117. Yu, H.; Guo, C.; Zhang, X.; Xu, Y.; Cheng, X.; Gao, S.; Huo, L. Recent Development of Hierarchical Metal Oxides Based Gas
Sensors: From Gas Sensing Performance to Applications. Adv. Sustain. Syst. 2022, 6, 2100370. [CrossRef]
118. Mirzaei, A.; Janghorban, K.; Hashemi, B.; Neri, G. Metal-core@metal oxide-shell nanomaterials for gas-sensing applications: A
review. J. Nanoparticle Res. 2015, 17, 371. [CrossRef]
119. Yamazoe, N. New approaches for improving semiconductor gas sensors. Sens. Actuators B Chem. 1991, 5, 7–19. [CrossRef]
120. Mirzaei, A.; Yousefi, H.R.; Falsafi, F.; Bonyani, M.; Lee, J.-H.; Kim, J.-H.; Kim, H.W.; Kim, S.S. An overview on how Pd on resistive-
based nanomaterial gas sensors can enhance response toward hydrogen gas. Int. J. Hydrogen Energy 2019, 44, 20552–20571.
[CrossRef]
121. Iordache, S.M.; Ionete, E.I.; Iordache, A.M.; Tanasa, E.; Stamatin, I.; Grigorescu, C.E.A. Pd-decorated CNT as sensitive material for
applications in hydrogen isotopes sensing-Application as gas sensor. Int. J. Hydrogen Energy 2021, 46, 11015–11024. [CrossRef]
122. Li, G.; Fan, Y.; Hu, Q.; Zhang, D.; Ma, Z.; Cheng, Z.; Wang, X.; Xu, J. Morphology and size effect of Pd nanocrystals on
formaldehyde and hydrogen sensing performance of SnO2 based gas sensor. J. Alloys Compd. 2022, 906, 163765. [CrossRef]
Chemosensors 2022, 10, 289 23 of 23

123. Shen, S.-K.; Cui, X.-L.; Guo, C.-Y.; Dong, X.; Zhang, X.-F.; Cheng, X.-L.; Huo, L.-H.; Xu, Y.-M. Sensing mechanism of Ag/α-MoO3
nanobelts for H2 S gas sensor. Rare Met. 2021, 40, 1545–1553. [CrossRef]
124. Kim, J.-H.; Kim, S.S. Realization of ppb-scale toluene-sensing abilities with Pt-functionalized SnO2 –ZnO core–shell nanowires.
ACS Appl. Mater. Interfaces 2015, 7, 17199–17208. [CrossRef]
125. Kim, J.-H.; Wu, P.; Kim, H.W.; Kim, S.S. Highly selective sensing of CO, C6H6, and C7 H8 gases by catalytic functionalization with
metal nanoparticles. ACS Appl. Mater. Interfaces 2016, 8, 7173–7183. [CrossRef]
126. Li, X.; Yu, J.; Wageh, S.; Al-Ghamdi, A.A.; Xie, J. Graphene in photocatalysis: A review. Small 2016, 12, 6640–6696. [CrossRef]
127. Schedin, F.; Geim, A.K.; Morozov, S.V.; Hill, E.W.; Blake, P.; Katsnelson, M.I.; Novoselov, K.S. Detection of individual gas molecules
adsorbed on graphene. Nat. Mater. 2007, 6, 652–655. [CrossRef]
128. Chatterjee, S.G.; Chatterjee, S.; Ray, A.K.; Chakraborty, A.K. Graphene–metal oxide nanohybrids for toxic gas sensor: A review.
Sens. Actuators B Chem. 2015, 221, 1170–1181. [CrossRef]
129. Pendolino, F.; Armata, N. Graphene Oxide in Environmental Remediation Process; Springer: Berlin/Heidelberg, Germany, 2017;
Volume 11.
130. Hummers, W.S., Jr.; Offeman, R.E. Preparation of graphitic oxide. J. Am. Chem. Soc. 1958, 80, 1339. [CrossRef]
131. Brodie, B.C. Hydration behavior and dynamics of water molecules in graphite oxide. Ann. Chim Phys. 1860, 59, 466–472.
132. Shewale, P.S.; Yun, K.-S. Synthesis and characterization of Cu-doped ZnO/RGO nanocomposites for room-temperature H2 S gas
sensor. J. Alloys Compd. 2020, 837, 155527. [CrossRef]
133. Liu, Z.; Yu, L.; Guo, F.; Liu, S.; Qi, L.; Shan, M.; Fan, X. Facial development of high performance room temperature NO2 gas
sensors based on ZnO nanowalls decorated rGO nanosheets. Appl. Surf. Sci. 2017, 423, 721–727. [CrossRef]
134. Jia, A.; Liu, B.; Liu, H.; Li, Q.; Yun, Y. Interface design of SnO2 @PANI nanotube with enhanced sensing performance for ammonia
detection at room temperature. Front. Chem. 2020, 8, 383. [CrossRef]
135. Amiri, V.; Roshan, H.; Mirzaei, A.; Neri, G.; Ayesh, A.I. Nanostructured metal oxide-based acetone gas sensors: A review. Sensors
2020, 20, 3096. [CrossRef]
136. Sharma, H.J.; Salorkar, M.A.; Kondawar, S.B. H2 and CO gas sensor from SnO2 /polyaniline composite nanofibers fabricated by
electrospinning. Adv. Mater. Proc. 2017, 2, 61–66. [CrossRef]