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 Journal of The Electrochemical Society, 2020 167 037537

Review—Metal Oxides: Application in Exhaled Breath Acetone

Chemiresistive Sensors
Milua Masikini,1,z Mahabubur Chowdhury,1,z and Ouassini Nemraoui2
1
Department of Chemical Engineering, Cape Peninsula University of Technology, Bellville-7535, South Africa
2
Department of Mechanical and Mechatronics Engineering, Cape Peninsula University of Technology, Bellville-7535, South
Africa

Human breath investigation offers a non-invasive and quick strategy for recognizing different volatile organic compounds (VOCs)
that are markers for various diseases. Scientists have shown that breath acetone is a successful biomarker of Type 2 diabetes which
is the most common type of diabetes. The generation of acetone is a consequence of the body processing fats as an alternative of
glucose to produce energy. Thus, detection of breath acetone can be a rapid, viable, and patient compliant alternative to the
conventional methods of blood glucose determination. To achieve this goal, metal oxide nanostructures with various shapes
through different synthesis routes in the nanometer scale, can be used. Owing to its properties such as high surface-to-volume ratios
and subsequently large number of surface sites exposed to acetone gas, metal oxide nanostructures facilitate a well-built gas-
sensing layer interaction and consequently compared to conventional materials, present a higher sensitivity. This work, presents the
progress in metal oxides nanostructures (semiconductor nanomaterials) as gas sensing materials for the exhaled acetone detection,
which offers the possibility to help people living with diabetes to screen their disease. The different types of metal oxides materials
used in Breath acetone sensors, their limitations and future perspectives have been highlighted.
© 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ab64bc]

Manuscript submitted September 18, 2019; revised manuscript received December 10, 2019. Published January 13, 2020. This
paper is part of the JES Focus Issue on Sensor Reviews.

Human breath contains volatile organic compounds (VOCs),
some of which are known as biomarkers on the grounds that their
concentration can be legitimately connected to a specific sickness or
medical problem and can give basic data to the analysis or the
diagnosis of particular diseases.1,2 Nevertheless, the earliest refer-
ence point of breath investigation previously began in antiquated
occasions, when Hippocrates showed his students how to utilize
breath smell so as to recognize patients with liver infection,
uncontrolled diabetes, and notwithstanding coming up failing
kidneys.3 At the point when a human body cannot discharge energy
from glucose, either in light of the fact that glucose is exhausted or
on the grounds that the body cannot use it, it can utilize fatty acid as
a substitute source of energy. In this procedure, the liver separates
fatty acid and creates ketone bodies including acetoacetic acid and,
as this immediately degrades, acetone (CH3)2CO) is brought into the
blood. At the point when acetone- rich blood reaches the lungs some
acetone (CH3)2CO) is discharged and breathed out with the breath.
There are a couple of extra significant crossroads in-breath history
that convey us to the present. In 1798, John Gallo described the
smell of exhaled breath from rotten apples and later in 1857 after 59
years, this smell was recognized as acetone,3 which was utilized as
an absolute first biomarker of diabetic unconsciousness. The under-
estimation of exhaled acetone throughout the years, for the most part
on the grounds that there were no appropriate devices to identify it in
exhaled breath and correspond it with explicit sicknesses, for
example, diabetes. In mid-70 s everything changed, when Linus
Pauling (1971) published an original article showing an investigative
strategy used to distinguish around 250 compounds in breath.4
The breath acetone concentration (BAC) can differ significantly
on a daily basis, principally influenced by three elements, which are:
diet,2,5 exercise.6,7 and medical condition.8,9 The breath acetone
concentration (BAC) is unequivocally affected by daily nature of
food eaten specifically the quantity of carbohydrates and fats. A
decrease in carbohydrates intake results in less availability of
glucose for consumption and the organism shifts to fatty acids to
work, leading to increase acetone in breath. After normal overnight
fasting or long periods without food intake, similar effect is gotten,
with the body consuming fats after depleting the willingly accessible
z
E-mail: masikinim@cput.ac.za; chowdhurym@cput.ac.za
resources of glucose. In the same way, during long period and/or
hard physical exercise, the body may exhaust its glucose supply and,
in this manner, consume fat as an energy source resulting in higher
breath acetone concentration. A higher level of acetone concentra-
tion in breath may likewise be an indicator of some metabolic
conditions, i.e. diabetes. In the breath of pregnant women and
infants, a higher concentration of acetone can likewise be found,
albeit still questionable, breath acetone concentration may depend
additionally on age and Body Mass Index (BMI).2 The well
established and known relationships between physiological state
and acetone in-breath (Fig. 1) made the evaluation of breath acetone
concentration to be a potentially powerful, non-invasive, pain-free,
cost-effective and easily repeatable instrument for way of life and
medical monitoring.10
According to the World Health Organization (WHO),12 the
number of diabetes patients is increasing yearly. Based on the actual
data published by World Health Organization (WHO), 422 million
adults have diabetes with 1.6 million deaths registered each year.
Hyperglycemia (high level of blood sugar in the body) is known to
provoke serious damages in the body, including cardiovascular
disease, diabetic nephropathy, diabetic retinopathy, diabetic neuro-
pathy, etc.13,14 Furthermore, diabete is considered as potential
sources of health problems such as heart attack, stroke, kidney
failure, leg amputation, vision loss, and nerve damagel.12,14 The
level of exhaled acetone is usually in the range of 0.2–1.8 ppm for fit
people and 1.25–2.5 ppm for people living with diabetes.3,15 and it
may increases up to 25 ppm for some people leaving with type-1
diabetes.3,16 The growinfce still based on blood samg number of
diabetics patients willing to control diabetes by a noninvasive
method, has created a market for portable exhaled breath analyzers,
while the current practice still based on blood sampling.11 At the
moment, the economically accessible gas sensors for acetone
identification work in the 50–5000 ppm, which is out of range for
exhaled acetone levels.3 There are still difficulties in understanding
these results with respect to all breath gas investigations, specifically
concerning breath testing methodology and deconvoluting the
distinctive origin of acetone. Though the main key prerequisite is
an innovative sensor adequately cost-effective and conservative to
be incorporated into individual breath analysers and point-of-care
instrumentation.2,17 Sample of commercial metal oxide acetone
sensor is shown in Fig. 2.
 Journal of The Electrochemical Society, 2020 167 037537

Figure 1. Correlation between breath acetone concentration and blood glucose level in (a) healthy patients and (b) diabetes patients. Figure edited with
permission from Ref. 11.

Metal oxides are efficient catalysts of oxidation-reduction

reaction.21 Semiconductor metal oxide (SMO) gas sensors are the
most explored group of gas sensors.22,23 in the field (Fig. 3). In this
review, we are going to summarize metal oxides based chemical
sensors for detection of VOCs, more especially for acetone. In the
following sections various types of oxygen-containing VOCs in
exhaled breath are summarized followed by a review of chemical
sensors with different groups. Finally, we described metal oxide
nanomaterials gas sensors principle and mechanism, and chemir-
esistive breath acetone sensors.

Volatile Organic Compounds in Exhaled-Breath

Figure 2. Picture of commercial metal oxide VOC gas sensor (Winsen
MQ138) .
Numerous investigations have been reported on a non-invasive
analysis of breath for detection of acetone, such as gas chromato-
graphy with mass spectrometry (GC–MS), proton transfer reaction
with mass spectrometry (PTR-MS), flame ionization detector (FID),
ion mobility spectrometry (IMS) and several other sensitive
techniques.18–20 Even though these techniques are sensitive and
reliable but they are not portable for daily monitoring. Recent studies
are focused on developing gas sensors to cover the exhaled acetone
range at room temperature.3
Volatile organic compounds (VOCs) are vaporous molecules that
can be sampled rapidly and non-invasively from breath. They are
generated either from inside the body so-called endogenous VOCs or
from external sources such as food ingestion, metabolization of drugs
and environmental exposure known as exogenous VOCs. The exhaled
human breath comprises nearly 3500 diverse VOCs. The presence of
biomarkers in the exhaled breath are suggestives for a number of
medical conditions, such as lung cancer,3,24 asthma,25 chronic obstruc-
tive pulmonary disease (COPD) 26, breast cancer,26 and diabetes.27,28
Deplorably, the accurate number of diseases that can be identified or
constrained by exhaled breath analysis is so far unidentified. Due to the
nature of this work, in this review, only oxygen-containing compounds
are highlighted in this review and presented in the section below.

Figure 3. Search results of literature review (2017–2019) of the exhaled acetone detection: (a) different methods: Selected‐ion flow‐tube mass spectrometry; Gas
Chromatograph—Ion Mobility Spectrometer; Proton‐transfer‐reaction mass spectrometry; Gas chromatograph—mass spectrometry (b) different materials used
as receptors in sensor applications presented in papers.
 Journal of The Electrochemical Society, 2020 167 037537
Figure 4. Schematic representation of the working principle of a chemical (biochemical) sensor.
Oxygen-containing compounds.—Ketone bodies is a term used
to represent three molecules, acetoacetate (AcAc), 3-hydroxybuty-
rate (3HB) also referred to as β-hydroxybutyrate and acetone that are
produced in the liver and generally found in the breath, blood, and
urine.29 (Fig. 4). Out of the three ketone bodies, acetoacetate (AcAc)
and 3-hydroxybutyrate (3HB) are used to convey energy from the
liver to other body tissues due to their energy-rich properties.
Acetone is the most abundant component in human breath,30,31
and a minor product in the ketone bodies.29 Acetone is generated by
spontaneous decarboxylation or enzymatic conversion of acetoace-
tate (AcAc).20,29 and the dehydrogenation of isopropanol.8 Acetone
is responsible for the sweet odor on the breath of individuals with
ketoacidosis. The conversion of acetoacetate process is done through
elimination of CO2:
CH3COCH2 COO- + H+  CH3COCH2 COOH
CH3COCH3 + CO 2 [1]
Chemical Sensors
Principle and composition.—A chemical gas sensor can be
defined as a device, that can change one or more of its physical
properties (mass, electrical conductivity, or dielectric properties)
once exposure to a gaseous species or molecules, so that the change
can be measured and quantified.32 These changes convey an
Figure 5. Transduction base classification of chemical sensors.
electrical signal, with a magnitude that is relative to the concentra-
tion of the gas under test, which is estimated as an amount of the gas
to which the measuring sensor is exposed.
Generally, chemical sensors contain two basic functional units: a
receptor element and a transducer element, as shown in Fig. 4. The
receptor is part of a sensor where the chemical information is
changed into a form of energy so that it can be measured by the
transducer. A transducer converts the energy carrying the chemical
information about the sample into a useful analytical signal.
In a chemical sensor, the analyte interacts first selectively (more
or less) with the recognition (or sensing) element, which should have
affinity for the analyte. In addition, the recognition and transduction
function are integrated in the same device. An analytical device
without recognition function included is called a concentration
transducer but not a chemical sensor.33
Classification of chemical sensors.—Classification of chemical
sensors is accomplished in different ways. In general, there are
different ways to categorize sensors in literature. According IUPAC
chemical sensors may be classified according to the operating
principle of the transducer.34 as listed in Fig. 5. Therefore, based
on their transduction methods and modes of measurement, they can
be classified into three main classes: (i) electrical and electroche-
mical properties, (ii) changes in the physical properties, and (iii)
optical absorption of the chemical analytes to be measured.35
 Journal of The Electrochemical Society, 2020 167 037537

Solid state gas sensors.—Solid state sensors principle is to
measure the changes in the physical property of the devices relative
to chemical on the surface of a sensing element.36 A very important
characteristic of solid state gas sensor is the reversible interaction of
the gas with the surface of a solid-state material. In addition to the
conductivity change of gas-sensing material, the detection of this
reaction is also done through the measurement in the change of
capacitance, work function, mass, optical characteristics or reaction
energy released by the gas/solid interaction.37,38 Solid state gas sensors
present the best possibility for the growth of commercial gas sensors
for various applications. Recently, scientists have grown interest on
solid-state sensors for detecting VOCs.39 for non-invasive diabetes
management. There are several types of solid-state gas sensors with
different detection principle i.e. Chemiresistive, chemical field effect
transistors, calorimetric, potentiometric and amperometric.
Chemiresistors are the simplest and most available gas sensing
platform. They have advantages over other platforms such as, simple
fabrication, low cost, and simple measurement electronics.32 These
sensors work based on the change in electrical resistance of the
sensing material in presence of target analytes. Chemiresistive
sensor translates chemical information through the changing of
electrical resistance.40 The basic device architecture of chemiresis-
tive sensors is generally made by coating an interdigitated electrode
(gold and chromium) with a thin film or by using a thin film or other
sensing material to bridge the single gap between two electrodes. In
both architectures, the chemiresistive sensing material controls the
conductance between the two electrodes with each device
architecture having its own advantages and disadvantages. The
performance of the sensor can be evaluated by evaluating parameters
such as, response, selectivity, sensitivity, response time, recovery
time, operating temperature, and limit of detection.40 Various
materials e.g. metal-oxides, conductive polymers, graphene, carbon
nanotubes have Chemiresistive properties. In this review more focus
has been given to metal oxides based chemiresistive sensors for
VOCs detection.
Metal Oxide Nanomaterials Gas Sensors
Semiconducting metal oxide materials (SMOMs).—Sensing be-
haviour is one of the most significant property of metal-oxide
materials. Beside their sensitivity to light (photon) energy and external
pressure, metal oxides display high sensitivity to their chemical
environment. They are also able to work in harsh environment; surpass
other chemical sensors in their sensitivity, reliability, and durability.32
Therefore, gas sensor industry heavily relies on metal oxide materials
as sensing element. Based on the conduction type, the metal oxide
semiconductors can be divided into n- and p-type,41 which exhibits
different sensing behaviours to the same detecting gas. N-type
semiconducting metal oxide materials such as ZnO, SnO2, In2O3,
WO3, TiO2, Fe2O3, MoO3, VO2 and CeO2 are the most reported
sensing materials for room temperature (RT) resistive gas sensors.
They are synthesized at different forms including nanoparticles,
nanorods, nanowires, nanoflowers, nanosheets, nanofilms, nanotubes,
porous structures and hierarchical nanostructures. These n-type metal

Table I. Summary of semiconducting metal oxide materials and their target VOCs at RT.

LOD
Material Shape Synthesis Process Type Target gas Agent (ppm) References

CuO Nanowires Thermal oxidation p C2H5OH Ox 10 45

CuO Nanoribbons Wet chemical p C2H5OH Ox 20 46
In2O3 Cubic crystals Hydrothermal n C2H5OH Ox 10 47
Au/In2O3 Nanofibres Electrospinning — C2H5OH Ox 20 48
β-MnO2 Thin films Spray pyrolysis p CH3COH Ox 10 49
V2O5 Nanoneedles Vapour deposition n CH3COCH3 Ox 0.941 50
SnO2 Nanoporous Hydrothermal n CH3COCH3 Ox 10 51
SnO2-Sb Nanowires CVD — C2H5OH Ox 40 52
SnO2/graphene Nanohybrids Electrochemical deposi- — HCHO Red 0.02 53
tion
SnO2/rGO Hybrid films Hydrothermal — CH3COCH3 Ox 10 54
TiO2 Nanotubes arrays Electrochemical anodi- n HCHO Red 0.04 55
zation
TiO2 Nanotubes Electrochemical n CH3COCH3 Ox 10 56
Ag/TiO2 Nanoparticles Sol-gel — C2H5OH Ox 0.15 57
Ag/TiO2 Nanorods Wet chemical — C2H5OH Ox 58
Co/TiO2 Nanoparticles Sol-gel — C2H5OH Ox — 59
TiO2/rGO Nanosheets Spray — HCHO Red 0.1 60
ZnO Thin films Thermal evaporation n C2H5OH Ox — 61
ZnO Tetrapod network Thermal oxidation n C2H5OH Ox 10 62
ZnO Nanorods Laser ablation n C2H5OH Ox 1 63
ZnO Nanorods Electrospinning n C2H5OH Ox 1 64
ZnO Nanowires Electrospinning n C2H5OH Ox 1 65
Au/ZnO Core-shells Sol-gel — HCHO Red 0.5 66
Al/ZnO Nanowires Electrodeposition — C2H5OH Ox — 67
Al/ZnO Hexagonal facets Sol-gel — C2H5OH Ox — 68
Ni/ZnO Nanorods Electrodeposition — CH3COCH3 Ox — 69
Na/ZnO Nanoflowers Solution route — CH3COCH3 Ox 0.2 70
VO2/ZnO Heteronanostructures Heteroepitaxial het CH3COCH3 Ox 10 71
α-Fe2O3/ZnO Nanowires Piezo-surface coupling het C2H5OH Ox 100 72
ZnO/MWCNT Nanorods Hydrothermal — C2H5OH Ox 5 73
WO3−x Quantum dots Solvothermal n HCHO Red 1.5 74
WO3 Nano-films Thermal evaporation n C2H5OH Ox 10 75
PANI/Cellulose/WO3 Granules Chemical solution p-n CH3COCH3 Ox 10 76

Note: Ox = oxidizing agent; Red = reducing agent; LOD = limit of detection; het = heterojunction (n-p; p-n; n-n; p-p).
 Journal of The Electrochemical Society, 2020 167 037537

oxide materials have been most utilised for the detection of hydrogen
sulphide (H2S), nitrogen dioxide (NO2), hydrogen (H2), ammonia
(NH3), acetone (CH3COCH3), ethanol (CH3CH2OH), formaldehyde
(HCHO), liquefied petroleum gas (LPG), carbon monoxide (CO), etc.
42,43
P-type semiconducting metal oxide are also showing promise in
gas sensing applications.44 So far, p-type semiconducting metal oxide
materials such as CuO, Co3O4, NiO, have been used in RT gas sensing,
and the main target gases include ammonia NH3, H2S and NO2.43
Summary of recent various types of semiconducting metal oxide
materials used in the detection of oxygen-containing VOCs at RT is
listed in Table I (from 2010 up today).
Principle and mechanism.—The sensing properties of chemir-
esistive gas sensors are controlled by three factors, i.e. the receptor
function, transducer function, and utility factor, as shown in Fig. 6.
The main concern of receptor, is how every constituent reacts to the
surrounding atmosphere containing oxygen and target gases. The
quantity of oxygen adsorbed in this procedure decides the sensing
properties, which is directly dependent on the specific surface area of
the sensing materials.77
The working temperature of gas sensors plays an important role
in the determination of the types of chemisorbed oxygen species
(ions).43,78 The oxygen species are formed depending on working
temperature as summarised in following equations.43
O2(gas) + e-  O2(ads) [2]
O2(ads) + e-  O2-(ads)( 100 C) [3]
O2-(ads) + e-  2O-(ads ) (100 - 300 C) [4]
The formation of oxygen species results in the capture of
electrons from conduction band of the surface layer, leading to an
alteration in conductivity of the semiconducting metal oxide.
Furthermore, that alteration in conductivity results from a change
in the charge carrier concentration.78 The increase or decrease in
conductivity of the semiconducting metal oxide material depends on
the type of majority carriers in the semiconducting metal oxide
material (n-type: electron and p-type: hole) and the nature of gas
molecules (either oxidizing or reducing) at room temperature.
Gas sensing mechanism of N and P-type SMOMs.—Generally
for n-type semiconducting metal oxide materials, electrons are removed
from the conduction band of the surface layer by the absorbed oxygen
molecules resulting in the formation of negatively charged chemisorbed
oxygen ions, and at RT the oxygen ions on the surface are basically
O2-ions.43 The decrease in the electron density brings the formation of
an electron depletion layer on the surface of SMOMs and formation of
a potential energy barrier. (see Fig. 6). As a result, the resistance of the
SMOMs increases,42 consequently the conductivity of the SMOMs
decreases. Since the target plays also important role in the performance
of the gas sensor. In the case of reducing gases (donors), such as H2S,
H2, NH3, HCHO, etc, the chemical reaction releases electrons, which
are reinjected back to the electron depletion layer. Then, the reduction
of the potential barrier energy occurs due to the decrease in the electron
depletion layer. Therefore, the surface resistance of semiconducting
metal oxide materials is decreased and conductivity increased.
Conversely, when the target gases are oxidizing gases (acceptors),
such as NO, NO2, CH3COCH3, Cl2 and O3, the reaction with the
chemisorbed oxygen ions will capture the electrons, which will expand
the electron depletion layer, resulting in an increase of the potential
barrier energy. Consequently, the surface resistance of the semicon-
ducting metal oxide materials is increased and the conductivity
decreased. In conclusion, in the presence of the oxidizing gases, n-
type SMOM based sensors resistance increases and decreases in the
presence of the reducing gases.
In contrast, for p-type SMOMs the sensing mechanism depends
on the changes of surface resistance resulting in the changes in the
concentrations of hole carriers due to the oxidation-reduction
reaction between SMOMs surface and the target gases. In the
presence of air at RT, two phenomena occurred on the surface of
p-type SMOMs, the formation of the oxygen ions of O2- due to the
oxygen molecules that have been adsorbed and electrons capture

Figure 6. Diagram description of the gas-sensing mechanism and the conduction model based on n-type and p-type Semiconducting metal oxides72 [Reprinted
with permission from Royal Society of chemistry].
 Journal of The Electrochemical Society, 2020 167 037537
from the conduction band. Thus, an increase of density of hole
carriers and a decrease in the surface layer’s Fermi level, are
observed. In the end, the sensors conductivity increases and their
resistance decreases due to an accumulation of hole layer formed on
the surface of p-type SMOMs, as shown in Fig. 6. In case the
reducing gas molecules are adsorbed on the surface of SMOMs,
electrons are released, which will combine with the holes, con-
sequential, Fermi level increases and the hole accumulation layer
decreases due to the reaction between the reducing gas molecules
and O2− ions. Therefore, the reduction of the conductivity of the
SMOMs layer is observed. Conversely, for the oxidizing gases, the
surface of the p-type SMOMs allows extra free electrons to be
captured. The molecules adsorbed on the sensor surface will capture
electrons from the p-type SMOMs to form a negatively charged
chemisorbed oxygen ions. Therefore, the concentrations of hole
carriers will significantly increase, consequently the conductivity of
the p-type SMOMs-based gas sensors increases. In brief, reducing
gases increase the resistance of p-type SMOM based sensors and it
decreases with the oxidizing gases. The mechanism for p-type
SMOM based sensors is opposite to the mechanism for n-type
SMOM based sensors discussed earlier.
Sensitizations of SMOMs.—The sensing performance of the
SMOMs gas sensors is prejudiced by its poor selectivity and addition
of a suitable quantity of additives such as Pd, Pt, Au, RuO2,etc can
enhance gas sensitivity and rate of response under certain conditions
by modifying its surface.37,44 The mechanism of sensitization or
response enhancement by additives depends on the type of metal
oxide materials and can be achieved through two different types of
sensitization mechanisms: chemical and electronic. In chemical
sensitization, chemical reactions between target gas and metal oxide
surface are assisted by the promoters that exist on the metal oxide
surface through a phenomenon called spill- over. For example noble
metals have been added on the metal oxides surfaces and remarkably
enhanced the sensing properties of SMOMs sensors, including
Pt/ZnO,79 Pd/ZnO,80 Pt/SnO2,81 Pd/SnO2,82 Pd/TiO2,83 Pt/TiO2,84
etc. In electronic sensitization, there is possibility of modification in
the electrical property of the metal oxide, which is done via change
in redox state of the promoter, by acceptor or donor charges from gas
molecules, for example Ag/SnO2,85 Sb/SnO2,86 Na/ZnO,70
Ni/ZnO,69 Zn/NiO,87 Al/NiO,88 Sb/WO3.89
Effect of grain size on the gas sensing performance of
SMOMs.—The morphology of the semiconducting metal oxide
materials also influences the performance of the gas sensor.
Parameters such as grain size, number of activated adsorption sites
and gas diffusion ability are responsible for remarkable low
performance of gas-sensing. In this review only grain size is
discussed since it affects the sensitivity of gas sensors. A reduction
of grain size to the nanoscale level is one of the most efficient
strategies for enhancing the gas-sensing properties.78,90
There are three cases which are related to the relationships
between the grain size (D) and the thickness of the depletion layer
(L). These mechanisms are described in terms of the boundary
control, neck control and grain control.
In case of large grains with a small surface-to-volume ratio, L is
significantly smaller than the single crystallite size (D ? 2L). Most
of the grains are unaffected by the surface interactions with the gas
phase. The electron conducting channels through necks are too wide
to be influenced by the surface effect. Fundamentally, the con-
ductivity of the gas sensors depends on the grain boundary barriers.
Thus, the gas-sensing mechanism is controlled by the grain
boundary and the sensitivity of the metal oxide materials is
independent of the grain size. In case of higher surface-to-volume
ratio, specifically smaller grains but still larger than twice the
depletion layer (D ⩾ 2L), that region extends into the grains forming
necks. As a consequence, the conductivity is a product of collabora-
tion between the cross-section area of these necks and the grain
boundary barriers, resulting in sensitivity enhancement (neck
controlled). Furthermore, the sensitivity of metal oxide materials
depends on the grain size and increases when the grain size reduces.
When D < 2L, the depletion layer extends throughout the whole
grain and the crystallites are almost completely depleted. Under this
situation, grains share a major part of the resistance and control the
gas sensitivity. Thus, the conductivity considerably decreases due to
absence of the conduction channels between the grains. The energy
bands are almost flat all through the entire structure of the
interconnected grains and lack of important barriers for intercrys-
tallite charge transport, thus mostly the grains size controls the
sensitivity (grain controlled). In theory and empirically the highest
gas sensitivity is gotten only if (D < 2L). Inspired by the model
proposed by Xu et al.,91 an excellent monodisperse α-Fe2O3
nanoparticles based acetone sensor was developed by Liang and co
authors.92 The almost fully depleted grains induced changes to the
overall conductivity, leading to improvement of the sensitivity.
Chemiresistive breath acetone sensors.—Noninvasive diabetes
detection is the future of point of care diabetes management. Hence,
the number of researches in this field is increasing significantly. The
recent chemiresistive breath acetone sensors for diabetes detection
are presented in Table II (2017–2019).
Metal oxide based chemiresistive acetone sensors.—It can be
seen from Table II that metal oxides such as, WO3, SnO2, FexOy,
TiO2, CuO, ZnO and In2O3, etc have been used mostly for the
detection and screening of diabetes. A brief review of some of the
latest publications (2017–2019) are highlighted in the sections
below.
WO3 based acetone chemiresistive sensors.—Due to its che-
mical and physical properties WO3 has been one of the metal oxides
that is frequently used for exhaled acetone detection and attracted
researchers’ interest. Its doping is very important in order to increase
its sensing properties. The first work on WO3 based thin film sensor
for automotive applications was developed and published by Gouma
et al.,130 in 2003. Early this year, wang et al.,128 have developed a
new acetone sensors using WO3 nanosheets and g-C3N4/WO3
composite with different amount of g-C3N4 loaded. Comparatively
to pristine WO3 nanosheets and g-C3N4 acetone sensors,
g-C3N4/WO3 gas sensor presented good response, excellent selec-
tivity, ephemeral response and trace detection ability to acetone
vapor. The results obtained with 1 wt% g-C3N4/WO3 at 340 °C
(100 ppm acetone) have shown better response (Ra/Rg) of 300%
higher than the response value of pure WO3 sensor with a fast
response/recovery speed (9 s /3.8 s) and large linear detection range
(0.5 ppm−500 ppm). Li et al.,116 have used Ru-loaded WO3
nanoparticles for acetone detection. The response obtained with
Ru-loaded WO3 sensors has been times higher than neat WO3 with a
low limit of detection (0.5 ppm). However, 1 wt% Ru loaded WO3
gave highest response (Ra/Rg) around 7.3 at 300 °C at 1.5 ppm
acetone vapour. Kim et al.,121 have presented WO3 nanofibers (NFs)
with hierarchically interconnected porosity (HP_WO3 NFs) acetone
sensor. The sensor exhibits response (Ra/Rg) of 10.80 at 1 ppm of
acetone with high humidity atmosphere (90% Relative Humidity
(RH)). Qiu et al.,124 prepared WO3 nanosheets dispersed with Rh at
its surface through a wet impregnation method. The resistance
response to acetone obtained with 1wt. and 2wt.% Rh-WO3 , were
about three orders of pristine at 250 °C with linear range of 0.5 to 10
ppm. Chen et al.,123 have worked on the acetone sensors using for
gravure-printed WO3/Pt-decorated rGO nanosheets composites. The
highest response for the sensor at 200 °C was 12.2 to 10 ppm. Shen
et al.,118 have used iron and carbon codoped WO3 with hierarchical
walnut-like microstructure to develop a selective acetone sensor. The
sensor showed better response to 10 ppm of acetone of almost 17
(Ra/Rg) at 300 °C for 0.992 at1 % Fe/WO3.
FexOy-based acetone chemiresistive sensors.—This group of
iron oxides involves commonly: FeO, Fe2O3, and Fe3O4, with Fe2O3
 Journal of The Electrochemical Society, 2020 167 037537

Table II. Electrochemical based Metal Oxides breath acetone sensors (2017–2019).

Sensing Materials LOD (ppm) Temperature (°C) Response (Ra/Rg) References

TiO2 functionalized In2O3 0.8 250 33.34 93

NiO/ZnO hollow spheres 100 275 94
ZnO decorated with Pt and Nb 50 450/400 5.2/45.8 95
TiO2 nanoporous 500 370 25.97 96
Au modified α-Fe2O3 50 150 42.0 97
SnO2/MWCNT 1 250 — 98
PPy-WO3 Hybrid 37 90 — 99
Pt-loaded α-Fe2O3 0.8 220 27.2 100
Ca-doped YbFeO3 0.1 250 1.72 101
C-doped WO3 0.9 350 5.1 102
CdMoO4 0.5 625 — 103
ZnO:Ni 116 340 68 104
Pd-ZnO/ZnCo2O4 0.4 250 — 105
C3N4-SnO2 0.067 380 29 106
In loaded WO3/SnO2 50 200 66.5 107
SnO2/SiO2 1 170 9.4 108
CdNb2O6 0.2 600 — 109
Mesoporous α-Fe2O3 nanospheres 0.1 170 16.0 110
Cuboid WO3 0.5 300 49.1 111
ZnO-Fe3O4 0.1 485 47 112
ZnO/TiO2 nanofibers 5 350 3.08 113
NiO/SnO2 0.01 300 6 114
PANI/Cellulose/WO3 10 RT (25) — 76
NiFe2O4 0.52 160 1.9 115
Ru-loaded WO3 0.5 300 — 116
Co1−xZnxFe2O4 0.3 650 — 117
Fe and C codoped WO3 0.9 300 7.3 118
Pt functionalized SnO2 0.0036 300 7.0 119
MgFe2O4/g-C3N4 500 320 — 120
Apo-Pt@HP_WO3 1 350 10.80 121
Sm2O3/SnO2 0.1 250 41.14 122
WO3/Pt-GNs 10 200 — 123
Rh/WO3 0.5 250 — 124
Sb-doped In2O3 50 240 64.3 125
Cr-doped CuO 0.32 450 — 126
Go-SnO2-TiO2 0.25 200 6.28 127
Pt@In2O3 0.01 320 6.23 28
g-C3N4/WO3 100 340 35 128
N-SnO2 0.007 300 357 129

Note: LOD = limit of detection; Ra/Rg = electrical resistance under exposure to air and target gas (acetone).

being the most used in gas-sensors. The high operating required for
Fe2O3-based gas sensors (450 °C–1075 °C), made its use less
compare to other metal oxides. Nevertheless, recently Zhang et
al.,120 have synthesized magnesium ferrite (MgFe2O4) decorated
with g-C3N4 porous microspheres composites to detect acetone. The
sensor response of MgFe2O4/g-C3N4 composites with 10 wt%
g-C3N4 based sensor showed an enhancement of ∼145 times at
lower temperature of 60 °C in comparison to a pristine MgFe2O4.
Another group Wang et al.,115 have presented the acetone sensor
working at low concentrations ∼1 ppm and lower temperatures
∼160 °C, which is based on NiFe2O4 nanocubes. The maximum
response R = Rg/Ra was 30.4 (160 °C/2 00 ppm) and around 12
under 50 ppm of acetone (160 °C).
SnO2-based acetone chemiresistive sensors.—SnO2 has high
chemical stability and exceptional electrical properties, with broad
band-gap energy (3.6 eV).39 SnO2 has been the most broadly used
material in gas sensors, including improved acetone detection,
especially when doped with other semiconductor metal oxides (e.
g. ZnO, CuO and Sm2O3). Recently, Guan et al.,129 have developed
Nitrogen-incorporated SnO2 nanostructure for high-performance
acetone gas sensing. The sensor showed sensor response of (Ra/Rg
− 1 = 357), low limit of detection (7 ppb) as well a wonderful
sensitivity for acetone gas at 300 °C. Du et al.,113 developed an
acetone vapour sensor using a synthesized hollow SnO2/ZnO
heterojunctions nanofibers. The SnO2/ZnO sensor exhibits the
highest response to each concentration, compared to the sensors with
SnO2 alone and ZnO alone. The SnO2/ZnO, SnO2, and ZnO based
sensors exhibited the responses of 3.08, 1.17, and 1.14, to 5 ppm
acetone at 375 °C, respectively. This result showed better response
for SnO2/ZnO compare to the other two alone, and has response time
of 12-s as well recovery time of 27-s. Hu et al.,114 synthesized
NiO/SnO2 (p/n) hierarchical structures via hydrothermal method for
acetone sensor in the temperature range of 210 °C–390 °C. The
maximum response obtained at 300 °C under 50 ppm of acetone was
20.18 (R = Ra/Rg). Kalidoss et al.,127 have investigated acetone in
diabetes mellitus patients’ breath in the linear range of 0.25 ppm to
30 ppm at 200 °C using of GO-SnO2-TiO2 ternary nanocomposites.
The GO-SnO2-TiO2 sensor exhibits the response of 60 (Ra/Rg) to 5
ppm acetone gas. Tomer et al.,107 have synthesized an indium loaded
WO3/SnO2 nanohybrid for acetone sensor. The results obtained from
In/WO3-SnO2 (2 wt% Indium) sensor were 66.5 (Ra/Rg) as sensor
response to 50 ppm of acetone with limit of detection ∼1 ppm at 200
°C, which were the highest compare to the other loaded. Asgari et
al.,108 have developed acetone sensors based on SiO2 decorated with
different wt% SnO2 in a wide temperatures range (70 °C–420 °C)
 Journal of The Electrochemical Society, 2020 167 037537
and concentrations (0.5–5 ppm) as well. The highest response
of ∼ 2193.7 with 300 ppm of acetone at 270 °C was obtained with
80 wt% SnO2/SiO2. The response (S = Ra/Rg − 1) of 80 wt%
SnO2/SiO2 sensor to 0.5, 1, 2.5, and 5 ppm of the exhaled acetone
was 1.4, 9.4, 24.1, and 37.5, respectively.
TiO2-based acetone chemiresistive sensors.—Its gas-sensing
properties are especially related to its structure; therefore many
research groups continue to utilize this material with specific
complement on its differing nanostructures. In 2017, Park.93 has
done measurements of exhaled acetone using TiO2 nanoparticles
functionalized with In2O3 nanowires for exhaled acetone measure-
ments. The results of measurements were completed as a function of
0.1, 0.2, 0.5, 1, 2, 5, and 10 ppm acetone at 250 ◦C with the
corresponding responses (Rg/Ra) of 4.07, 4.83, 6.17, 8.8, 12.25,
20.55, and 33.34, respectively. Chen et al.,96 synthesized nanoporous
TiO2 by a facile hydrothermal method which does not use surfactant
or template. It was discovered an improvement in the gas response of
TiO2 to acetone due to a high concentration of Oads in the
nanoporous TiO2 that was synthesized. Excellent response/recovery
time, good linear dependence, certain selectivity as well as repeat-
ability and long-term stability at 370 °C were also obtained with
nanoporous TiO2, which making it as a potential material for acetone
sensing.
In2O3-based acetone chemiresistive sensors.—Indium oxide
(In2O3), especially in its cubic form, has been generally utilized in
the microelectronic field, including gas sensors. Its use in gas sensing
depends strongly on its synthesis conditions, which will decide the
atomic structure formation, phase composition, and electronic states in
the sensing material.10 In 2018, Liu et al.,125 have developed a sensor
based on Sb-doped In2O3 microstructures for acetone detection. 2 mol
% Sb composite sensor presented the maximum response (Ra/Rg) of
64.3 with 50 ppm of acetone at 240 °C as well fast response/recovery
time of (8/27 s), and long-term stability.
ZnO-based acetone chemiresistive sensors.—Zinc oxide (ZnO)
is a n-type material and a promising semiconducting metal oxide for
gas-detecting applications. In 2017, Wongrat et al.,95 reported on Pt
and Nb decorated ZnO nanostructures. Maximum sensor response
values of 188.0 and 240.0 respectively were obtained for sensors
based on ZnO:Pt and ZnO:Nb upon exposure toward acetone vapor
at 1000 ppm concentration at 400 °C.
CuO-based acetone chemiresistive sensors.—Among the copper
oxides, due to its p-type semiconducting property, CuO is the most
reported material used in gas sensors. Late in 2018, Szkudlarek, A.,
et al.,126 have investigated the effect of Cr-doping on the electronic
structure of CuO and Cr-doped CuO thin films, deposited via DC-
pulsed magnetron sputtering at 100 °C. The results showed that the
highest response was obtained with 3.2 ppm of acetone at 450 °C
and limit of detection ∼0.4 ppm. The developed sensor shows high
sensitivity to acetone at lower concentrations with very high
operating temperature compared to the latest achievement in this
field. Bernascon et al., developed an ultra-low cost, a single-use
flexible electrochemical sensor based on plated Ni/Pt and inkjet
printed with CuO NPs, with a PET as supporting layer. The results
obtained the sensor showed a good reproducibility, high sensitivity
(around 1600 μA mM−1 cm−2), a wide linear range and a low
detection limit, coupled with a good insensitivity to other sugars
present in blood sample.131
Challenges in metal oxides-based breath acetone sensors.—
Current challenges in metal oxide based chemiresistive gas sensors
are the management of improvement of sensitivity, selectivity and
stability.132 A better management of these challenges can lead to a
good breath sensor with low detection limit, fast response time and
stability. Few of the strategies to improve sensor characteristics are
presented in the section below.
General strategies for improvement of sensor characteristics.—
As mentioned above, management of particle size and porosity of
the material can improve the sensitivity of the material in gas
sensing. For instance, usually nanostructured metal oxide shows
better electrocatalytic activities than its corresponding bulk material
leading to the surface interactions and curvature properties
enhancement.133 Another way to have a high sensitivity is the
synthesis of small size metal oxides materials especially in nan-
ometers level.20,134 Doping of metal oxides with low concentration
of metals, such as gold, silver, copper, palladium, platinum and
fluorine enhance sensitivity of metal oxides gas sensors as well.
The enhancement of selectivity of metal oxides gas sensors is
achieved through two different ways. The first way consists on the
synthesis of a material that is strictly sensitive to analyte of interest
having a low or zero cross-sensitivity to other analytes that are
present in VOCs. This is possible by initially optimizing the working
temperature, doping elements and their concentrations during
synthesis.20,135 The second way is based on the preparation of
materials for discrimination between several analytes in a mixture.
This can be done by using one sensor signal; which is normally done
either by doing sensor temperature modulation.20,136 or by using
sensor arrays.20,137
The low stability of metal oxides gas sensor leads to problems
such as false alarms, uncertain results and finally the sensor
replacement. Synthesis of Metal oxides nanomaterials such as
nanorods, nanotubes, nanowires and so on does not solve totally
the problems since those nanomaterials can be easily degraded
because of their high reactivity. However, the stability of metal
oxides gas sensor can be improved by calcination during preparation
and annealing of the film as the post-processing treatment and
furthermore reducing the working temperature of the sensor
element.20 Another way of increasing stability of metal oxides
breath sensor is to synthesize a mixed metal oxides or/and dope
metal oxides with carbon nanotubes.135 Zhang and coauthors.122
managed to increase the response of pure SnO2 by more than 2.29
times after loading samarium oxide (Sm2O3). The lowest detection
limit (LOD) obtained (around 100 ppb) due to the increase in oxygen
vacancies created by the substitution of samarium in the SnO2
lattice. Moon et al.,119 functionalized SnO2 hemipill network with a
hollow Pt. The result of functionalized SnO2 has shown high quality
response compared to non-functionalized one with detection limit of
3.6 ppb obtained with 200 ppb of acetone and high humidity (RH
80%). Shen et al.,102 developed a porous C-doped WO3 hollow
spheres biosensor that has managed to get selectivity and selectivity
for breath acetone detection. The sensor has shown better response
with good selectivity ∼ to 0.1ppm over other VOCs such as ethanol,
toluene, methanol, benzene, NH3 and CO. Kim and coauthors.138
worked on an important factor, the catalytic sensitization of the
sensing layers to increase sensor selectivity. The functionalization of
WO3 nanofibers (NFs) by Rhodium nanoparticles (Rh2O3NPs) has
been used to achieve highly sensitive and selective breath acetone
detection. A biosensing layer based on maize straw-templated
hierarchical porous Ni doped ZnO (STHPS ZnO:Ni) has been
synthesized by Zhang et al.,104 The breath acetone measurement
result has shown the short response of 6 s, recovery times of 2 s with
detection limit of 116 ppb. The stability of breath acetone sensor for
more than one year was obtained by Narjinary et al.,98 using
nanocomposites of multiwall carbon nanotubes (MWCNT)–SnO2.
Because of the MWCNT loaded in pristine SnO2, the sensor
response increases from 50% to 80%.
Effects of operational temperature and relative humidity.—
Operational temperature is another major limitation that affects
sensing application. Even though a lot of work has been done to
overcome sensitivity and selectivity of the breath acetone sensors,
high operational temperature still the main disadvantage. The
disadvantage associated are lack of flexibility, high power consump-
tion, safety hazards, reduced device lifetime,139 unfeasible accom-
modation of inflammable substances and other ecological impacts.10
 Journal of The Electrochemical Society, 2020 167 037537
Many researches have been performed to develop room temperature
acetone sensor. Conducting polymers due to their possible high
sensitivity, short response time, room temperature operation, etc are
useful in overcoming the problem. For example, a conductive
polymeric matrix of PANI-WO3 nanomaterial doped with cellulose
was applied to the detection of acetone at room temperature and low
concentrations. A limit of detection of 10 ppm was obtained for the
developed sensor after repeated exposure of acetone, showing its
suitability for room temperature sensing of acetone without the
major shortcomings of larger systems required by high operating
temperatures.76
Relative humidity (R.H) or moisture is one of the environmental
conditions that affect the performance of gas sensors. In this way,
the acetone sensing should be imperatively be optimized at around
80%–98% (R.H) before measurement because of the high humidity
of breath acetone. Therefore, consistent acetone detection needs to
be insensitive to relative humidity or moisture. For example,
Righettoni et al.,140 have developed a new breath acetone sensing
material based on Si:WO3. A significant decrease in sensitivity over
humidity of 4.5% between 80 and 90% R.H was obtained. In 2014,
Salehi et al.,141 have measured the effect of competition between
acetone and water adsorption on Carbon nanotubes–SnO2 nanocom-
posite based human breath gas sensor at 85% RH as well at low
temperature of 37 °C. The response of sensor was within tolerable
range, while it was decreasing. Early research was done by Yu et
al.,142 which confirmed irrelevant relative humidity effect to their
Polypyrrole based sensor with unfortunate maximum investigated
relative humidity effect of 45%.
Conclusions and Future Perspectives
Different conventional and sophisticated techniques, such as,
GC-MS, SIFT-MS, PTS-MS, HPLC, etc are used for the detection of
diabetes as mentioned in this review. Unfortunately, those techni-
ques are invasive and expensive. Development of chemiresistive
metal oxide-based acetone sensors are the future of non-invasive
point of care diabetes management. However, use of metal oxides
present some challenges in chemiresistive sensing applications, i.e.
sensitivity, selectivity and stability. The improvement of those
challenges will lead to better diabetes management. In this review
article, challenges and better strategies to enhance the chemiresistive
behaviour of metal oxides for acetone detection have been presented
as a guide for future perspective. In addition, the need for more work
on selected doped metal oxide materials, are highlighted.
Acknowledgments
The authors would like to thank the National Research
Foundation South Africa for funding the project (Grant UID).
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