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org/acssensors Article

Wireless Gas Sensor Based on the Mesoporous ZnO−SnO2

Heterostructure Enables Ultrasensitive and Rapid Detection of
3‑Methylbutyraldehyde
Zizheng Wang, Ping Li, Bingxi Feng, Youyou Feng, Dong Cheng, and Jing Wei*
Cite This: https://doi.org/10.1021/acssensors.4c00306 Read Online

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ABSTRACT: Achieving ultrasensitive and rapid detection of 3-

methylbutyraldehyde is crucial for monitoring chemical inter-
mediate leakage in pharmaceutical and chemical industries as well
as diagnosing ventilator-associated pneumonia by monitoring
exhaled gas. However, developing a sensitive and rapid method
for detecting 3-methylbutyraldehyde poses challenges. Herein, a
wireless chemiresistive gas sensor based on a mesoporous ZnO−
SnO2 heterostructure is fabricated to enable the ultrasensitive and
rapid detection of 3-methylbutyraldehyde for the first time. The
mesoporous ZnO−SnO2 heterostructure exhibits a uniform
spherical shape (∼79 nm in diameter), a high specific surface
area (54.8 m2 g−1), a small crystal size (∼4 nm), and a large pore
size (6.7 nm). The gas sensor demonstrates high response (18.98@
20 ppm), short response/recovery times (13/13 s), and a low detection limit (0.48 ppm) toward 3-methylbutyraldehyde.
Furthermore, a real-time monitoring system is developed utilizing microelectromechanical systems gas sensors. The modification of
amorphous ZnO on the mesoporous SnO2 pore wall can effectively increase the chemisorbed oxygen content and the thickness of
the electron depletion layer at the gas−solid interface, which facilitates the interface redox reaction and enhances the sensing
performance. This work presents an initial example of semiconductor metal oxide gas sensors for efficient detection of 3-
methylbutyraldehyde that holds great potential for ensuring safety during chemical production and disease diagnosis.
KEYWORDS: semiconductor metal oxide, microelectromechanical systems, gas sensor, mesoporous material, heterojunction

■ INTRODUCTION
3-Methylbutyraldehyde (also known as isovaleraldehyde),
chemically defined as a branched-chain aliphatic aldehyde
with the molecular composition C5H10O, assumes a pivotal
role as a natural spice renowned for its versatile applications
within the food and wine industry, specifically in the control of
aroma and color profiles. Beyond its culinary significance, 3-
methylbutyraldehyde emerges as a vital intermediary in the
synthesis of diverse pharmaceuticals and pesticides, including
compounds such as octamylamine, butizide, and pinacolone.1,2
Furthermore, the disinfection process employed in treating
drinking water unveils 3-methylbutyraldehyde as a potential
byproduct, contributing to the manifestation of odorous issues
in the water supply.3−5 The recent surge in interest
surrounding the utilization of 3-methylbutyraldehyde as a
biomarker for precise diagnosis of ventilator-associated
pneumonia (VAP) through exhaled gas analysis is particularly
noteworthy.6 Filipiak et al.7 proposed that 3-methylbutyr-
aldehyde can be specifically absorbed by Pseudomonas
aeruginosa and released by Staphylococcus aureus, suggesting
the potential of 3-methylbutyraldehyde as a promising
biomarker for the early detection of pulmonary bacterial
infections. Nevertheless, invasive diagnostic methods remain
the most common approach for diagnosing VAP8 despite their
disadvantages such as patient discomfort and time inefficiency.
The potential health hazards (e.g., nausea, irritation of skin and
respiratory mucosa, metabolic syndrome, etc.) and the risk of
fire and explosion caused by leaked 3-methylbutyraldehyde,9 as
well as the urgent need for its detection as a biomarker, make
the detection of 3-methylbutyraldehyde essential. Gas
chromatography−mass spectrometry (GC−MS) has been
used for the detection of 3-methylbutyraldehyde.10 However,
these traditional detection methods have disadvantages
involving bulky instruments, long detection time, high cost,
high technical level, and so on. Therefore, it is imperative to
develop 3-methylbutyraldehyde gas sensors that have low cost,
Received: February 8, 2024
Revised: March 25, 2024
Accepted: April 11, 2024

© XXXX American Chemical Society https://doi.org/10.1021/acssensors.4c00306

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Scheme 1. (a) Synthesis Process of Mesoporous ZnO−SnO2 Heterostructures and (b) Potential Application Scenarios of 3-
Methylbutyraldehyde Gas Sensors Based on Mesoporous ZnO−SnO2 Heterostructures
easy operation, high sensitivity, rapid response, and a low limit
of detection (LOD).
Semiconductor metal oxide (SMO) gas sensors exhibit
unique features including low cost, ease of fabrication and
integration, high sensitivity, and fast detection speed.11−15
They have been widely used in industrial production, smart
homes, food safety, environmental monitoring, and disease
diagnosis.16−18 Therefore, SMO gas sensors would be an ideal
tool to detect the leakage of the 3-methylbutyraldehyde vapor
and the concentration of 3-methylbutyraldehyde in oral
exhaled gas, which could be applied in the chemical industry
and detection of pulmonary bacterial infections. The selection
of SMOs, such as SnO2, ZnO, WO3, NiO, and CuO, plays a
pivotal role in determining the sensing performance of such
chemiresistive gas sensors.19,20 Among them, ZnO and SnO2
are both n-type semiconductors and have been widely used as
gas sensors to detect different kinds of gaseous compounds.
Moreover, constructing ZnO−SnO2 heterojunctions has been
widely accepted as a feasible method to enhance the gas
sensing performance.21,22 When metal oxides with different
energy band structures are hybridized, heterojunctions (i.e., n−
n and p−n) would be formed, resulting in the redistribution of
electrons or holes and adjustment of the depletion/
accumulation layer of SMOs.23−25 This ultimately manifests
as the change of material resistance and surface chemisorbed
oxygen species, which significantly improve the gas sensing
performance.26−30 However, as far as our current knowledge
extends, SMO gas sensors have not yet been employed for the
detection of 3-methylbutyraldehyde vapor.
Herein, a 3-methylbutyraldehyde gas sensor is fabricated
based on mesoporous ZnO−SnO2 heterostructures for the first
time. The mesoporous ZnO−SnO2 heterostructure is synthe-
sized by direct calcination of metal-polyphenol colloidal
spheres (Scheme 1a), which are obtained by the assembly of
tannic acid (TA) and metal ions (Zn2+ and Sn2+). The
obtained mesoporous ZnO−SnO2 heterostructure reveals a
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Article
uniform spherical morphology with a diameter of ∼79 nm, a
high specific surface area (54.8 m2 g−1), and a large pore size
(6.7 nm). The mesoporous ZnO−SnO2 heterostructures are
further deposited on the ceramic tube electrode to fabricate the
gas sensor, which exhibits a high response value of 18.98
toward 20 ppm 3-methylbutyraldehyde at 225 °C. The gas
sensors also show short response−recovery times (13/13 s)
and good selectivity to 3-methylbutyraldehyde. The LOD is as
low as 0.48 ppm. Low concentrations of 3-methylbutyralde-
hyde vapor in oral exhaled gas can be easily detected,
indicating the potential application of such gas sensors in
noninvasive diagnosis of pulmonary S. aureus infection
(Scheme 1b). The wireless gas sensors are further fabricated
to monitor the leakage of 3-methylbutyraldehyde in real time.
■ EXPERIMENTAL SECTION
Synthesis of Mesoporous ZnO−SnO2 Heterostructures.
Mesoporous ZnO−SnO2 heterostructures were synthesized via a
self-template strategy by direct calcination of metal-phenolic colloidal
spheres.31−33 The chemicals and detailed synthesis process are
meticulously documented in the Supporting Information. The metal-
polyphenol colloidal spheres were denoted as xZn−Sn−TA (x = 0.07,
0.10, and 0.12), where x refers to the molar ratio of Zn to Sn species
in the metal source. After calcination, mesoporous ZnO−SnO2
heterostructures were denoted as xZnO−SnO2 (x = 0.07, 0.10, and
0.12). When no Zn precursor was used, the obtained mesoporous
SnO2 nanospheres were denoted as mesoSnO2.
Gas Sensing Performance Tests. Gas sensing performances of
mesoporous ZnO−SnO2 heterostructures were tested on a MA1.0 gas
sensing system platform. In brief, gas sensing chips were prepared by
smearing the mesoporous ZnO−SnO2 heterostructure paste [dis-
persed by ethanol (EA)] on alumina tubes, which were then calcined
at 300 °C for 1 h and aged at 250 °C for 3 days. In the process of
testing, specific concentrations of different liquid samples were
injected into the gas sensing system by a micro syringe and then
heated and evaporated into gas.
The internal standard method was used for a simulative exhaled
sample test. Exhaled gases were collected from 3 healthy volunteers
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Figure 1. SEM images of (a) 0.10Zn−Sn−TA, (b) mesoSnO2, and (c) 0.10ZnO−SnO2. (d) TEM image, (e) HRTEM image, (f) SEAD pattern,
and (g−i) element mapping of 0.10ZnO−SnO2.
and were divided into two groups. One of the two groups was left
untreated to represent exhaled gas from healthy volunteers, while the
other group was supplemented with 10 ppm 3-methylbutyraldehyde
to mimic the exhalation of patients with VAP. A 0.10ZnO−SnO2
based gas sensor was used to do the tests, and all the tests were
conducted at 225 °C.
The practical application potential of a mesoporous ZnO−SnO2
heterostructure-based gas sensor was investigated through the real-
time monitoring device designed by us. Mesoporous ZnO−SnO2
heterostructures were integrated into the microelectromechanical
systems (MEMS) chip and connected with other components
through the printed circuit board (PCB). The manufacturing process
for the wireless gas sensor could be succinctly divided into three
primary phases: circuit diagram design, component selection, and
component soldering. To enhance device integration and minimize its
size, all components were soldered onto the PCB by using surface
mount technology (SMT). Following the soldering process, the PCB
underwent testing with a multimeter. Finally, the wireless gas device
was tested for its response to 3-methylbutyraldehyde.
■ RESULTS AND DISCUSSION
Synthesis and Characterization of Mesoporous ZnO−
SnO2 Heterostructures. Mesoporous ZnO−SnO2 hetero-
structures were fabricated by a self-template synthesis method.
TA is a kind of plant polyphenols that can coordinate with
different metal ions. TA was cross-linked by formaldehyde to
form the TA/formaldehyde oligomers in the presence of the
block copolymer F127. After introducing different molar ratios
of Zn2+ and Sn2+, strong coordination bonds will form between
metal species and TA, resulting in the formation of metal-
polyphenol colloidal spheres. The metal-polyphenol colloidal
spheres were denoted as xZn−Sn−TA (x = 0.07, 0.10, and
0.12), where x refers to the molar ratio of Zn to Sn species in
the metal precursors. Figures 1a and S1a−c show the scanning
electron microscopy (SEM) images of metal-polyphenol
colloidal spheres including Sn−TA, 0.07Zn−Sn−TA,
0.10Zn−Sn−TA, and 0.12Zn−Sn−TA. The average diameters
of four samples were around 147.8, 137.8, 154.2, and 168.8
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nm, respectively (Figure S2a−d). Eventually, the obtained
metal-polyphenol colloidal spheres were calcined in air to
remove the organic constituent, oxidize the metal species, and
produce mesoporous ZnO−SnO2 nanospheres. The formation
of the mesoporous structure was potentially attributed to the
synergistic effect between the release of gases resulting from
organic matter decomposition and the stacking of metal oxide
nanocrystals.34,35 The obtained mesoporous metal oxides were
denoted as xZnO−SnO2 (x = 0.07, 0.10, and 0.12). All of the
samples had uniform spherical structures (Figures 1b,c and
S1d,e). The diameters of mesoSnO 2 , 0.07ZnO−SnO 2 ,
0.10ZnO−SnO2, and 0.12ZnO−SnO2 were concentrated at
102.2, 98.8, 79.1, and 61.3 nm, respectively (Figure S2e−h),
indicating that the increase of the ZnO content led to a gradual
decrease in the particle size of the mesoporous metal oxide
(ZnO−SnO2) nanospheres.
The transmission electron microscopy (TEM) image of
0.10ZnO−SnO2 demonstrated that the mesoporous structure
was formed (Figure 1d). The high-resolution transmission
electron microscopy (HRTEM) image revealed that inter-
planar spacings of nanocrystals in mesoporous nanospheres
were 0.32 and 0.17 nm, corresponding to the (110) and (211)
planes of SnO2, respectively (Figure 1e). Furthermore, the
presence of SnO2 restrained the formation and growth of ZnO
nanocrystals,36,37 resulting in the formation of amorphous ZnO
within the interstices between SnO2 nanocrystals. There were
polycrystalline structures in the samples of 0.10ZnO−SnO2,
which was confirmed by selected area electron diffraction
patterns (Figure 1f). Besides, Sn, Zn, and O elements were
evenly distributed in the mesoporous metal oxide nanospheres
based on elemental mapping of 0.10ZnO−SnO2 (Figure 1g−
i). In addition, the energy-dispersive spectroscopy (EDS)
images further demonstrated that all of the samples contained
the three elements Sn, Zn, and O (Figure S1f).
The nitrogen adsorption−desorption isotherms of xZnO−
SnO2 samples exhibited type-IV curves with a prominent H1-
type hysteresis loop, which demonstrated that all of the
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Figure 2. (a) N2 sorption isotherms, (b) pore size distributions, and (c) XRD patterns for mesoSnO2, 0.07ZnO−SnO2, 0.10ZnO−SnO2, and
0.12ZnO−SnO2. XPS spectra of (d) Zn 2p for 0.10ZnO−SnO2, (e) Sn 3d for 0.10ZnO−SnO2, and (f) O 1s for mesoSnO2, 0.07ZnO−SnO2,
0.10ZnO−SnO2, and 0.12ZnO−SnO2.
samples have a mesoporous structure. The pore sizes of
mesoSnO2, 0.07ZnO−SnO2, 0.10ZnO−SnO2, and 0.12ZnO−
SnO2 were approximately 7.8, 6.7, 6.7, and 5.1 nm, respectively
(Figure 2a,b). The specific surface areas of mesoSnO2,
0.07ZnO−SnO2, 0.10ZnO−SnO2, and 0.12ZnO−SnO2 were
54.3, 52.6, 54.8, and 75.4 m2 g−1, respectively. In terms of
crystal phase analysis, all diffraction peaks in X-ray diffraction
(XRD) patterns of xZnO−SnO2 samples matched well with
the peaks in the standard phase of crystalline SnO2 (JCPDS no.
77-0447) (Figure 2c). No impurity peaks were observed.
Through the enlarged XRD patterns at 2θ = 34°, diffraction
peaks of different samples did not exhibit a significant shift,
indicating that Zn2+ did not enter the lattice of SnO2 (Figure
S3). Meanwhile, there were no characteristic peaks of ZnO in
XRD patterns, which indicated the formation of amorphous
ZnO. Due to the low content and calcination temperature,
amorphous ZnO was obtained. Upon further increasing the
molar ratio of the Zn to Sn precursor and increasing the
calcination temperature to 600 °C, the XRD pattern of
0.60ZnO−SnO2 exhibited distinct diffraction peaks corre-
sponding to Zn2SnO4 and SnO2 crystal phases (Figure S4).
The average crystal sizes of mesoSnO2, 0.07ZnO−SnO2,
0.10ZnO−SnO2, and 0.12ZnO−SnO2 were measured to be
4.3, 4.1, 4.0, and 3.9 nm, respectively. The textual properties of
mesoporous metal oxide heterostructures are summarized in
Table S1.
X-ray photoelectron spectroscopy (XPS) spectra of xZnO−
SnO2 indicated that the three elements (i.e., Zn, Sn, and O)
were on the surface of the samples (Figure S5a). According to
the Zn 2p spectrum of xZnO−SnO2 (Figures 2d and S5b), two
peaks belonging to Zn 2p1/2 and Zn 2p3/2 were centered at
1044.8 and 1021.9 eV, respectively.38,39 Two peaks of Sn,
located around 487 and 495 eV, could be observed in all
samples and belong to Sn 3d5/2 and Sn 3d3/2, respectively
(Figures 2e and S5c). After the process of peak differentiating
and imitating, the peaks of adsorbed oxygen (Oads), oxygen
vacancies (Ovac), and lattice oxygen (Olatt) can be determined
around 533.7 ± 0.3, 532.4 ± 0.3, and 531.0 ± 0.4 eV,
respectively, in different samples. The ratios of Oads, Ovac, and
Olatt in 0.10ZnO−SnO2 were 14.65, 23.24, and 62.11%,
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respectively (Figure 2f and Table S2). It is generally believed
that the adsorbed oxygen on the surface of the material is
conducive to enhancing the sensing performance.40 The Oads
contents of mesoSnO2, 0.07ZnO−SnO2, 0.10ZnO−SnO2, and
0.12ZnO−SnO2 were 6.11, 9.37, 14.65, and 8.37%, respec-
tively, indicating that 0.10ZnO−SnO2 had the highest Oads
content. In addition, the results of inductively coupled plasma
optical emission spectrometry (ICP-OES) showed that the
content of Zn in 0.10ZnO−SnO2 was 4.74 wt %.
Gas Sensing Performance. The performances of
mesoSnO2, 0.07ZnO−SnO2, 0.1ZnO−SnO2, and 0.12ZnO−
SnO2 gas sensors were investigated by a MA1.0 gas sensing
system platform. All of the samples were dispersed by EA and
coated on the ceramic tubes for tests. All data were measured
three times in air with the humidity controlled at 30% (unless
otherwise specified). In order to explore the optimum working
temperature, 20 ppm 3-methylbutyraldehyde was used to test
sensing performance of the gas sensors at different temper-
atures, ranging from 175 to 275 °C. With the change of
working temperature, the response values of 0.10ZnO−SnO2
were 11.96, 14.85, 18.98, 13.67, and 6.77, which showed a
volcanic trend, and the maximum point was observed at 225
°C. In addition, other gas sensors also showed the same trend
in response toward 20 ppm 3-methylbutyraldehyde upon
changing the working temperature. This indicated that the
optimal working temperature of the mesoSnO2 and xZnO−
SnO2 gas sensors was 225 °C. The decrease in response for all
of the sensors at temperatures above 225 °C was attributed to
the increased desorption rate of 3-methylbutyraldehyde
molecules at higher temperatures. Furthermore, the optimum
working temperature of different samples was 225 °C, also
indicating that heterojunctions did not have a great influence
on the working temperature in this system. As for mesoSnO2,
the highest response value toward 20 ppm 3-methylbutyr-
aldehyde was 5.56. After the modification of amorphous ZnO
on mesoporous SnO2 spheres, n−n heterojunctions would
form between SnO2 and ZnO, which could lead to the
electrons flowing from SnO2 to ZnO and the enhancement of
the gas sensing performance. The response values of
0.07ZnO−SnO2, 0.10ZnO−SnO2, and 0.12ZnO−SnO2 gas
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Figure 3. (a) Responses of mesoSnO2, 0.07ZnO−SnO2, 0.10ZnO−SnO2, and 0.12ZnO−SnO2 gas sensors toward 20 ppm 3-methylbutyraldehyde
at different working temperatures (175−275 °C). (b) Response/recovery curves of 0.10ZnO−SnO2 gas sensors toward different concentrations of
3-methylbutyraldehyde (0.5−20 ppm) at 225 °C. (c) Fitting of the linear relationship between the responses of mesoSnO2 and xZnO−SnO2
toward different concentrations of 3-methylbutyraldehyde at 225 °C. (d) Response−recovery curve of the mesoSnO2 gas sensor toward 20 ppm of
3-methylbutyraldehyde at 225 °C. (e) Response−recovery curve of the 0.10ZnO−SnO2 gas sensor toward 20 ppm 3-methylbutyraldehyde at 225
°C. (f) Responses and recovery times of xZnO−SnO2 gas sensors toward 20 ppm 3-methylbutyraldehyde at 225 °C. (g) Ten cycles of response−
recovery curves toward 20 ppm 3-methylbutyraldehyde of the 0.10ZnO−SnO2 gas sensor. (h) Response of the 0.10ZnO−SnO2 gas sensor toward
20 ppm 3-methylbutyraldehyde under different humidity conditions at 225 °C. (i) Long-term stability of the 0.10ZnO−SnO2 gas sensor over 110
days.

sensors at 225 °C were 8.93, 18.98, and 7.22, respectively,
which were 1.6, 3.4, and 1.3 times higher than that of the
mesoSnO2 gas sensor, respectively. It demonstrated that the
modification of ZnO effectively improved the response value
toward 3-methylbutyraldehyde of the gas sensors. Moreover,
the response value of 0.10ZnO−SnO2 was the highest among
all the samples at different working temperatures (Figures 3a
and S6).
The response curves of mesoSnO2 and xZnO−SnO2 gas
sensors toward different concentrations of 3-methylbutyralde-
hyde (0.5, 1, 2, 5, 10, and 20 ppm) revealed that the response
values of mesoSnO2 increased from 1.35 to 5.56 while those of
0.10ZnO−SnO2 increased from 1.64 to 18.98 (Figure 3b). The
response values of 0.07ZnO−SnO2 and 0.12ZnO−SnO2
increased from 1.51 and 1.06 to 8.93 and 7.22, respectively
(Figure S7). The concentration−response curves were
calculated and fitted to further investigate the relationship
between the concentration and response. The results revealed
significant linear associations among all samples (Figure 3c).
The response values of xZnO−SnO2 gas sensors exhibited a
greater increase with concentration than that of the mesoSnO2
gas sensor, and the LOD of 0.10ZnO−SnO2 was 0.48 ppm as
calculated by linear least-squares. The sensitivity of 0.10ZnO−
SnO2 was 0.89 ppm−1, which was 4.2, 2.3, and 2.8 times higher
than that of mesoSnO2, 0.07ZnO−SnO2, and 0.12ZnO−SnO2,
respectively (Table S3). The baseline resistance of the gas
sensors at 225 °C increased from 766 kΩ to 3.25 GΩ when the
amount of ZnO increased (Figure S8). The increase in baseline
resistance was attributed to the increase in amorphous ZnO
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and the formation of heterojunctions. The formation of
heterojunctions would lead to the thickening of the electron
depletion layer and increase the baseline resistance. In practical
applications, the response−recovery time has been taken as
one of the important criteria to evaluate the performance of gas
sensors. Therefore, the response−recovery curves of mesoSnO2
and xZnO−SnO2 gas sensors were plotted (Figure 3d,e). The
response times for mesoSnO2 and 0.10ZnO−SnO2 gas sensors
were 86 and 13 s, respectively. Besides, the recovery times at
the desorption stage of mesoSnO2 and 0.10ZnO−SnO2 gas
sensors were 49 and 13 s, respectively. The average response
times of mesoSnO2 and xZnO−SnO2 gas sensors were 79, 66,
13, and 26 s, respectively. The average recovery times were 56,
16, 13, and 14 s respectively (Figure 3f). This indicated that
the 0.10ZnO−SnO2 gas sensor had the shortest response and
recovery time. Compared with pure mesoSnO2, the mod-
ification of amorphous ZnO significantly expedited the
response and recovery speed. Ten cycles of the response−
recovery test toward 3-methylbutyraldehyde (20 ppm, 225 °C)
illustrated that the 0.10ZnO−SnO2 gas sensor had excellent
repeatability. Meanwhile, the average response of 10 cycles was
15.32, indicated that the response values of 0.10ZnO−SnO2
did not change obviously (Figure 3g).
In order to explore the influence of humidity on the gas
sensing performance, the response of 0.10ZnO−SnO2 toward
20 ppm 3-methylbutyraldehyde was tested under different
humidity values (30−70%) at 225 °C. As the relative humidity
increased from 30 to 70%, the response value of the 0.10ZnO−
SnO2 gas sensor toward 3-methylbutyraldehyde gradually
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Figure 4. (a) Responses of mesoSnO2 and xZnO−SnO2 gas sensors toward various gases at the concentration of 20 ppm. (b) Selectivity coefficient
(RIVA/Rx) of the 0.10ZnO−SnO2 gas sensor at 225 °C (x: BA, AA, MA, EA, AMN, AcN, and AT). (c) Response ratio for 20 ppm 3-
methylbutyraldehyde + 20 ppm of other interfering gas (x: BA, AA, MA, EA, AMN, AcN, and AT) at 225 °C. (d) Schematic diagram of the exhaled
breath collection process. Response−recovery curves of the 0.10ZnO−SnO2 gas sensor toward (e) exhaled gas of a healthy volunteer and (f)
exhaled gas mixed with 10 ppm 3-methylbutyraldehyde. (g) Response of the 0.10ZnO−SnO2 gas sensor toward exhaled gases of the healthy group
and diseased group. (h) Response/recovery curve of 0.10ZnO−SnO2 gas sensors toward different concentrations of 3-methylbutyraldehyde (0.5−
20 ppm) mixed with exhaled gas at 225 °C. (i) Fitting of the linear relationship between the response of 0.10ZnO−SnO2 toward different
concentrations of 3-methylbutyraldehyde mixed with exhaled gas at 225 °C.

decreased from 18.98 to 2.63 (Figures 3h and S9). The
significant decrease of the response value with the increase of
relative humidity was attributed to the production of inactive
hydroxyl groups during the reaction between water molecules
and reactive oxygen species.41 To reveal the long-term stability
of 0.10ZnO−SnO2, the repeated experiments of the 0.10ZnO−
SnO2 gas sensor toward 20 ppm 3-methylbutyraldehyde over a
period of 110 days were performed. The response value of
0.10ZnO−SnO2 remained stable for 110 days, which
demonstrated the excellent long-term stability of the gas
sensor. Furthermore, the baseline resistance of the 0.10ZnO−
SnO2-based gas sensor remained relatively stable over a period
of 110 days (Figure 3i). The above experimental results
showed that the 0.10ZnO−SnO2 gas sensor had excellent long-
term stability.
Gas sensors could be interfered by nontarget gases in the
environment during the working process, so the selectivity of
xZnO-SnO2 gas sensors was tested. Gases that may be present
in industrial environments and human-exhaled gas were
selected as potential interference gases for testing, including
benzaldehyde (BA), acetaldehyde (AA), methanol (MA), EA,
ammonia (AMN), acetonitrile (AcN), and acetone (AT). It
can be noticed that all the gas sensors showed the highest
responses toward 3-methylbutyraldehyde (IVA) and relatively
low responses toward all the other interfering gases (Figure
4a). The selectivity coefficient (calculated by the ratio of the
response toward 3-methylbutyraldehyde and interfering gases)
values of 0.10ZnO−SnO2 toward BA, AA, MA, EA, AMN,
AcN, and AT were 1.9, 15.9, 15.2, 9.5, 17.2, 18.3, and 15.9,
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respectively (Figure 4b). In real situations, the gas sensors
usually need to face a mixture of gases. Thus, the anti-
interference capability of the 0.10ZnO−SnO2 gas sensor was
tested using mixed gases. The response ratios of the 0.10ZnO−
SnO2 gas sensor toward the double gas mixtures of 20 ppm 3-
methylbutyraldehyde and 20 ppm interfering gases (BA, AA,
MA, EA, AMN, AcN, and AT) were 109, 115, 105, 103, 102,
85, and 110%, respectively (Figure 4c). These results exhibited
that adding 20 ppm of other interfering gases into 20 ppm 3-
methylbutyraldehyde did not significantly affect the response
value of the 0.10ZnO−SnO2 gas sensor. The above results
demonstrated the good selectivity and anti-interference
capability of the 0.10ZnO−SnO2 gas sensor. To investigate
the potential of the ZnO−SnO2 gas sensor for the diagnosis of
VAP, exhaled gas samples from healthy volunteers were mixed
with 10 ppm 3-methylbutyraldehyde to simulate the exhaled
gas of patients with VAP. The exhaled gases of three volunteers
were collected using gas bags (Figure 4d) and divided into two
groups. One group was added with 3-methylbutyraldehyde
(denoted the diseased group), while the other group remained
untreated (denoted the healthy group). Both groups were
tested by the 0.10ZnO−SnO2 gas sensor at 225 °C. When the
healthy group was injected, the response curve of 0.10ZnO−
SnO2 did not show significant change. However, when the
diseased group was injected, the resistance value decreased
rapidly (Figure 4e,f). The average response value of the
diseased group was 8.23, which was apparently higher than
1.17 of the healthy group (Figure 4g). Furthermore, one of the
healthy volunteers was selected randomly to collect exhaled gas
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ACS Sensors pubs.acs.org/acssensors Article

Figure 5. (a) Preparation process of the MEMS gas sensing chip. (b) Photograph of the MEMS chip, MEMS chip with the base, and MCU. (c)
Structure of the real-time monitoring device. (d) Top view of the real-time monitoring device. (e) Bottom view of the real-time monitoring device.
(f) Real-time monitoring of 3-methylbutyraldehyde.

and mixed with different concentrations (0.5−20 ppm) of 3-
methylbutyraldehyde. A 0.10ZnO−SnO2 gas sensor was used
to test. The response showed a linear trend with the increase of
the concentration of 3-methylbutyraldehyde (Figure 4h).
Based on the response curves, the LOD and sensitivity of
the 0.10ZnO−SnO2 gas sensor were 0.38 and 0.87 ppm−1,
respectively. These findings demonstrate the potential
application of ZnO−SnO2 gas sensors in the diagnosis for
VAP (Figure 4i).
Realizing the transition from material design to practical
devices is a crucial aspect of sensor research. Therefore, a
wireless gas sensor of 3-methylbutyraldehyde based on
mesoporous ZnO−SnO2 heterostructures was designed and
used to evaluate the actual application potential. The gas
sensing components were prepared by utilizing MEMS chips to
load mesoporous ZnO−SnO2 heterostructures, and the
preparation process of the MEMS gas sensing chip can be
succinctly summarized as follows: mesoporous ZnO−SnO2
heterostructures were dispersed in water to form a slurry,
which was subsequently deposited onto the interdigital
G https://doi.org/10.1021/acssensors.4c00306
electrode of the MEMS chip and dried to form a thin film
(Figure 5a). The dimensions of the MEMS chip were
approximately 2 mm in length and width. Additionally, the
photograph also provides the dimensions of the MEMS chip
with the base and microcontroller unit (Figure 5b). Before
using a MEMS gas sensor to fabricate the real-time monitoring
device, the performance of the 0.10ZnO−SnO2 MEMS gas
sensor was tested. After being exposed to different concen-
trations of 3-methylbutyraldehyde (20, 10, 5, 2, 1, and 0.5
ppm), the response of the 0.10ZnO−SnO2 MEMS gas sensor
changed accordingly. As the concentration of 3-methylbutyr-
aldehyde decreased from 20 to 0.5 ppm, the response value
also decreased from 4.4 to 1.5 (Figure S10a). Besides, based on
the concentration−response fitting curve, the LOD of the
MEMS gas sensor was 0.38 ppm (Figure S10b). The real-time
monitoring device was mainly composed of a microcontroller
unit (MCU, model: STM32F103C8T6), Bluetooth (model:
HC-06), an organic light emitting diode (OLED) screen, a
power circuit, a gas sensing unit, and a signal detection circuit.
As the core component of the device, the gas sensing unit and
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ACS Sensors pubs.acs.org/acssensors
Figure 6. Energy band diagrams of (a) SnO2, (b) ZnO, and (c) ZnO−SnO2 heterojunctions and (d) schematic diagrams of the gas sensor exposed
to air and 3-methylbutyraldehyde, respectively.
signal detection circuit consisted of an MEMS chip coated with
mesoporous ZnO−SnO2 heterostructures, reference resistance,
and heating electric power. In addition, the real-time
monitoring device was powered by a Type-C port. Upon
exposure to 3-methylbutyraldehyde, the MEMS chip exhibited
a decrease in resistance, consequently leading to a decrease in
the voltage. The voltage of the MEMS chip was monitored
through an analog to digital converter by the MCU to calculate
the resistance of the MEMS. The calculated data were sent to
the mobile phone through the Bluetooth at a rate of 100 ms
per transmission, and the voltage data were displayed on the
OLED display (Figures 5c and S11). Detailed information
about the components used in the device is listed in the
Supporting Information. Each component of the monitoring
device was integrated through the designed PCB. The
Bluetooth module, the OLED display screen, and the MEMS
sensor chip were connected to the upper layer of the PCB
through the female headers, and the remaining components are
mounted on the lower layer of the PCB through SMT. Besides,
the dimensions of the PCB were 61 mm length and 33 mm
width (Figure 5d,e). The real-time monitoring device was
tested at 225 °C (heating voltage of 2.2 V). Upon exposure to
10 ppm 3-methylbutyraldehyde, the resistance value of the
device exhibited a rapid decline, and the response−recovery
curve demonstrated a trend similar to that observed in the
previous test. The test result proved that the ZnO−SnO2 gas
sensor had practical application potential (Figure 5f and Video
S1).
Gas Sensing Mechanism of Mesoporous ZnO−SnO2
Heterostructures. The sensing performance of the SMO gas
sensor is closely related to the adsorption, dissociation, and
conversion of gas on the interface of metal oxide. In this work,
the mesoporous SnO2 nanospheres show a highly porous
structure, which promotes the gas diffusion in the sensing film.
Moreover, the high specific surface area is beneficial for the
adsorption of gas on the active sites of the metal oxide (e.g.,
defects). This study fabricated mesoporous SnO2 nanospheres
as the sensing material. The gas sensing mechanism of
H https://doi.org/10.1021/acssensors.4c00306
Article
mesoporous SnO2 nanospheres was explained by the electron
depletion layer mode.15,42,43 Oxygen was absorbed on the
surface of SnO2 in the air and got electrons to form oxygen
anions such as O2− and O−, resulting in the formation of the
electron depletion layer in SnO2. When the 3-methylbutyr-
aldehyde molecules contacted with SnO2 and were absorbed
on the surface of SnO2, they would undergo a redox reaction
with oxygen anions and lead to a concurrent release of
electrons. In this way, the electron depletion layer became
thinner, appearing as a reduction in the resistance of the SnO2
sensing film. During the desorption process, oxygen was
reabsorbed on the surface of SnO2, electrons were acquired,
and the restoration of resistance was observed. To further
boost the sensing performance, amorphous ZnO was modified
on the mesoporous SnO2 nanospheres. The work function of
SnO2 (4.9 eV) was lower than that of ZnO (5.2 eV).44,45 Upon
contact, electron transfer occurred from SnO2 to ZnO until the
Fermi levels of both reached equilibrium, resulting in the
formation of n−n heterojunctions (Figure 6a−c). This process
also led to the establishment of electron depletion layers
around the heterojunction. 46 Under the influence of
heterojunctions between SnO2 and ZnO, the resistance of
the 0.10ZnO−SnO2 gas sensor (around 700 MΩ) was
significantly higher than that of the mesoSnO2 gas sensor
(around 700 kΩ). The formation of heterojunctions would
increase the thickness of the electron depletion layer, resulting
in a high resistance.47−49 Furthermore, according to the results
of XPS, the adsorbed oxygen content on the surface of
mesoporous ZnO−SnO2 heterostructures (14.65%) was
significantly higher than that of mesoporous SnO2 nanospheres
(6.5%). This result indicated that the modification of
amorphous ZnO on mesoporous SnO2 would promote the
adsorption and dissociation of oxygen, producing more oxygen
anions (Figure 6d). Comparing with crystalline ZnO, the
amorphous ZnO exhibits a higher density of surface defects,
resulting in an increased presence of adsorbed oxygen
species.50−52 This observation is supported by XPS analysis,
which reveals a greater abundance of surface-adsorbed oxygen
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ACS Sensors pubs.acs.org/acssensors
and oxygen vacancies in mesoporous ZnO−SnO2 hetero-
structures than in mesoSnO2. The formation of oxygen anions
could further increase the thickness of the electron depletion
layer, resulting in the large resistance. When the reducing gas
(i.e., 3-methylbutyraldehyde) was introduced, more 3-methyl-
butyraldehyde could be oxidized by oxygen anions. As a result,
more electrons would return to the SnO2 materials, leading to
the remarkable decrease of the resistance. Therefore,
mesoporous ZnO−SnO2 heterostructures have higher sensi-
tivity than mesoporous SnO2 nanospheres. The modification of
ZnO on the mesoporous SnO2 nanospheres can significantly
influence the physicochemical properties of sensing materials,
encompassing the porous structure, specific surface area,
crystal defects, charge distributions, and adsorption and
transfer mechanisms of gas molecules. All these aforemen-
tioned factors exert a profound impact on the overall sensing
performance. By precisely optimizing the Zn to Sn ratio,
0.10ZnO−SnO2 exhibits superior performance compared to
other mesoporous ZnO−SnO2 heterostructures.
■ CONCLUSIONS
In summary, SMO gas sensors for sensitive and rapid detection
of 3-methylbutyraldehyde are fabricated using a mesoporous
ZnO−SnO2 heterojunction for the first time. The mesoporous
ZnO−SnO2 heterostructures have a mesoporous framework
with a pore size of around 6.7 nm, a small crystalline size (∼4
nm), and a high specific surface area (52.6−75.4 m2 g−1).
Benefiting from the mesoporous framework and heterojunc-
tions formed between ZnO and SnO2, the mesoporous ZnO−
SnO2 heterostructure gas sensors show a high response (18.98
@ 20 ppm), a short response time (13 s), and excellent long-
term stability (110 days). Moreover, the gas sensors exhibit
excellent selectivity. The response hardly changes when testing
with the gas mixture, even real expiratory air with the same
concentration of 3-methylbutyraldehyde. Moreover, the
MEMS gas sensors are fabricated and integrated with
Bluetooth. The wireless gas sensors can be used to monitor
the leakage of 3-methylbutyraldehyde in real time. The
excellent sensing performance could be attributed to the
mesoporous framework and the large specific surface area,
which could facilitate gas diffusion and adsorption. Most
importantly, the modification of amorphous ZnO on
mesoporous SnO2 spheres can form the n−n heterojunction,
which promotes the adsorption and dissociation of oxygen, as
well as the electron transfer capacity. Consequently, the
modification with ZnO significantly enhances the sensing
performance. This work provides a wireless gas sensor for
sensitive and rapid detection of 3-methylbutyraldehyde using a
mesoporous metal oxide heterostructure as a sensing material.
Based on the widespread usage of 3-methylbutyraldehyde, the
gas sensors in our study exhibit significant potential for
continuous monitoring of 3-methylbutyraldehyde in various
industries, including the food, chemical, and medical sectors,
thereby offering promising prospects for practical applications.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssensors.4c00306.
The use of the chemical reagent; synthesis process of the
materials; SEM images and EDS spectra; particle size
distributions; partially enlarged XRD patterns and XPS
I https://doi.org/10.1021/acssensors.4c00306
Article
survey spectra; the dynamic response−recovery curves
toward different concentrations of 3-methylbutyralde-
hyde of gas sensors; the baseline resistance of gas
sensors; the sensing performance of the response−
recovery curves toward 3-methylbutyraldehyde at differ-
ent humidity values; gas sensing performance test of
MEMS gas sensors; the schematic diagram of the real-
time monitoring device; the table of textual properties of
different samples; the table of relative contents of the O
element for the materials; and the table of the gas
sensing performance of the gas sensors (PDF)
Real-time monitoring of 3-methylbutyraldehyde using
the wireless gas sensor (MP4)
■ AUTHOR INFORMATION
Corresponding Author
Jing Wei − Institute of Analytical Chemistry and Instrument
for Life Science, The Key Laboratory of Biomedical
Information Engineering of Ministry of Education, School of
Life Science and Technology, Xi’an Jiaotong University, Xi’an,
Shaanxi 710049, P. R. China; orcid.org/0000-0001-
9413-2650; Email: jingwei@xjtu.edu.cn
Authors
Zizheng Wang − Institute of Analytical Chemistry and
Instrument for Life Science, The Key Laboratory of
Biomedical Information Engineering of Ministry of
Education, School of Life Science and Technology, Xi’an
Jiaotong University, Xi’an, Shaanxi 710049, P. R. China
Ping Li − Institute of Analytical Chemistry and Instrument for
Life Science, The Key Laboratory of Biomedical Information
Engineering of Ministry of Education, School of Life Science
and Technology, Xi’an Jiaotong University, Xi’an, Shaanxi
710049, P. R. China
Bingxi Feng − Institute of Analytical Chemistry and
Instrument for Life Science, The Key Laboratory of
Biomedical Information Engineering of Ministry of
Education, School of Life Science and Technology, Xi’an
Jiaotong University, Xi’an, Shaanxi 710049, P. R. China
Youyou Feng − Institute of Analytical Chemistry and
Instrument for Life Science, The Key Laboratory of
Biomedical Information Engineering of Ministry of
Education, School of Life Science and Technology, Xi’an
Jiaotong University, Xi’an, Shaanxi 710049, P. R. China
Dong Cheng − Institute of Analytical Chemistry and
Instrument for Life Science, The Key Laboratory of
Biomedical Information Engineering of Ministry of
Education, School of Life Science and Technology, Xi’an
Jiaotong University, Xi’an, Shaanxi 710049, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssensors.4c00306
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Key
Research and Development Program (no. 2022YFE0100400),
the National Natural Science Foundation of China (no.
21701130), the Key Research and Development Program of
Shaanxi (no. 2024GX-YBXM-317), the Innovation Capability
Support Program of Shaanxi (no. 2023-CX-TD-62), the
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ACS Sensors pubs.acs.org/acssensors
Fundamental Research Funds for the Central Universities, and
the Xiaomi Young Scholars Fellowship. We thank Zijun Ren at
the Instrument Analysis Center of Xi’an Jiaotong University for
their assistance with SEM analysis.
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