10.1515 - Revac 2021 0127

Reviews in Analytical Chemistry 2021; 40: 33–57
Review Article Open Access
Vardan Galstyan*, Annalisa D’Arco, Marta Di Fabrizio , Nicola Poli , Stefano Lupi,
and Elisabetta Comini
Detection of volatile organic compounds: From

chemical gas sensors to terahertz spectroscopy
https://doi.org/10.1515/revac-2021-0127 1 Introduction
received: November 02, 2020; accepted: February 16, 2021
Volatile organic compounds (VOCs) belong to the family
Abstract: Volatile organic compounds are released by
of toxic chemicals including hydrocarbons, alcohol,
different sources causing air pollution. Moreover, some
ketones, chlorine, and nitrogen-based compounds [1-4].
of these carbon-based organic chemicals are conside-
VOCs are produced by natural and/or anthropogenic
red as biomarkers in the exhaled breath of individuals
sources [5-7]. Natural sources represent the metabolic
and can be used to identify various kinds of diseases.
processes in animals and living beings. Furthermore, the
Hence, the increasing demand to control air quality
concentration variation of some VOCs in human exhaled
and human health has promoted the development of
breath is a symptom of gastrointestinal, respiratory, or
monitoring systems based on high-performance gas
metabolic pathologies [8,9]. For example, relatively high
sensing structures. This review highlights the achie-
concentrations of acetone can be observed in the exhaled
vements in sensing technologies for the detection of
breath of diabetic patients. In addition, VOCs are emitted
volatile organic compounds. Particularly, chemiresis-
from industrial areas, waste burning, cooking, plants
tive gas sensors and detection systems based on the
and many other sources resulting in the formation of
terahertz spectroscopy method are outlined. The pro-
oxidants, which are harmful to the ecosystem and human
gress in research studies is discussed and the potential
health [6-10].
of both techniques is evaluated considering the current
Most of the VOCs have low boiling points and vapo-
challenges. Afterward, a brief summary is also provided
rize even at room temperature (RT) resulting in a rapid
along with the advances and issues for future investi-
spread in the environment [6]. Hence, VOCs are consi-
gations and the manufacturing of highly sensitive and
dered indoor and outdoor air pollutants [7,8]. Therefore,
selective monitoring systems.
the detection of VOCs to ensure the indoor and outdoor
air quality is an important issue. Thus, the increasing
Keywords: VOCs, metal oxide nanomaterials, chemical
demand for sensing systems for air quality and human
gas sensors, THz spectroscopy
health monitoring stimulates the development of advan-
ced detection technologies [11-15].
There are different analytical methods based on
chemical and physical principles for the detection of
* Corresponding author: Vardan Galstyan, Sensor Lab, VOCs [16-18]. In this respect, the small size chemical
Department of Information Engineering, University of Brescia, gas sensors based on semiconductor materials can be
Via Valotti 9, 25133 Brescia, Italy,
applied as an effective tool for the detection and quan-
e-mail: [email protected]
Annalisa D’Arco: INFN-Rome1 P.le A. Moro 5, 00185, Rome, Italy;
tification analysis of VOCs [19-23]. The conductance of
University of Rome ‘La Sapienza’, P.le A. Moro 5, 00185, Rome, Italy semiconductors is changed due to their interaction with
Marta Di Fabrizio: University of Rome ‘La Sapienza’, P.le A. Moro 5, reducing or oxidizing gases, which is used as a signal
00185, Rome, Italy to identify the presence of different VOCs [24,25]. The
Nicola Poli and Elisabetta Comini: Sensor Lab, Department of importance of chemiresistive gas sensors has been high-
Information Engineering, University of Brescia, Via Valotti 9,
lighted by a large number of studies performed over the
25133 Brescia, Italy
Stefano Lupi: University of Rome ‘La Sapienza’, P.le A. Moro 5, last few years, where the response, selectivity, stability,
00185, Rome, Italy; INFN-LNF Via E. Fermi 40, 00044 Frascati, and operating temperature of the sensing structure have
Rome, Italy been improved to meet the requirements of modern
Open Access. © 2021 Vardan Galstyan et al., published by De Gruyter. This work is licensed under the Creative Commons
Attribution 4.0 International License.
34 Vardan Galstyan et al.
monitoring systems [26-31]. The solid-gas interface plays 2 Operation principles

a significant role in the interaction between the semi-
conductor and analyte [32]. Hence, the morphology of
2.1 Chemical gas sensors
sensing material has a crucial effect on the improvement
of its functionalities. Great emphasis has been placed
Metal oxide nanomaterials are commonly used for the
on the preparation of nanostructured semiconductor
fabrication of chemical gas sensors [53-58]. They are solid
materials. The increase in surface area to volume ratio,
structures that contain positively charged metal cations
the variation of the shape and morphology of semicon-
and the negative oxide anion [59]. The high-temperature
ductor nanostructures affect their sensing performance
stability, the tunable band gap and the established syn-
[31,33-38]. Meanwhile, the doping and functionalization
thesis techniques of oxide materials make them very
of semiconductors may enhance their interaction with a
attractive for a wide range of applications [11,23,28,60-65].
specific analyte [39-42]. In this context, morphological,
Metal oxide nanostructures with different shapes and sizes
compositional, and structural effects on the sensing pro-
can be synthesized by top-down and bottom-up methods
perties of metal oxide nanomaterials have been exten-
using chemical and physical procedures (Figure 1a). The
sively studied for their integration into chemiresistive
detailed description of the synthesis methods we have
sensing devices [43-45].
reported in our previous works [25,37,66]. A typical chemi-
In the meantime, progress has been made towards the
resistive gas sensor based on metal oxide nanostructures
development of new systems for the detection and identi-
is fabricated as follows: The sensing material is prepared
fication of VOCs by spectroscopy methods including the
on an insulating substrate. To perform the sensing mea-
vibrational spectroscopy [46-52].
surements at different operating temperatures a platinum
Furthermore, new and advanced technologies based
(Pt) heater element and electrical contacts are deposited
on optical sensors (including vibrational spectroscopy)
on the backside of the substrate and on the surface of
may provide complementary approaches to conventio-
semiconductor material, respectively (Figure 1b).
nal analytical methods for the detection and recognition
The operating principles of chemical gas sensors are
of VOCs. Although these techniques have been proven to
based on the interaction mechanism of the analyte mole-
be able to detect various VOCs, the optical gas sensing
cules with the sensing material. The atmospheric oxygen
systems can overcome issues related to chemiresistive
(O2) adsorbs on an n-type semiconductor nanomaterial
gas sensors and exhibiting detection limits, demonstra-
extracting electrons from its conduction band (Eq. 1 and
ting sensing characteristics comparable with gas chro-
2, [32,68]).
matography. Among the optical sensing systems, the
Terahertz (THz) spectroscopy is of increasing interest as O2 + e −  O2− (1)
a rapidly emerging technology in the field of analytical
O2− + e −  2O− (2)
chemistry. It provides selective non-intrusive identifica-
tion of polar gas molecules, through the interrogation of Consequently, an electron depleted layer and a poten-
molecular roto-vibrational modes with THz radiation. Its tial barrier are formed at the grain boundaries of the mate-
potential is related to numerous absorption and emis- rial (Figure 2). The depletion width (W) and the height of
sion molecular lines of interest suitable to recognize the potential barrier (qVs) are determined as follows:
gas-phase VOCs, ensuring high selectivity and sensiti-
vity. Thus, THz spectroscopy and the variability of the εε 0VS
W= (3)
optical schemes offer several advantages, especially for
qN d
practical applications in optically harsh environments,
such as atmospheric, combustion, and industrial safety
q 2 N S2
monitoring. qVS = (4)
Herein, we outline the recent achievements in the 2εε 0 N d
detection of VOCs using two different approaches, namely
the chemiresistive gas sensors and the THz spectroscopy. where ε0 and ε are the permittivity of vacuum and metal
After a brief overview of both technologies, the discussion oxide material (unit, F⋅m-1), respectively, VS is the band
will be focused on the studies of chemical gas sensors and bending (unit, eV), q is the electrical charge of carrier
detection systems based on THz spectroscopy conside- (unit, Coulomb), Nd is the concentration of charge car-
ring their potential for application in environmental and riers (unit, m-3), NS is the density of surface states (unit,
health monitoring systems. number⋅cm-2). The surface charge is determined by the
Detection of volatile organic compounds: From chemical gas sensors to terahertz spectroscopy 35
Figure 1: (a) The schematic representation of the top-down and bottom-up approaches for the fabrication of metal oxide nanostructures.
Reprinted from Ref. [67]. (b) The schematic of a chemiresistive transducer (original image).
Figure 2: (a) A model showing the ionosorption of atmospheric oxygen and the formation of a potential barrier at the grain boundaries of
metal oxide material. (b) The illustration of the band bending in the metal oxide structure due to the ionosorption of atmospheric oxygen on
its surface, where EC, EV, and EF are the energy of the conduction band, valence band, and the Fermi level, respectively (original image).
concentration of ionosorbed oxygen and the Debye length The formation of ionosorbed oxygen species on the
(LD, in nm, Eq. 5), where k is the Boltzmann constant surface of the sensing materials is varied depending on
(units, eV⋅K-1, J⋅K-1) and T is the absolute temperature in its operating temperature. It has been demonstrated that
Kelvin. O− is a more active form and dominates at relatively high
operating temperatures of semiconductor material (200-
εε 0 kT
LD = (5) 400°C) [32]. Therefore, most of the chemiresistive gas
q2 Nd sensors operate above 200°C [69]. If the sensing structure
is an n-type oxide material, its electrical conductance will a continuous and simultaneous monitoring of multicom-
decrease due to the reduction of the concentration of free ponent gaseous compounds compatible with online data
electrons (Figure 2). When a VOC (rvoc) is present in the processing [71-79].
atmosphere, it will react with the ionosorbed oxygen and The fundamentals of vibrational spectroscopy and
will be oxidized restoring the conductance of the sensing the instrumental optical schemes have been widely dis-
structure (Eq. 6 and 7, [32,68]). Consequently, the conduc- cussed elsewhere [80-82]. In particular, for infrared (IR)
tance of p-type semiconductor materials will be varied in and THz spectroscopy, the common approach is based
the opposite direction due to the adsorption of oxidizing on the irradiation of the confined gaseous compounds
and reducing gases on its surface. by light and the acquisition of their spectral information
(Figure 3). The vibration transitions by mono and polyato-
rvoc + O2− → rvoc O2 + e − (6) mic molecules, that involve a change in dipole moment,
rvoc + O− → rvoc O + e − (7) result in the absorption of photons. For example, in many
gases, IR/THz radiation excites molecular bonds (rotatio-
The aforementioned changes in the electrical para- nal and vibrational) resulting in specific absorption lines
meters of sensing material affected by the gaseous species or bands in these electromagnetic spectral regions.
are used as the signal to detect the target VOCs [70]. Hence, In the near-IR (4000-14000 cm-1) spectral region,
the composition, structure, and morphology of the metal the overtones of fundamental vibrations present in the
oxides including the chemical structure of the VOC are the mid-IR are observed. Here, powerful sensor technolo-
key factors to determine the response, selectivity, and sta- gies are available from telecommunication applications.
bility of gas sensors. However, many gases of interest for pollution and human
breath analysis do not have absorption lines in this region
or they are significantly weaker compared to the ones
2.2 THz spectroscopy in mid-IR spectral range (400-4000 cm-1). In contrast,
the majority of gases have main absorption lines in the
Vibrational spectroscopy is a non-destructive optical spectral window of mid-IR, while polyatomic gases show
approach that became one of the most promising dense and complex absorption spectra making difficult
directions in gas sensing technologies, due to its high recognition of gas mixtures with the reduction of sensi-
sensitivity and selectivity, as well as its reagent free cha- tivity without spectral deconvolution. Instead, in the THz
racteristic. Vibrational spectroscopy technique allows the spectral region (from nearly 3 to 300 cm-1, corresponding
development of high-performance detection systems for to 0.1-10 THz), the polar gases have relatively few lines
Figure 3: The interaction scheme in IR/THz vibrational spectroscopy with single- or multi-component gas mixtures. Typical frequency and
wavelength ranges are shown for THz, MIR, and NIR (original image).
showing superior properties to the IR technique in terms The most used system as substance identification
of spectral resolution, thus facilitating their specific and tool is the THz-TDS technique, both in single and in
selective recognition [83]. This high selectivity in the THz multi-component VOCs mixtures in liquid- and gas-phase
region is a crucial point to define the analytical utility for [93-102]. The working principle of a THz-TDS scheme is
gas-phase sensing applications. based on the detection (mostly in transmission or reflec-
First of all, THz radiation has a low photon energy tion modes) of a broadband THz source (typically ranging
(4meV @ 1THz) that cannot ionize molecules and is not from hundreds of GHz to some THz) after its interaction
sufficient to cause combustion in inflammable materials with the sample [85,103]. Many schemes and materials
[84-86]. Moreover, it strongly interacts with polar mole- can be used for THz wave collection in THz-TDS [104-106]
cules (more than the microwave spectral region [87-90]), with coherent detection mode [107]. Thus, both amplitude
while nonpolar materials (like paper, cloths, and plastic) and phase of the THz pulse electric field can be simulta-
are usually transparent in THz range [91]. The strength neously measured and the optical parameters including
of the absorption in the THz spectral range for gas mole- sample absorption coefficient and refractive index can be
cules is on the same order of magnitude of mid-IR range extracted without using Kramers-Kronig relations [84,85].
and from 103 to 106 times stronger than that in the mic- The optical features of sample may be evaluated by coll-
rowave region [92]. In addition, the THz time-domain ecting the THz waveform after the interaction with the
spectroscopy (THz-TDS) has advantages compared to the sample and comparing it with the reference THz pulse
Fourier-transform IR (FT-IR) spectroscopy: it is not sensi- (no sample inserted in the optical path). Figure 4a reports
tive to the thermal background, shows a higher SNR and the schematic layout of the THz-TDS setup available at
does not require the use of cooled detectors [82]. Terahertz laboratory (University of Rome ‘La Sapienza’,
Moreover, the photon energy of THz waves coin- [108,109]).
cides with energy levels corresponding to low-fre- The spectral resolution depends on the total length
quency motions, such as vibration, rotation, and of the optical delay line (DL) scanning used to reconstruct
translation modes of molecules in their condensed phases the THz pulse. Consequently, the longer the length, the
as well as the intermolecular vibrations, such as hydrogen higher the resolution. A spectral resolution of some GHz
bonds [85]. can be reached with a typical THz-TDS scheme [92].
Figure 4: (a) Schematic layout of a typical THz-TDS setup in transmission mode based on switched photoconductive antennas (PCAs).
A femtosecond near-IR (NIR) laser beam is divided in two parts by a beam splitter. Some mirrors (M) convey the laser beams to the THz emitter
and receiver, where they are focused by a NIR lens. Here the THz beam is produced and detected, respectively. A stack of transparent THz
lenses collimates and focuses THz radiation along the path and a gas cell is inserted into the THz propagation region. The acquisition chain
consists of a Lock-in amplifier (LIA), a data acquisition card (DAQ) and a personal computer for data collection and analysis. The optical delay
line is used to sample the THz pulse in the time domain. (b) Temporal profile of THz electric field. (c) Power spectrum as a function of THz
frequency. The presented THz-TDS setup is available at Terahertz laboratory, University of Rome ‘La Sapienza’ (original image).
Figure 5: Schematic layout of THz-FDS setup. Two continuous wave tunable lasers at adjacent frequencies beat in a laser combiner and
illuminate the THz emitter and receiver for THz generation and detection. Optical fibers are used to carry out laser signals. A 4-parabolic
mirror (PM) system collimates and focuses THz radiation along the path. If only 2-PM system is used the sample is placed in the collimated
region of the THz beam. The acquisition chain is based on lock in detection (original image).
THz-FDS is closely related to TDS in physical proces- they exhibit enhanced functionalities compared to those
ses, measurement and detection scheme [110]. It typically of bulk materials [27,29,45,112]. The sensing parameters of
operates in the frequency range of 0.05 to 3 THz [111]. metal oxide nanostructures for the detection of VOCs are
In comparison to the TDS, the main advantages of FDS listed in Table 1. It is well known that the most popular
are the high frequency resolution ~MHz, the possibility metal oxide that has been used for the manufacturing of
to work at a fixed frequency or in frequency range, the chemiresistive gas sensors is the tin dioxide (SnO2). The
relatively low cost of system and the fact that does not preparation of SnO2 nanostructures with different shapes
need Fourier Transform algorithms for spectral analysis. increases the specific surface area of the material affec-
Figure 5 shows the schematic representation of a typical ting its sensitivity towards a wide range of VOCs [113-116].
THz-FDS setup. Like the THz-TDS, the coherent detec- Hence, the grain size plays a crucial role in the enhance-
tion mode is adopted, however, no delay line is present ment of sensing properties of SnO2 [117]. When the grain
because no temporal profile of THz pulse is acquired size of SnO2 is comparable to 2LD, the grains are fully
during the measurement. depleted by electrons enhancing the sensing response
of the material. For example, the reduction of SnO2 par-
ticle size to 2-5 nm increased the concentration of surface
3 Functionalities of chemical gas oxygen vacancies and improved the sensing performance
of structure to ethanol at a relatively low operating tem-
sensors perature (230°C) [33]. Li et al. obtained SnO2 spherical
structures with a crystallite size of 8 nm and the material
Extensive efforts have been made on the integration of exhibited a high sensing response towards formaldehyde
oxide nanostructures in chemical sensing devices since (H2CO) at 200°C [113]. In order to improve the performance
Table 1: Sensing parameters of metal oxide nanostructures for the detection of VOCs at their optimum operating conditions
Material/ Operating Analyte, Response Response/ LOD Stability/ Ref.

morphology temperature concentration (ppm) recovery (ppb) reproducibility
(°C) time (s)
SnO2 microspheres 200 H2CO, 100 Ra/Rg, 38 17/25 ‒ 6 cycles† [113]
SnO2 microspheres 230 Ethanol, 100 Ra/Rg, 25 3/24 500 6 cycles [33]
SnO2 nanowire 450 Ethanol, 25 Vg/Va 6.1 15/41 ‒ ‒ [114]
SnO2 hollow spheres 250 H2CO, 200 Ra/Rg, 194 190/35 ‒ ‒ [115]
SnO2 hollow spheres 250 2-propanol, 200 Ra/Rg, 237 145/100 ‒ 15 days [115]
SnO2 hollow spheres 350 Toluene, 200 Ra/Rg, 14 130/200 ‒ ‒ [115]
SnO2 hollow spheres 250 Methanol, 200 Ra/Rg, 79 340/130 ‒ ‒ [115]
SnO2 nanorings 250 Isopropanol, 100 Ig/Ia, 7.3 7/39 1000 10 cycles [116]
a‒Fe2O3 nanowires 280 Ethanol, 100 Ra/Rg, 45 16/28 ‒ 6 cycles [118]
WO3 nanoparticles 400 Acetone, 0.5 (Ig-Ia)/Ia, 2.3 330/180 170 ‒ [120]
In2O3 nanoparticles 100 H2CO, 10 Ra/Rg, 68 122/39 1000 1 month [34]
NiO nanocuboinds 120 acetoin, 50 Rg/Ra, 302 92/82 500 36 days [35]
ZnO nanorods 300 Ethanol, 100 Ra/Rg, 45 6/31 ‒ 30 days [36]
ZnO nanobristles RT Ethanol, 100 Ra/Rg, 464 19/12 ‒ 3 cycles [122]
TiO2 nanograins 450 Ethanol, 150 Ra/Rg, 6 ‒/600 700 3 cycles [119]
Pt‒TiO2 300 Acetone, 200 Ra/Rg, 29 13/30 ‒ 30 days [137]
Pd‒In2O3 nanoparticles 350 Ethanol, 5 Ra/Rg, 159 ‒ ‒ ‒ [121]
Pt‒In2O3 nanofibers 180 Acetone, 50 Ra/Rg, 105 6/9 10 50 days [126]
Pd‒Au-SnO2 nanosheets 250 Acetone, 2 Ra/Rg, 6.5 5/4 45 6 cycles [41]
Ag‒SnO2 nanofibers 100 Acetone, 50 Ra/Rg, 40 6/10 ‒ 4 cycles [127]
Y‒SnO2 flower-shaped 180 H2CO, 50 Ra/Rg, 18 ‒ 1000 2 months [42]

nanostructures
Ni‒SnO2 nanorods 450 Ethanol, 50 Ra/Rg, 2000 30/600 ‒ ‒ [128]
Fe‒ZnO Nanosheet-Spheres 300 H2CO, 10 Ra/Rg, 33 42/11 ‒ ‒ [138]
Al‒NiO nanofibers 325 Methanol, 200 Rg/Ra, 10 199/15 ‒ 4 cycles [139]
Ag‒ (TiO2/SnO2) 275 Ethanol, 50 Ra/Rg, 53 3.5/7 1000 30 days [134]
CuO/Ti3C2Tx nanoparticles 250 Toluene, 50 Rg/Ra, 11 270/10 320 ‒ [13]
NiO/SnO2 nanoparticles RT Ethanol, 100 Rg/Ra, 140 23/13 1000 ‒ [136]
SnO2/NiO/Au hollow sphere 75 Ethanol, 40 (Ra-Rg)/Rg, 38 ‒ ‒ 35 days [133]
TiO2/SnO2 branched mesopores 350 Ethanol, 50 Ra/Rg, 40 7/5 200 30 days [131]
TiO2/WSe2 nanospheres/ RT Ethanol, 30 Rg/Ra, 10 2/2 ‒ 1 month [29]

nanosheets
Y2O3/ZnO nanoparticles RT 2-methoxyethanol, 100 Rg/Ra, 599 17/21 ‒ 30 days [135]
Ra and Rg are the resistance values of structures in air and in the presence of analyte, respectively. Ia and Ig are the conductance values of
structures in air and in the presence of analyte, respectively. Va and Vg are the voltage drop measured across the reference resistor in pre-
sence of the analyte and in air. † Cycles of sensing tests performed at the same operating conditions.
of conventional gas sensors, the functional proper- The conductance of metal oxide nanostructures can
ties of many other metal oxide nanostructures, such as be affected due to the adsorption and desorption pro-
ZnO, Fe2O3, TiO2, WO3, NiO, and In2O3 have been studied cesses of different VOCs on their surface. Therefore, the
[34-36,118-120]. selectivity of chemical sensors is one of the major issues
The stability of the functional parameters of the fab- that should be overcome. Different strategies to enhance
ricated sensors was analyzed from a few cycles to a few the response and selectivity of metal oxide sensors have
tenths of days using the same test protocol (Table 1). been utilized. One of the most common approaches to
The obtained results mainly indicate the reliability of improve the performance of chemiresistive sensors is the
chemical sensors based on metal oxide nanomaterials. functionalization of oxide materials with catalytic mate-
However, the tests should be performed for longer periods rials. Noble metals can be used to activate the reactions
to confirm their long-term stability. between the oxide materials and specific VOCs. Gold (Au),
In general, the high activation energies are in need palladium (Pd), and Pt nanoparticles affect the disso-
to improve the interaction between the semiconduc- ciation of atmospheric O2 on the surface of metal oxides
tor materials and VOCs [32,67,114,121]. As can be seen in increasing the concentration of adsorption sites for VOCs,
Table 1, some sensing structures based on pure oxide while the response of the sensors towards oxidizing gases
nanomaterials showed a good response towards VOCs at will be decreased (Figure 7, [121,126]). Meanwhile, the
relatively low operating temperatures, which is another electronic sensitization of noble metals plays a signifi-
important achievement and favorable for the manufac- cant role in the functionalities of chemical sensors due
turing of low power consumption detection systems. to the formation of a potential barrier (Schottky barrier)
For example, In2O3 nanoparticles with the dimension and the increase of the thickness of the depletion layer at
of 2-15 nm exhibited a high response towards H2CO, at the interface between oxide material and catalyst. Hence,
100°C [34]. Moreover, ZnO nanobristles showed good the electrons are released more readily from the surface
and reproducible sensing performance towards ethanol reactions at the noble metal/metal oxide interface to the
at room temperature (RT) [122]. However, the water (H2O) conduction band and affect the electron charge transfer
vapor can be adsorbed on the chemical gas sensors at RT dynamics [42,121]. Moreover, the functionalization of SnO2
affecting their functionalities [66]. Therefore, the humi- nanofibers with silver (Ag) nanoparticles and further oxi-
dity effect on the VOC sensors should be considered in dation of Ag to the Ag2O leads to the formation of a p-n
detail to determine their operating temperature. In the heterojunction. Consequently, the formed heterojunction
meantime, the crystal structure of oxide materials may between the n-type SnO2 and p-type Ag2O increases the
affect their sensing response [123]. Recently, it has been width of the depletion layer of SnO2 affecting the structure
demonstrated that the crystalline phase of WO3 nano- response to acetone [127]. However, the aforementioned
particles has a significant effect on their response and investigations indicate that the catalytic layers accelerate
selectivity towards acetone [122]. In particular, the mono- the interaction processes of oxide materials with VOCs
clinic γ-WO3 crystalline phase is more reactive compared mainly enhancing the response of sensors. Therefore,
to the orthorhombic β-WO3. Furthermore, the large dipole understanding the behavior of each catalyst to make the
moment of monoclinic γ-WO3 can enhance the interaction sensors sensitive to a particular VOC is an important issue
of the material with a polar compound such as acetone and should be further studied.
affecting its selectivity (Figure 6). The doping of metal oxide nanomaterials is another
The overall findings suggest that metal oxide nano- effective way to enhance their response and selectivity
materials with various shapes are very promising structu- towards VOCs. The incorporation of dopant materials
res for the application in VOC detection systems (Table 1). into the structure of metal oxides will introduce crystal
It should be noted that the harmful effects caused by defects, which will lead to the formation of oxygen vacan-
VOCs depend on their type and concentration [6,7]. Fur- cies enhancing the interaction of the material with VOCs
thermore, the identification of the exact concentration of [40,42,123,128]. Furthermore, the dopants with a higher
VOCs in human exhaled breath is important to evaluate oxidation state may replace the atoms of metal oxides
the human health status [124,125]. In this respect, it is of maintaining the same oxidation state of the nanostruc-
great significance to identify the smallest concentration of ture, and thus increase its electrical conductivity [39,129].
the analyte (so-called limit of detection (LOD)) that can be This is an important factor to read out the conductance
detected by the chemical gas sensors. Unfortunately, the change (sensing signal) of metal oxide gas sensors using
LOD of most of the fabricated sensors was not evaluated cost-effective and small size electrical devices. As we have
(Table 1). mentioned before, the crystal structure of material may
Figure 6: (a) Raman spectra of WO3‒1† and WO3‒2‼ structures. The blue arrows in the spectrum of WO3‒2 show the orthorhombic β-WO3
phase. (b) FTIR reflectance spectra of WO3‒1 and WO3‒2 in the spectral region between 600 and 1200 cm-1. (c) Conductance dependence
of WO3‒1 and WO3‒2 from the concentration of RH at 400°C. (d) Response values of WO3‒1 and WO3‒2 to 500 ppb and 2 ppm of acetone
at different concentrations of RH. (e) Response of WO3‒1 and WO3‒2 towards acetone, ethanol, ammonia (NH3), ethylene, methane (CH4),
carbon dioxide (CO2), and carbon monoxide (CO) at 400°C. (f) Selectivity of WO3‒1 and WO3‒2 against interfering gases at 400°C (ks was
calculated using the response values of sensors towards 10 ppm of acetone with respect to their response values towards ethanol (10 ppm),
NH3 (10 ppm), ethylene (10 ppm), CH4 (100 ppm), CO2 (800 ppm), and CO (50 ppm). Because the WO3‒1 and WO3‒2 structures are almost
not sensitive to NH3 and CH4, for our calculations, we considered the response values of both materials to the aforementioned gases to
be 0.9. † WO3 nanoparticles crystallized into the monoclinic γ-WO3 phase. ‼ WO3 nanoparticles crystallized into the monoclinic γ-WO3 and
orthorhombic β-WO3 phase. Reprinted with permission from Ref. [120]. Copyright 2020, The Royal Society of Chemistry (RSC).
affect its reactivity [123]. The semiconductor gas sensors at high operating temperatures and stabilize the sensing
mainly operate at elevated temperatures, where is possi- performance of metal oxides [123].
ble a structural phase transition in the sensing material To improve the electronic and sensing properties
[123,130]. The phase transition will destabilize the func- of metal oxides is possible by coupling them in more
tional properties of sensing devices. In this regard, some complex structures achieving a synergetic effect between
dopant materials may inhibit the phase transition effect different materials (Figure 8, [131,132]). Recent studies
Figure 7: (a) The sensors’ response to 1 ppm acetone versus the working temperature, (b) the dynamic response curves in the concentration
range of 0.3-5 ppm, (c) the linear relationship between response and acetone concentrations, (d) the selectivity tests for the pristine In2O3
PNFs‡ and 20/50/100 Pt−In2O3 PNFs sensors. ‡ Porous nanofibers. Reprinted with permission from Ref. [126]. Copyright 2019, Elsevier.
suggest that this is a very efficient strategy to improve However, the investigations on composite structures
the response and selectivity of chemical sensors towards for sensing applications indicate that this topic is still
a specific VOC. A wide range of oxide materials can be in its infancy. Therefore, the combination of different
used for the development of sensors based on composite materials in composite sensing structures may open new
structures [131,133-135]. Moreover, the research findings possibilities to improve their functionalities. In addition,
show that the coupling of semiconductor nanomateri- further studies should be carried out considering the com-
als with different types of conductivity will result in the position of composite and the concentration of materials
formation of a p-n heterojunction, where the modulation in the structure to improve its selectivity towards a speci-
of the junction due to the interaction of the composite fic VOC. Furthermore, more investigations are needed to
structure with VOCs plays a critical role in the perfor- evaluate the stability of metal oxide nanomaterials, which
mance of the sensing device at low operating temperatu- is important for the development of sensing devices with
res. Jayababu, et al. reported that the formation of a p-n the reproducible functional properties.
junction between the n-SnO2 and p-NiO resulted in the
transfer of electrons from SnO2 to NiO and in the trans-
fer of holes in the opposite direction creating a depletion
layer at the interface of both materials [136]. The electrons
4 Sensing systems based on THz
will be trapped by the atmospheric oxygen resulting in spectroscopy
an increase of the depletion layer width at the p-n junc-
tion. Thus, the increase in the concentration of adsorbed Analytical spectroscopy represents a complementary
oxygen species will improve the interaction of the sensing approach for the detection of VOCs. A large part of these
structure with ethanol at RT. Moreover, Motsoeneng et al. common techniques uses IR spectral regions. The spec-
obtained similar results confirming the aforementioned troscopic methods include non-dispersion IR (NDIR),
hypothesis [133]. They also suggested that the concentra- differential absorption LIDAR (DIAL), differential optical
tion of materials in the composite structure may have a absorption spectroscopy (DOAS), tunable diode laser
significant effect in its sensing response. absorption spectroscopy (TDLAS), Fourier transform
Figure 8: (a) Responses of HMT, SnO2 NCs, and SHMT‐based sensors toward 50 ppm ethanol at different operating temperatures
(150-500°C). (b) Response curves of gas sensors based on SnO2 NCs, HMT, and SHMT materials toward different concentration of ethanol
(50-400 ppm) at 350°C, (c) responses of the sensors based on SnO2 NCs, HMT, and SHMT sensors to ethanol vapor under different
concentrations (50-400 ppm). (d) Dynamic response‐recovery curve of the SHMT to 50 and 400 ppm ethanol. (e) Responses of SHMT sensor
to various gases at 50 ppm to test the selectivity. (f) Comparison of the response and response/recovery time based on SMO sensors
Reprinted with permission from Ref. [131]. Copyright 2019, John Wiley & Sons.
infrared (FTIR) spectroscopy [81], open-path FTIR (OP- between the magnitude of the absorptions in the spect-
FTIR) useful for measuring atmospheric gas species [140], rum and the gas concentration [148]. Simple models,
and dual-comb spectroscopy (DCS) [141-143]. such as the single-linear-regression (SLR) and the multi-
Among the aforementioned approaches, FTIR spec- ple-linear-regression (MLR) can be used to evaluate the
troscopy is largely adopted and recommended as an concentrations.
optical technique for the detection of VOCs showing high The accuracy of the identification of each component
sensitivity, signal-to-noise ratio (SNR) and spectral reso- is crucial in multi-component gas mixtures (for example,
lution [144,145]. The LOD of the sensors based on FTIR in air quality monitoring). It may have drawbacks of low
technology strongly depends on the optical path length recognition rate in the extraction of useful features due
resulting in the detection of changes in gas concentration to the complex pattern of spectral lines. Moreover, the
at ppb level [145,146]. For example, X. Zhang et al. studied inability to carry out real-time online analysis for the
the decomposition products of SF6 designing a gas cell overlapping of absorption peaks for each gas component
with a 20-m-long optical path, based on the principle of and H2O vapor interferences is a delicate point. Thus, dif-
White-cell and matching with FTIR [147]. Comparing the ferent post-processing analysis methods can be adopted:
results achieved through FTIR equipped with the long library searching is useful for single spectral components
gas cell and the gas chromatographic analysis, the FTIR and absorption peaks rarely overlapped [149]; chemo-
sensitivity is able to discriminate a greater number of SF6 metrics models and pattern recognition methods [150].
decomposition products than gas chromatography. In addition, a variety of artificial neural network (ANN)
Although FTIR can be used for on-line monitoring algorithms are proposed for more complex FTIR spectrum
[77,78], the gas cell and the quantitative analysis algo- identification [151,152]. For example, Yang and Griffiths
rithm must be customized. The quantitative analysis in encoded the spectra of five alcohols, identifying them cor-
IR spectroscopic gas sensing is based on the relationship rectly from more than 100 spectra of different compounds
through Hopfield network [151]. Li et al. used Back- the THz range in an absorption cell at a fixed pressure
Propagation Artificial Neural Network for simultaneous while its spectral response is acquired, which gives the
quantification of a mixture of methylene chloride (CH2Cl2), fingerprint feature or decay signals of the pulse [87-89].
chloroform (CHCl3), and acetone, where strong overlaps Different systems are reported in literature: THz-TDS
between the main absorption peaks of three gases do not [182-187] and THz-FDS [188] based on photomixing [76,188],
ensure the ordinary calculation of Path Integrated Con- photoconductive antennas [104], and non-linear crystals
centration [152,153]. [105], heterodyne detection and/or chirped-pulse [79].
The technical progress has allowed the production Figures 9a,b report the THz-TDS absorption coeffici-
[104,154-163] and the coherent detection of sub-picosecond ent of acetone and CH3OH in gaseous-phase between 0.2 to
(ps) pulses of THz radiation [160,164,165]. Its potential 2.5 THz with 15 GHz spectral resolution, obtained by means
applications span in various research fields [109,166-171], of a home-made THz-TDS spectrometer at Terahertz labo-
from biomedicine [108,172-174], material investigation ratory (University of Rome, ‘La Sapienza’) [93,108].
[175-177] and particle acceleration [178-179] to environ- They exhibit a different trend in the THz region.
mental and security monitoring [93,180]. The technologi- Acetone exhibits a single and broad absorption band from
cal availability and the high selectivity in THz region have 0.2 to 1.2 THz (centered at 0.562 ± 0.015 THz) assigned to a
led to an increasing interest in THz spectroscopy for the convolution of many hindered rotation transitions, which
detection of toxic compounds [75,94-98], especially VOCs, is in agreement with a previous report [189]. Instead,
and the validation of THz spectroscopy-based systems CH3OH has many constant spaced absorption lines related
as complementary spectroscopic tools. In addition, the to the rotational transitions. They are almost equally
request for fast, non-destructive and low-cost detection spaced of 50 GHz and the most intense absorption peak is
and chemical identification is easily fulfilled looking at located at 2.038 ± 0.015 THz [189]. Thanks to the different
the variation of gas optical features [87-89]. Thus, THz characteristic spectral features, THz-TDS has great poten-
spectroscopy exhibits many advantages for gas sensing tialities in identification of different gaseous substances
applications compared to conventional IR techniques. due to their specific optical response in the THz region.
Depending on the molecule structures, the strong rota- In gas sensing applications, a higher selectivity of
tional transitions are located at low frequencies, around THz-TDS compared to IR spectroscopy was demonstra-
0.1-0.5 THz [181]. For example, common breath gases ted by examining various gases, such as acetaldehyde
identify more than 1,000 absorption lines within the (C2H4O), acetonitrile (C2H3N), NH3, ethanol, CH3OH, propi-
0.2-0.3 THz range. In addition, methanol (CH3OH) exhi- onaldehyde, propionitrile (C3H5N), and H2O vapor in the
bits a strong transition between 0.2-0.3 THz with a line range between 0.03-3.9 THz [184].
intensity of 8.3×10-23 cm-1/(molecule/cm2) at 10 Pa per 1 m The LOD for a commercial THz-TDS system is around
absorption length [92]. In order to perform sensing mea- 40 ppm for CO [187]. This value can be optimized by speci-
surements, the gaseous target is generally irradiated in fic customized THz-TDS systems. For example, it has been
Figure 9: (a) Acetone and (b) CH3OH absorption coefficients in gaseous phase within 0.2-2.5 THz range (15 GHz spectral resolution). The
measurements were performed with the THz-TDS setup at Terahertz laboratory, University of Rome ‘La Sapienza’ (original image).
demonstrated that lower concentrations can be detected was demonstrated by Demers and Garet that mounted the
(less than 10 ppm for C2H3N, CO, CH3OH, and H2O) with device to a consumer drone UAV [196].
50-60 dB SNR on a single measurement [185]. Recently, optical frequency combs have combined
Medvedev et al. acquired spectra of triflouromethane with the photomixing technique leading to the higher fre-
(CHF3), difluoromethane (CH2F2), iodoform (CHI3), and quency accuracy, stability, and resolution at some expense
carbon disulfide (CS2) using a THz-TDS scheme [183]. of bandwidth. The aforementioned improvements have
They proposed a quantification of the gas complex been demonstrated in the detection of methanol vapor at
rotational spectrum at a rate of 105 spectral resolution various atmosphere concentrations using a fiber-based
elements/second with a high SNR. In addition, they ana- photomixing THz spectrometer with bandwidth between
lyzed gas mixtures spectra in combination with powerful 50-1200 GHz [197]. Due to the achieved high frequency
signal processing. resolution, Zhang et al. resolved absorption spectrum for
Unlike IR spectroscopy, where the aerosol scattering methanol and assigned the absorption peaks to energy
reduces the performance of the detection system, THz levels from J = 7 to J = 21 with J total angular momentum
spectroscopy may provide dynamic analysis of mole- quantum. Meanwhile, they performed a post-processing
cular gases for environmental monitoring providing approach to remove the H2O vapor contribution [197].
spectral information of rotational transitions without Hsieh et al. performed photomixing THz synthesizer
aerosol scattering effect. Hsieh et al. performed dynamic phase-locked to dual optical frequency combs demonst-
analysis of gas-phase C2H3N in presence of smoke at rating efficacy of the THz synthesizer in gas sensing and
atmospheric pressure using a fiber-based asynchronous- operating with a gas cell at a pressure of 20 Pa [188].
optical-sampling THz-TDS spectrometer with a spectral THz-FDS characterization of gas-phase C2H3N and its
resolution of 1 GHz [186]. Without the influence of scat- isotope (CH313CN) was carried out in the frequency range
tering and/or absorption by the smoke, many rotational of 0.600-0.720 THz and their rotational transitions were
transitions were spectrally resolved at a measurement assigned with a frequency resolution of 520 kHz [194].
rate of 1 Hz from 0.1 to 1 THz. The transparency of opti- Nevertheless, to improve the detection range of gases
cally opaque medium to THz radiation, as demonstrated from ppm to ppb level, spectroscopic systems should be
for smoke, can be exploited to identify the presence of equipped with a chamber, a long folded multipass gas
reaction products of industrial processes. Hydrogen cell [198], a cryo/sorbent pre-concentration system and a
cyanide (HCN) and H2O molecules generated by the heating apparatus [75]. Hepp et al. used the FDS system
combustion of a urethane foam block can be detected equipped with a multipass cell and evacuated to 1 mbar
[190], suggesting possible applications related to the to detect trace amounts of gases released in a blaze or a
detection of hazardous gases in remote locations [191]. chemical spill in an industrial facility. The achieved LOD
The experiment was conducted at a low concentration of the system was in the range of 20 ppm for NH3 and
of dinitrogen monoxide (N2O, 25% in air) with a gas cell 100 ppm for sulfur dioxide (SO2) [198]. Hence, the applica-
1-m-long. The possibility of remote detection of nitrous tion of a preconcentration enhances the detection perfor-
compounds (NxOy) confirms the capability of THz-TDS for mance and reduces the LOD.
the applications in monitoring systems, which may be Neese et al. developed a system based on submillime-
also exploited to identify explosives and toxic pollutants ter/THz (mm/THz) technology that sorbents to capitalize
in the atmosphere [191]. on the small sample requirements of the spectroscopic
The remote sensing in the atmosphere is strictly technique and computational algorithm approach in
related to the propagation of broadband coherent THz order to use the information contained in the complex
radiation and depends on various humidity levels [192]. rotational fingerprints [75]. In the spectral region from 210
The ultrashort THz pulses propagation in a 100-m-long to 270 GHz, 14 mixtures of gases were characterized inclu-
path at 10% RH was extensively investigated, as well as ding hydrochloric acid (HCl), NH3, acetylene (C2H2), CO,
the absorption study for THz radiation (0.2-2 THz), gene- nitrogen oxide (NO), and cyanogen chloride (ClCN), con-
rated by optoelectronic antennas in the presence of H2O fined in a cell coupled with the pre-concentration system.
vapor in a 6.2-m-long path [193,194]. Generally, high THz The LOD for deuterated C2D3N was 69 ppt.
power with strong electric fields of several hundreds of THz custom-designed systems were used to identify
kVcm-1 is advantageous due to the excellent response to alcohol and several biomarker gases in human exhaled
the target gas offering new perspectives to increase the breath [79,199-201]. In particular, Rothbart et al. employed
open space distances in remote sensing [164,195]. The a specially designed gas cell reported in Figure 10 [201].
portability of THz spectrometer for real-time gas analysis The probe beam traverses it multiple times (11 passes) in
Figure 10: Setup of the mm/THz gas spectrometer for breath analysis. Reprinted from Ref. [201].
order to extend the interaction length with the contained concentration in the resonator’s environment. The com-
gas, thus increasing the absorption signals. They detec- parison of two curves reported in Figure 12 shows the
ted 21 gases in the frequency range from 220 to 330 GHz broadening (lower Q-factor) of the interesting resonances
observing a clear distinction between smoker and non- with absorption of H2O vapor. In this proof-of-concept
smoker samples. Figure 11 reports the line shape for the demonstration, less than 4 ppm of H2O vapor at atmos-
smoker’s sample. pheric pressure was readily detected.
Other methods have been proposed to increase the Different porous materials [212-217], such as porous
minimum detectable gas concentration, such as THz reso- silicon (PS) [212], porous zinc oxide [214], carbon nano-
nance field in a photonic crystal [202-206] and plasmonic tubes [215], mesoporous photonic crystals [213,216], and
[207,208] or a waveguide device [209,210]. The last two polymers [217] have been extensively used in optical gas
methods, in particular, are sensitive to slight variations of sensors for highly sensitive detection of ultrasmall quan-
the refractive index. For example, a dielectric pipe wave- tities of analytes. Porous and sponge-like structures can
guide can be successfully validated as THz refractive-index adsorb large amounts of gas molecules inside the pores
sensor for powder and liquid-vapor sensing. The proven modifying the original optical properties of the sensing
LOD is approximately 1.6 nmol/mm3 [208] and the highest system. In particular, the increase in the concentration
sensitivity was observed at around 22.2 GHz/refractive- of gas molecules inside the nanopores induces evident
index-unit, which is comparable to high-performance THz changes in the refractive index resulting in the apparent
molecular sensor [208]. spectral shifts of interference fringes. The resonant peaks
1-dimensional photonic crystal cavity based on silicon or dips were significantly enhanced [212]. The interaction
slabs [204] and 2-dimensional photonic crystal resonators length between the electromagnetic waves and analytes
[205] based on pillar arrays were proposed for non-specific can also be easily decreased to obtain a compact size for
gas sensing in the THz frequency range. In particular, the sensing unit. Meanwhile, the multilayer stack of porous
Chen et al. proposed a resonator structure that has a high- materials enables the reduction of the sensor size and
quality factor and is able to detect slight changes in the increases the amount of adsorbed gas molecules. Porous
refractive index [204]. The developed system even detected materials can be fabricated with different configurations,
a 6% variation in the concentration of the analyte [204]. such as multilayer-stacked photonic crystal devices, peri-
Although this THz gas sensor is relatively compact, odically colloidal beads and as the membrane for gas
portable, and low power consumption, its short interac- sensing [212]. The application of porous polymers, mostly
tion length essentially leads to no-excessive sensitivity transparent in the THz region, is an effective strategy to
and selectivity and no-high quality factor. However, pre- develop optical sensing systems. Stacking multiple layers
cisely designed ultrahigh quality factor THz disc micro- of flexible plastic porous membranes, with different poro-
resonators allow the implementation on compact and sities, can be used to distinguish various VOCs. Moreover,
highly sensitive THz-gas sensing spectrometers [211] that the changes in the concentration of VOCs can be detec-
monitor a change in Q-factor under variation of the gas ted analyzing the THz wave attenuation and the refractive
Figure 11: Line scans of the smoker’s sample with the largest signal for each molecular species. Reprinted from Ref. [201].
index variation induced by the adsorption of analyte in THz spectral range, the noninflammability and no effects
the microporous structure. For example, You et al. carried from aerosol scattering ensure its application in various
out an experiment, where 17 ppm of acetone vapor was monitoring fields.
successfully detected at RT and ambient atmosphere However, THz radiation strongly interacts with polar
[217]. Furthermore, they estimated the LOD from the linear molecules such as H2O [93,106,108]. This fact limits its
fitting curve, which was 7 ppm (corresponds to a mole- application in real atmosphere due to the strong attenu-
cular density of 125 pmol/mm3). The main schemes and ation of THz radiation by the atmospheric H2O vapor.
sensing parameters for the detection of VOCs using THz To overcome this issue, two different approaches have
spectroscopy are reported in Table 2. been suggested: (i) application of a chamber to isolate
Overall, the THz technology offers an alternative the target gas from the outside atmosphere; (ii) applica-
experimental approach for the gas sensing recognition. tion of a strong electric field using air plasma-based THz
The specific and unique roto-vibrational transitions in generation methods. In presence of gaseous mixtures,
Figure 12: The measured intensity and phase profiles (blue dots) of the resonance at 0.5561 THz at (a) 7 ppm per volume and (b) 120 ppm
per volume H2O vapor concentrations. Reprinted from Ref. [211].
Table 2: Sensing parameters of schemes and devices based on THz spectroscopy for the detection of VOCs
Technique Spectral range Spectral resolution Analyte LOD (ppm) Ref.
THz−TDS 0.1-2.5 THz 1.5 GHz C2H3N, CO, CH3OH, H2O <10 [185]
THz−FDS 0.5-1.5 THz 7 MHz NH3; 100, SO2 20 [198]
THz−TDS 0.03-3.9 THz 7 GHz C2H4O, NH3, C2H3N, C2H5OH, H2O, 1 [184]
C3H6O, CH3OH, C3H5N
Fiber THz-TDS 0.2-1 THz 1 GHz CH3CN 36 [186]
THz−FDS 0.6-0.72 THz 5 MHz CH3CN, CH CN3

13
− [188]
THz−TDS 0.1-1.8 THz ~15 GHz H2O, H2S − [218]
THz−TDS 238-252 GHz 500 kHz C2H4O, CH3OH, C3H8O, CH3OD, C3H6O, − [219]
CH3CN, C2H6O
THz−TDS 119.1-119.5 cm-1 0.004 cm-1 (HCN)2 − [220]
THz−TDS + concentrator 0.5-6.2 THz 30 GHz CO2, C2H6, C4H10 − [221]
THz−TDS 2 THz − CO2 − [196]
THz−TDS 246.8-261.2 GHz 3 GHz COS, CH3F, CH2F2, CH3I − [183]
Continuous wave THz 1026-1028 GHz 50 kHz H232S, H233S 20 [222]
THz−TDS 0.1-2 THz 37.5 GHz CO, NO − [89]
SMM 210-270 GHz 0.5 GHz HCN, H3CN, C2H4Cl2, CH3CN, C2H3CN, In ppt level [97]
C2H5CN, C2H3F
Chirped pulse THz spectroscopy 230-620 GHz − CH3OH, N2O, COS, C2H5OH, C3H6O, H2O 2−8000 ppb [88]
THz−TDS 0.1-3 THz 7.3 GHz CH3OH, C3H6O − [189]
THz−FDS 200-500 GHz 0.5 GHz HCN, H2O 640 [190]
THz−TDS 0.2-2 THz 6.1 GHz H2O − [194]

THz−TDS 0.2-3 THz 7 GHz CH3CN − [195]
partial overlapping of absorption lines shows complex the conductance change of the sensor using cost-effective
absorption spectra making difficult the recognition of and small size electrical devices. Furthermore, the
each compound. In this case, post-processing methods dopants may introduce crystal defects in the metal oxide
may be carried out taking the advantage of the network nanomaterial resulting in the formation of oxygen vacan-
analysis, machine learning, and principal components cies and enhancing the adsorption of VOCs on the sensing
analysis algorithms. Some preliminary research findings structure.
have been reported based on the studies of human breath. Noble metals with their catalytic features can affect
Meanwhile, gas concentrators have been suggested for the the dissociation of atmospheric O2 and increase the
detection and identification of ultra-small concentrations concentration of adsorption sites on the oxide material
of VOCs. The application of metamaterials, plasmonic, activating the surface reactions between the VOCs and
and resonant structures may extend the use of the natural sensors. The electronic sensitization of noble metals
dielectric response in the long-wavelength regime and plays an important role in the improvement of the
overcome the optical resolution limit. response of metal oxides due to the formation of the
Alternatively, microporous structures for the adsorp- potential barrier at the grain boundaries increasing the
tion of the analyte can be used as gas filters. Interrogating width of the depletion layer at the interface between the
these structures with THz wave, as well as the analysis of sensing structure and catalyst. Thus, the charge carriers
the THz wave attenuation and the refractive index varia- are released more easily from the surface reactions at the
tion will improve the efficiency of the detection and quan- catalyst/metal oxide interface to the conduction band
tification of VOCs. improving the functionalities of chemiresistive sensors.
As a result of these studies, the response of the metal
oxides towards VOCs has been improved at the relatively
5 Conclusions and outlook low operating temperatures, which reduces the power
consumption of the final sensing device. However, it is
The increasing number of experimental studies on the important to distinguish each VOC in the presence of
development of new strategies and advanced techno- more complex mixtures, and therefore the enhancement
logies for the detection of VOCs confirms the relevance of the selectivity of chemical gas sensors remains a chal-
of the systems for monitoring of air quality and human lenging issue.
health status. Meanwhile, in the development of high- In this regard, the fabrication of chemiresistive
performance detection systems, an effective methodology sensors based on metal oxide nanocomposites has proven
and planning are required to successfully achieve the a very promising strategy to improve their response and
expected objectives. Therefore, the application field can selectivity. The studies indicate that the coupling of
play a significant effect on the design and fabrication of p- and n-type metal oxides in a composite structure may
sensing systems. Herein, we have discussed two different open a new avenue for the preparation of emerging func-
types of sensors that have been used for the manufactu- tional nanomaterials and their integration in detection
ring of monitoring systems. systems. In this case, the formation of a p-n heterojunc-
Chemiresistive sensors based on metal oxide mate- tion and its modulation due to the adsorption/desorption
rials take advantage of the fact that their conductance processes of VOCs may have a significant effect on the
changes with the concentration of VOCs. Moreover, the sensing performance of the composite material. However,
size reduction of oxide materials to the nanoscale will this is a relatively new strategy and a deeper understan-
dramatically change the performance of chemical gas ding of the contribution of each material in the sensing
sensors. Overall, the research studies indicate that metal properties of gas sensors is needed considering different
oxide nanomaterials with different shapes and morpho- metal oxides and concentrations. Meanwhile, the stabi-
logies are sensitive towards a wide range of VOCs. In the lity of the functional properties of metal oxides should
meantime, the crystal structure, shape, and size of metal be tested for longer periods (more than a few months) for
oxides affect their response towards VOCs. The response their integration in monitoring systems. Unfortunately,
and selectivity of chemiresistive sensors can be enhanced sometimes the LOD of the fabricated sensors was not con-
by doping and functionalization with different materi- sidered in the investigations, which makes difficulties to
als. In particular, dopant materials with higher oxidation compare the sensing parameters of different structures
states substitute the atoms of the metal oxides and main- and compositions.
tain the same oxidation state of the structure increasing Currently, the field of vibrational spectroscopy is
its electrical conductivity, which is beneficial to read out expanding extensively. In particular, optical gas sensors
based on THz spectroscopy take advantage of the fact that was also supported through the bilateral cooperation ag-
many gases show specific roto-vibrational transitions in reement between Italy and China of the Italian Ministry
the THz spectral region. Compared to the common mid-IR of Foreign Affairs and of the International Cooperation
region, polar gases have relatively unique set of absorp- (MAECI) in the framework of the project of major relevan-
tion lines in this spectral range facilitating their selective ce No. PGR00772.
recognition. Various optical schemes have been reported
in the research studies. The capability of THz spectroscopy Author contributions: Vardan Galstyan: conceptualiza-
for the detection and identification of VOCs with a wide tion, supervision, visualization, writing – original draft,
range of concentrations and low LOD has been demons- writing – review and editing; Annalisa D’Arco: conceptua-
trated. Furthermore, the developed cost-effective devices lization, investigation, resources, writing – original draft,
show easy availability and portability with low absorption writing – review and editing; Marta Di Fabrizio: investi-
loss. Considering the advantages of THz radiation (nonin- gation, formal analysis, visualization, writing – original
flammability and no effects from aerosol scattering), THz draft; writing – review and editing; Nicola Poli: metho-
sensors are suitable for the detection of VOCs at ambient dology, resources, investigation, writing – original draft,
conditions and for applications in human breath analysis writing – review and editing; Stefano Lupi: funding acqui-
and environmental/occupational monitoring. sition, supervision, writing – original draft, writing – re-
However, THz waves show strong absorption due view and editing; Elisabetta Comini: funding acquisition,
to humidity, limiting the functionality of the sensing project administration, writing – original draft, writing –
devices, especially in atmospheric environmental monito- review and editing.
ring. The limitations can be overcome by isolating the gas
target from the outside atmosphere and/or by applying Conflict of interest: Authors state no conflict of interest.
strong THz electric fields achieved with air plasma-based
THz generation methods. The latter is more effective due
to its strong response to the target VOC through the high References
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Reviews in Analytical Chemistry 2021; 40: 33–57

Review Article  Open Access

Detection of volatile organic compounds: From

monitoring systems [26-31]. The solid-gas interface plays 2 Operation principles

Material/ Operating Analyte, Response Response/ LOD Stability/ Ref.

SnO2 microspheres 200 H2CO, 100 Ra/Rg, 38 17/25 ‒ 6 cycles† [113]

SnO2 nanowire 450 Ethanol, 25 Vg/Va 6.1 15/41 ‒ ‒ [114]

SnO2 hollow spheres 350 Toluene, 200 Ra/Rg, 14 130/200 ‒ ‒ [115]

SnO2 hollow spheres 250 Methanol, 200 Ra/Rg, 79 340/130 ‒ ‒ [115]

a‒Fe2O3 nanowires 280 Ethanol, 100 Ra/Rg, 45 16/28 ‒ 6 cycles [118]

In2O3 nanoparticles 100 H2CO, 10 Ra/Rg, 68 122/39 1000 1 month [34]

ZnO nanorods 300 Ethanol, 100 Ra/Rg, 45 6/31 ‒ 30 days [36]

ZnO nanobristles RT Ethanol, 100 Ra/Rg, 464 19/12 ‒ 3 cycles [122]

Pt‒TiO2 300 Acetone, 200 Ra/Rg, 29 13/30 ‒ 30 days [137]

Pd‒In2O3 nanoparticles 350 Ethanol, 5 Ra/Rg, 159 ‒ ‒ ‒ [121]

Pt‒In2O3 nanofibers 180 Acetone, 50 Ra/Rg, 105 6/9 10 50 days [126]

Pd‒Au-SnO2 nanosheets 250 Acetone, 2 Ra/Rg, 6.5 5/4 45 6 cycles [41]

Ag‒SnO2 nanofibers 100 Acetone, 50 Ra/Rg, 40 6/10 ‒ 4 cycles [127]

Y‒SnO2 flower-shaped 180 H2CO, 50 Ra/Rg, 18 ‒ 1000 2 months [42]

Ni‒SnO2 nanorods 450 Ethanol, 50 Ra/Rg, 2000 30/600 ‒ ‒ [128]

Fe‒ZnO Nanosheet-Spheres 300 H2CO, 10 Ra/Rg, 33 42/11 ‒ ‒ [138]

Al‒NiO nanofibers 325 Methanol, 200 Rg/Ra, 10 199/15 ‒ 4 cycles [139]

Ag‒ (TiO2/SnO2) 275 Ethanol, 50 Ra/Rg, 53 3.5/7 1000 30 days [134]

CuO/Ti3C2Tx nanoparticles 250 Toluene, 50 Rg/Ra, 11 270/10 320 ‒ [13]

NiO/SnO2 nanoparticles RT Ethanol, 100 Rg/Ra, 140 23/13 1000 ‒ [136]

SnO2/NiO/Au hollow sphere 75 Ethanol, 40 (Ra-Rg)/Rg, 38 ‒ ‒ 35 days [133]

TiO2/WSe2 nanospheres/ RT Ethanol, 30 Rg/Ra, 10 2/2 ‒ 1 month [29]

Technique Spectral range Spectral resolution Analyte LOD (ppm) Ref.

THz−FDS 0.5-1.5 THz 7 MHz NH3; 100, SO2 20 [198]

Fiber THz-TDS 0.2-1 THz 1 GHz CH3CN 36 [186]

THz−FDS 0.6-0.72 THz 5 MHz CH3CN, CH CN3

THz−TDS 0.1-1.8 THz ~15 GHz H2O, H2S − [218]

THz−TDS 119.1-119.5 cm-1 0.004 cm-1 (HCN)2 − [220]

THz−TDS + concentrator 0.5-6.2 THz 30 GHz CO2, C2H6, C4H10 − [221]

THz−TDS 2 THz − CO2 − [196]

THz−TDS 246.8-261.2 GHz 3 GHz COS, CH3F, CH2F2, CH3I − [183]

Continuous wave THz 1026-1028 GHz 50 kHz H232S, H233S 20 [222]

THz−TDS 0.1-2 THz 37.5 GHz CO, NO − [89]

THz−TDS 0.1-3 THz 7.3 GHz CH3OH, C3H6O − [189]

THz−FDS 200-500 GHz 0.5 GHz HCN, H2O 640 [190]

THz−TDS 0.2-2 THz 6.1 GHz H2O − [194]

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