Sensors & Actuators: B.

Chemical 403 (2024) 135239

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Sensors and Actuators: B. Chemical

journal homepage: www.elsevier.com/locate/snb

Trace PdO and Co-MOF derivative modified SnO2 nanofibers for rapid
triethylamine detection with little humidity disturbance
Yilin Wang , Ziqi Liu , Yueyue Li , Yueying Liu , Xishuang Liang , Fengmin Liu *, Geyu Lu *
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, 2699 Qianjin Street, Changchun 130012, China

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

Keywords: Triethylamine (TEA) is a significant compound, but it is toxic and flammable. Since the humidity in the envi­
Pd@ZIF-67 ronment is constantly changing, it is meaningful to develop a sensor that can detect TEA efficiently and is less
SnO2 nanofibers disturbed by humidity. Here, Pd nanoparticles with a small particle size (about 4 nm) were prepared by reduction
Gas sensor
method and dispersed on Co-MOF (ZIF-67). Pd@ZIF-67-derived trace PdO and Co3O4 nanoparticles were evenly
Triethylamine
Humidity resistant
decorated on SnO2 nanofibers by electrospinning and calcination. The ratios of PdO to SnO2 in PdO-Co3O4-SnO2
were 0.012 wt% and 0.048 wt%, respectively. The response of the sensor based on 0.012 wt% PdO-Co3O4-SnO2
to 20 ppm TEA was 14 at 240 ◦ C. The response time was 3 s and the lowest concentration actually detected was 1
ppm. The synergistic effects of oxygen vacancy, p-n junction, electron sensitization of PdO and morphology of
composite improved sensing performance. In addition, due to the inhibition of hydroxyl poisoning by PdO and
the oxidation assisting effect of Co3O4, the composite had excellent humidity resistance.

1. Introduction formaldehyde [8]. Gschwend et al. reported that Pd (0–3 mol%)-loaded

Triethylamine (TEA) is widely used in medicine, coatings, dyes and
plastics, as a volatile organic compound (VOC) with fishy taste [1].
However, TEA can corrode the skin and mucous membranes, causing
pulmonary edema and even death when inhaled [2]. In addition, TEA
vapor also has flammable and explosive hazards. Therefore, it is
particularly important to study the sensor for detection of triethylamine.
In recent years, more and more researchers have realized the
detection of triethylamine using metal oxide semiconductor (MOS). As
an n-type MOS, SnO2 is the most commonly used sensitive materials for
gas sensors [3]. Among them, one-dimensional (1D) SnO2 has been
extensively studied because of its large specific surface area, good uni­
formity and high porosity [4]. Zou et al. used hollow SnO2 microfiber to
detect TEA at 270 ◦ C, which response time was 14 s [5]. Since the hu­
midity in the environment is constantly changing, it is meaningful to
develop a sensor that can is less disturbed by humidity. However, either
there was lack of research on humidity interference, or the response of
the sensor was not ideal under high humidity [6,7]. Hence, it is neces­
sary to further improve the performance of the sensor by modifying pure
SnO2.
Noble metal modification is a common way for increasing sensitivity.
Broek et al. prepared Pd-doped SnO2, which could detect 5 ppb
SnO2 had improved performance compared with pure SnO2[9]. In
addition, Suematsu et al. reported that Pd could act as a
humidity-resistant additive [10]. However, the prone agglomeration of
noble metals is a problem, which affects the utilization rate.
Metal organic framework (MOF) has the characteristics of diverse
structure and high porosity, which can encapsulate noble metal nano­
particles in its cavity. This method allows the noble metals to be evenly
divided in the MOF, without agglomeration. For example, Zhou et al.
introduce the ZIF-8 encapsulated Pt nanoparticles into the 3DIO ZnO,
which realized H2S detection[11]. Till now, PdO and Co-MOF derived
Co3O4 nanoparticles modified SnO2 nanofibers has not been studied.
In this work, Pd nanoparticles (NPs) were encapsulated in Co-MOF
(ZIF-67) by reduction method. Then Pd@ZIF-67 was added to the pre­
cursor and PdO-Co3O4-SnO2 nanofibers (NFs) was synthesized by elec­
trospinning and calcination. PdO and Co3O4 nanoparticles was evenly
dispersed on the SnO2 NFs. After gas sensing tests, the material provided
the possibility to improve triethylamine detection and reduce the
disturbance of humidity.

* Corresponding authors.
E-mail addresses: liufm@jlu.edu.cn (F. Liu), lugy@jlu.edu.cn (G. Lu).

https://doi.org/10.1016/j.snb.2023.135239
Received 17 November 2023; Received in revised form 17 December 2023; Accepted 24 December 2023
Available online 26 December 2023
0925-4005/© 2024 Elsevier B.V. All rights reserved.
Y. Wang et al.
Fig. 1. Diagram of material preparation process.
2. Experimental section
2.1. Synthesis of ZIF-67 and Pd@ZIF-67
As shown in Fig. 1, ZIF-67 was prepared by static precipitation [12].
0.01 mol Co(NO3)2⋅6 H2O and 0.079 mol 2-Methylimidazole (C4H6N2)
were dissolved in 200 mL methanol, respectively. Then, the above so­
lutions were mixed and stirred for 6 h. Let the mixture sit overnight and
centrifuge with 3000 rpm for 1 min. The products were washed several
times with ethanol and dried in an oven at 60 ◦ C overnight to obtain
ZIF-67.
Disperse 40 mg above ZIF-67 in 3 mL deionized (DI) water. After
stirring, add 10 mg K2PdCl4 and stir for another 1 h. 1.5 mg⋅mL− 1
NaBH4 solution was then slowly added into the solution. The products
were centrifuged with DI water and ethanol for several times. Finally,
Pd@ZIF-67 was dispersed in 4 mL ethanol for storage.
2.2. Synthesis of PdO-Co3O4-SnO2 composite materials
Pd@ZIF-67 was added to the precursor and PdO-Co3O4-SnO2 nano­
fibers (NFs) was synthesized by electrospinning and calcination [13].
Above 80 μL Pd@ZIF-67 dispersion solution, the mixed solution of
Fig. 2. (a) SEM image and (b) XRD pattern of ZIF-67; (c) SEM image; (d) TEM image; (e) HRTEM image and (f) EDS elemental mapping images of Pd@ZIF-67.
2
Sensors and Actuators: B. Chemical 403 (2024) 135239
2.62 g ethanol and 2.7 g N,N-dimethylformamide (DMF), 0.7 g Poly­
vinylpyrrolidone (PVP, ~1 300 000 g⋅mol− 1) and 0.5 g SnCl2⋅2 H2O
were mixed and stirred for 6 h. During the electrospinning at 25 ◦ C with
20% RH, the distance between the tip of the syringe needle (25 gauge)
and foil collector was 15 cm, and the voltage between them was 16 kV.
The syringe pump was used to maintain the feeding rate of 0.6 mL⋅h− 1.
Finally, as-spun Pd@ZIF-67/PVP/Sn was calcined at 600 ◦ C with a
heating rate of 10 ◦ C every minute for 1 h. The products were named as
pure SnO2 and PdO-Co3O4-SnO2-n (n = 1, 2, 3, 4) severally, according to
the quality of Pd@ZIF-67 (0, 20, 80, 320, 800 μL) and ethanol (2.7, 2.68,
2.62, 2.38, 1.9 g). For comparison, add Pd NPs synthesized by tradi­
tional method [14] and ZIF-67 in the precursor solution, respectively.
The products were named as PdO-SnO2 and Co3O4-SnO2.
2.3. Characterization
SEM (JEOL JSM-7500 F), TEM and HRTEM (JEOL JSM-2100 F) were
used to analyze morphology and microstructure of samples. EDS
elemental mapping measurements were carried out to investigate
elemental distribution. XRD (Rigaku D/MAX-2550, Cu-Kα radiation,
λ = 1.5418 Å) was applied to examine the crystal structure. The chem­
ical binding energy of samples was investigated by X-ray photoelectron
spectroscopy (XPS, ThermoFischer ESCALAB 250Xi). Inductively
Coupled Plasma-Atomic Emission Spectrometry (ICP-AES, Perkin Elmer
Optima 8000) was used to analyze element content.
2.4. Fabrication and gas measurement
The fabrication and gas measurement of the sensor were similar to
the previous work [15]. The prepared material was mixed with ethanol
to form a paste so that it was uniformly covered on the gold electrode of
the alumina ceramic tube (length, outer diameter and inner diameter of
4 mm, 1.2 mm and 0.8 mm, respectively). It was then calcined in a
Muffle furnace at 300 ◦ C for 2 h. The nickel-chromium heating wire was
inserted into the tube, and welded to a six-legged base.
The test was carried out in a static gas chamber (1 L). After the
resistance of the sensor was stabilized in the air chamber, it was trans­
ferred to the TEA chamber. Then, the sensor was moved to the air
chamber again. HCHO atmosphere was obtained from 40% aqueous
Y. Wang et al.
Fig. 3. (a) and (b) SEM images of Pd@ZIF-67/PVP/Sn and PdO-Co3O4-SnO2-2; (c) XRD patterns of samples; (d) TEM image; (e) HRTEM image and (f) EDS elemental
mapping images of PdO-Co3O4-SnO2-2.
solution, while TEA and other VOCs atmosphere were obtained from
analytical grade liquid reagents using microsyringes. The humidity was
about 20% RH and set at 25 ◦ C. During the test, the response is S = Ra/
Rg, where Ra and Rg indicated the resistance of the sensor when stabi­
lized in air and TEA, respectively. In addition, the response time (tres) is
defined as the time required for the sensor resistance to change by 90%,
and the recovery time (trecov) is the time required for the resistance to
return to 90% of the initial resistance.
3. Results and discussion
3.1. Characterization of ZIF-67 and Pd@ZIF-67
As shown in Fig. 2a, ZIF-67 nanoparticle was a dodecahedron
structure with an edge length of about 200 nm. XRD patterns of ZIF-67
could correspond to those previously reported (Fig. 2b) [16]. After Pd2+
entered the ZIF-67 cavity and was reduced to Pd nanoparticles, the
surface morphology had been changed. From the SEM image of Fig. 2c
and TEM image of Fig. 2d, it showed the structure of Pd@ZIF-67 was still
dodecahedron, but the surface had changed from the original smooth to
wrinkled. This phenomenon may be due to corrosion of ZIF-67 during
the reduction process. Similar results have been reported in the litera­
ture [17]. As shown in Fig. 2e, the area to the left of the purple line was
ZIF-67. The lattice spacing of nanoparticle in the circle was about
0.226 nm, which corresponded to (111) lattice plane of Pd. And its
particle size was about 4.14 nm. EDS elemental mapping images of
Pd@ZIF-67 was shown in Fig. 2f. The results further indicated that
Pd@ZIF-67 was successfully prepared and Pd NPs was uniformly
dispersed on ZIF-67. In addition, the mass ratio of Pd and Co was 14:86
measured by ICP-AES.
3.2. Characterization of PdO-Co3O4-SnO2 composite materials
Since there was no significant difference in the morphology of
composites with different proportions, PdO-Co3O4-SnO2-2 was used as
the representative to describe the morphology. As shown in Fig. 3a and
b, Pd@ZIF-67/PVP/Sn exhibited a smooth 1D structure, which average
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Sensors and Actuators: B. Chemical 403 (2024) 135239
diameter was 332 nm. Due to the small size of Pd@ZIF-67, they may be
evenly embedded in composite NFs. After calcination, the organic
compounds were broken down to form nanofibers with average diam­
eter of 183 nm, which composed of PdO, Co3O4 and SnO2 nanoparticles.
As shown in Fig. 3c, the XRD patterns of pure SnO2, PdO-SnO2, Co3O4-
SnO2 and PdO-Co3O4-SnO2-n (n = 1, 2, 3, 4) corresponded to the stan­
dard card (PDF #41–1445). Because the content of PdO and Co3O4 were
small, there was no peak in the XRD patterns. However, the peaks of
PdO-Co3O4-SnO2 were slightly shifted to lower 2θ values compared with
pure SnO2. The reason for this phenomenon may be that during calci­
nation, cobalt ions were released from ZIF-67 and incorporated into the
SnO2 lattice. In addition, the width of peaks explained that the SnO2 NPs
had a small size. The size of PdO-Co3O4-SnO2-2 at the (110) and (101)
planes were 13 and 13.9 nm, respectively, which were calculated by
Scherrer equation. The TEM image in Fig. 3d showed PdO-Co3O4-SnO2-2
was a solid nanofiber composed of nanoparticles, corresponding to SEM
images. As shown in HRTEM image (Fig. 3e), the pink spacing was
measured at an average of 0.335 nm, consistent with the (110) plane of
SnO2. The interplanar spacing of green was about 0.243 and 0.284 nm,
which matched (311) and (220) crystal planes of Co3O4, respectively.
There was no crystal plane of PdO observed due to the too low content.
Fig. 3 f showed the EDS elemental mapping images, which contained
four elements of Sn, O, Co and Pd. It demonstrated that all elements were
evenly distributed on the nanofibers and the size of the nanoparticles
was small. The results further indicated that PdO-Co3O4-SnO2 NFs was
successfully prepared.
As shown in Fig. S1, there were the peaks of Sn, O and Co elements in
the survey spectrum. However, no peak of Pd was observed due to its
low content. Fig. 4 showed the XPS spectra of samples. Sn 3d spectrum
appeared symmetrical doublets (Fig. 4a) [18]. The binding energy of
PdO-Co3O4-SnO2-2 shifted 0.106 eV or 0.056 eV to a lower energy,
which explained that Cox+ was doped into the SnO2 lattice, reducing the
electron density of SnO2[19]. This also corresponded to the XRD results
(Fig. 3c). For the O 1 s spectrum (Fig. 4b), the spectrum of pure SnO2 and
PdO-Co3O4-SnO2-2 could be classified into three peaks, corresponding
to lattice oxygen (Olat), oxygen vacancy defects (Odef) and chemisorbed
oxygen (Oads). The proportion of oxygen species was calculated by peak
Y. Wang et al. Sensors and Actuators: B. Chemical 403 (2024) 135239

Fig. 4. (a) Sn 3d and (b) O 1 s XPS spectra of pure SnO2 and PdO-Co3O4-SnO2-2; (c) Co 2p and (d) Pd 3d XPS spectra of PdO-Co3O4-SnO2-4.

3.3. Gas sensing property

Table 1
The proportion of Olat, Odef, Oads for SnO2 and PdO-Co3O4-SnO2-2.
Research on optimum working temperature is beneficial to maximize
Materials Olat Odef Oads the performance of the sensor. When the temperature was below 200 ◦ C
SnO2 73.44% 22.22% 4.34% or above 280 ◦ C, the response was low. As shown in Fig. 5a, the response
PdO-Co3O4-SnO2-2 69.27% 25.49% 5.24% increased first and then decreased with the increase of temperature from
200 to 280 ◦ C, which was related to activation energy and molecular
dynamics. The sensor based on PdO-Co3O4-SnO2-2 exhibited the highest
area, and the results were shown in Table 1. Compared with pure SnO2,
response at 240 ◦ C, and the response to 20 ppm TEA was 14. The sensing
Odef and Oads contents of PdO-Co3O4-SnO2-2 increased from 22.22% and
properties of all samples to TEA were shown in Table S1. The addition of
4.34% to 25.49% and 5.24%. Because Cox+ replaced Sn4+, the lattice
excessive Pd@ZIF-67 may lead to the reduction of the space between the
was distorted, resulting in more oxygen vacancies[20]. In addition, due
NPs after calcination, thus reducing the response [19]. Fig. 5b showed
to the catalytic activity of PdO, more Oads was absorbed. However, the
that as the amount of Pd@ZIF-67 increased, the resistance gradually
environment of XPS was a vacuum at room temperature, the content
became larger due to the increase in heterojunction. However, all
increased was not significant. Besides, in order to observe the spectrums
resistance were larger than pure SnO2 except PdO-Co3O4-SnO2-1. This
of Co and Pd more clearly, PdO-Co3O4-SnO2-4 was tested. As shown in
phenomenon may be due to the high conductivity of Co3O4, but when
Fig. 4c, Co 2p spectra could be fitted into Co2+ 2p3/2, Co3+ 2p3/2, Co2+
the heterojunction was dominant, the resistance increased. Fig. 5c
2p1/2 and Co3+ 2p1/2, which proved the formation of Co3O4[19]. Simi­
showed the dynamic responses to 1 - 50 ppm TEA, indicating the sensor
larly, the two peaks of Pd 3d represented Pd2+ 3d3/2, Pd2+ 3d5/2, indi­
based PdO-Co3O4-SnO2-2 could recognize different concentrations of
cating Pd element existed in the oxidation state (Fig. 4d)[21].
TEA excellently. And the lowest concentration actually detected was
Moreover, according to ICP results and feed ratio, the ratios of PdO to
1 ppm (S = 1.55). Surprisingly, the theoretical Limit of Detections (LOD)
SnO2 in PdO-Co3O4-SnO2-2 and PdO-Co3O4-SnO2-3 were 0.012 wt%
was calculated to be 82.96 ppb. The fitting curve of the PdO-­
and 0.048 wt%, respectively.
Co3O4-SnO2-2 responses was shown in Fig. S2. In addition, Fig. 5d
showed that all sensors had a smaller resistance in N2 than in air. The
resistance variation of sensors in N2 and air at 240 ◦ C was shown in

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Y. Wang et al. Sensors and Actuators: B. Chemical 403 (2024) 135239

Fig. 5. (a) Effect of temperature on response of six sensors based on SnO2, PdO-SnO2, Co3O4-SnO2 and PdO-Co3O4-SnO2 to 20 ppm TEA; (b) Corresponding
resistance; (c) Dynamic responses of TEA in the range of 1 - 50 ppm; (d) Comparison of resistance in N2 and air at 240 ◦ C.

5
Y. Wang et al.
Table 2
The resistance variation of sensors in N2 and air at 240 ◦ C.
Samples SnO2 PdO- Co3O4- PdO- PdO-
SnO2 SnO2 Co3O4- Co3O4-
SnO2-1 SnO2-2
S′ 123% 156% 145% 215% 394%
a
S′= (Ra-Rn)/Rn * 100%, Rn represents the resistance in N2.
Table 2. The results confirmed the effect of Oads on the resistance,
indicating that the surface of PdO-Co3O4-SnO2-2 had more Oads, which
corresponded to the results of XPS.
Moreover, as shown in Fig. 6, the response time was 5 - 8 s for pure
SnO2, 3 s for PdO-Co3O4-SnO2-2, and 15 - 21 s for PdO-Co3O4-SnO2-3.
Normally, the recovery time was 233 s, 282 s and 522 s for them,
respectively. While the higher temperature caused rapid desorption of
triethylamine. Recovery time of them was reduced to 24 s, 47 s and 64 s,
respectively (Fig. 6d – f). The sensor based on PdO-Co3O4-SnO2-2 had a
fast response speed, and the recovery time was slightly increased
compared to pure SnO2, possibly due to the adsorption of more TEA. In
addition, the large amount of oxygen and rapid desorption of TEA made
sensor resistance higher than Ra, when transferred from TEA to air at
high temperature. After that, electron transfer stabilized the resistance.
Fig. 7a showed the response of six sensors toward eight gas atmo­
spheres under the concentration of 20 ppm. Obviously, the sensor based
on PdO-Co3O4-SnO2-2 showed the highest response to TEA. One reason
was that C-N bond energy of triethylamine was lower, which was prone
to break [22]. Besides, SnO2 was an acidic oxide, which was conducive
to the adsorption of the alkaline gas triethylamine. Another reason was
that the lone pair electrons of triethylamine made it more easily
adsorbed [23].
In addition, it was worth noting that the sensors based PdO-Co3O4-
SnO2 were less disturbed by humidity (Fig. 7b). As shown in Table 3,
PdO, Co3O4 and PdO-Co3O4 improved the humidity resistance compared
with pure SnO2. In general, water molecules could compete with Oads
and TEA molecules, reducing the response. Therefore, the more sensitive
Fig. 6. Resistance curves of (a, d) pure SnO2; (b, e) PdO-Co3O4-SnO2-2 and (c, f) PdO-Co3O4-SnO2-3 to 20 ppm TEA, severally.
Sensors and Actuators: B. Chemical 403 (2024) 135239
PdO-Co3O4-SnO2-2 was more disturbed by humidity than PdO-Co3O4-
SnO2-3. The excellent humidity resistance of PdO-Co3O4-SnO2-3 made it
PdO- stable when humidity changed. One reason was that Pd could be used as
Co3O4- a humidity-resistant additive because it could inhibit hydroxyl
SnO2-3 poisoning [10]. Besides, it was reported that Co3O4 had stability
271%
dependent on humidity due to oxidation assisting effect [24].
Fig. 7c was the response curve of sensors for 6 consecutive times. The
good repeatability of sensor made the response value change less. The
response of PdO-Co3O4-SnO2-2 fluctuated slightly within 21 days,
possibly due to humidity. While the response of PdO-Co3O4-SnO2-3 was
almost unchanged, which explained the sensor had outstanding long-
term stability (Fig. 7d).
A comparison of the performance of different sensors in TEA detec­
tion was shown in Table 4. The SH% /SL% of PdO-Co3O4-SnO2-3 was
110.9% higher than others, indicating the sensor could be used at
different humidity with little interference. And the sensor based PdO-
Co3O4-SnO2-2 enabled rapid detection of triethylamine.
3.4. Gas sensing mechanism
In general, change of resistance due to exposure to different atmo­
spheres can be used to illustrate gas sensing mechanism of MOS. At
working temperature of 240 ◦ C, Oads existed in the form of O-[29]. As
shown in Fig. 8, when the sensor was exposed to TEA, the Oads on its
surface would react with the adsorbed triethylamine. The corresponding
reaction equations are as follows [30]:
(C2 H5 )3 N(gas) →(C2 H5 )3 N(ads) (1)
2(C2 H5 )3 N(ads) + (39 + 2x)O−(ads) →2NOx + 12CO2 + 15H2 O + (39 + 2x)e−
(2)
For PdO-Co3O4-SnO2, the reasons for the enhanced property can be
explained in several ways. Firstly, the results of XRD and XPS showed
that Co2+ and Co3+ took the place of Sn4+ in SnO2 lattice and formed
Co′Sn and Co′Sn , which increased the content of oxygen vacancy [19,31].
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Y. Wang et al. Sensors and Actuators: B. Chemical 403 (2024) 135239

Fig. 7. (a) Selectivity of six sensors (the sensor based on SnO2 operated at 260 ◦ C, PdO-SnO2 at 220 ◦ C, and other sensors at 240 ◦ C); (b) Effect of humidity on
response to 20 ppm TEA (the relative humidity was set at 25 ◦ C); (c) Repeatability and (d) Response within 21 days of PdO-Co3O4-SnO2-2 and PdO-Co3O4-SnO2-3.

layer decreased and the resistance changed significantly.

Table 3 Thirdly, as shown by XPS results, Pd element existed in the oxidation
Effect of humidity on response to 20 ppm TEA. state (Pd2+). When the material was exposed to a reducing gas, PdO was
Samples SnO2 PdO- Co3O4- PdO- PdO- PdO- reduced to Pd0, resulting in electron transfer and lower resistance [13].
SnO2 SnO2 Co3O4- Co3O4- Co3O4- In addition, Pd0 could reduce the activation energy of reaction (2),
SnO2-1 SnO2-2 SnO2-3
making the reaction more likely to occur. Similarly, after the sensor was
S40%/ 61.1% 122.2% 98.6% 90.8% 95.7% 112.5% exposed to air, Pd0 was oxidized to PdO, which made the resistance
S20%
increase.
S60%/ 40.4% 98% 76.2% 54.5% 74.0% 111.8%
S20% Finally, the morphology of the composite also had an effect on the
S80%/ 34.0% 72.0% 60.6% 50.4% 57.8% 110.9% response. Nanofibers consisted of a large number of nanoparticles, and
S20% the space between the particles made them have a large specific surface
b
SX% represents the response at X% RH. The sensor based on SnO2 operated at area. Unique structure allowed the electrons to transfer along the axial
260 ◦ C, PdO-SnO2 at 220 ◦ C, and other sensors at 240 ◦ C. direction of the 1D structure and adjust the resistance of the sensor [4].
In addition, the unique preparation method may make the dispersion of
The increase of oxygen vacancy was beneficial to increase the active site PdO catalyst increase, which explained the trace amount of PdO. The
and thus contributing to adsorption of oxygen. The equations involved more surface atoms exposed, the higher catalytic activity was, thus
are as follows: increasing the utilization rate. Besides, PdO and Co3O4 NPs were evenly
dispersed on the surface of SnO2 NFs by encapsulating noble metal in
Co3 O4
SnO2
̅̅̅→ Co′Sn + 2Co′Sn + 4OXO + 2V••
O (3) MOF and using electrospinning. The synergistic effect of them could
maximize the catalytic effect.
Secondly, the formation of heterojunction enhanced the sensing
performance. SnO2 is an n-type MOS, while PdO and Co3O4 are p-type
4. Conclusions
MOS. The presence of p-n junction increased the resistance of the ma­
terial (Fig. 5d) and had a positive effect on the response. Electrons
In this work, trace PdO and Co3O4 nanoparticles were evenly deco­
flowed from SnO2 (4.4 eV) to PdO (7.9 eV) and Co3O4 (6.5 eV) because
rated on SnO2 nanofibers by electrospinning and calcination. Material
of the difference in work function, causing depletion layers to form [13,
characterization and gas sensing property were studied, showing that
32,33]. When the sensor was exposed to triethylamine, the depletion
0.012 wt% and 0.048 wt% PdO-Co3O4-SnO2 had excellent properties for

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Y. Wang et al. Sensors and Actuators: B. Chemical 403 (2024) 135239

Table 4
Comparison of the performance of triethylamine detected by different sensors.
Materials Noble metal amount T C S(Ra/Rg or Rg/ Ra) tres/trecov(s) RH range (%) SH% /SL% Ref.
(℃) (ppm)

Co3O4/carbon nanofibers - 150 50 3.8 27/28 57 - 88 ~66% [25]

SnO2 nanotube - 235 50 54.9 19/10 20 - 80 ~4.3% [7]
SnO2-AuAg 0.5 at% 240 100 61.3 4/24 30 - 90 ~29.7% [26]
Mo-SnO2 - 250 100 14 15/25 6.6 - 95 69.9% [27]
Au@SnO2/MoS2 40.3 wt% 300 100 76 12/66 25 - 85 30.3% [28]
PdO-Co3O4-SnO2-2 0.012 wt% 240 20 14 3/47 20 - 80 52.4% This work
PdO-Co3O4-SnO2-3 0.048 wt% 240 20 11 21/64 20 - 80 110.9% This work
c
SH% and SL% represent the response at high humidity and low humidity, respectively.
d
In this work, the sensors were heated up to 280 ◦ C to quickly desorb TEA.

References

Fig. 8. Sensing mechanism of PdO-Co3O4-SnO2 exposed in triethylamine.
the detection of TEA such as fast response and good humidity resistance,
due to the synergistic effect of PdO and Co3O4. These results confirmed
that PdO-Co3O4-SnO2 provided ideas for reducing the disturbance of
humidity and efficiently detecting triethylamine.
CRediT authorship contribution statement
Liang Xishuang: Writing – review & editing. Liu Fengmin: Writing
– review & editing. Lu Geyu: Writing – review & editing. Wang Yilin:
Writing – original draft, Methodology, Formal analysis, Data curation,
Conceptualization. Liu Ziqi: Validation, Data curation. Li Yueyue:
Validation. Liu Yueying: Validation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgment
This work was supported by the National Key Research and Devel­
opment Program of China (2021YFB3201301), National Natural Science
Foundation of China (Nos. 62271225 and 61871198), and Project on
Industrial Innovation Capability of Jilin Province (No. 2020C048).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.snb.2023.135239.
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Yilin Wang received a bachelor’s degree in electronic science and technology from Jilin
University in 2020. Currently studying for a Doctor’s degree at Jilin University. Her work
is to study the gas-sensing properties of alloy nanoparticles modified metal oxide
semiconductors.
Ziqi Liu received a bachelor’s degree in automation in 2020 and she is currently studying
for a master’s degree in College of Electronic Science and Engineering, Jilin University,
China.
Yueyue Li obtained a bachelor’s degree in electronic science and technology in 2019 and
is currently studying for her PhD degree in the College of Electronic Science and Engi­
neering, Jilin University, China.
Yueying Liu received the PhD degree in 2023 from College of Electronic Science and
Engineering, Jilin University, China. Now she is an engineer in Jilin University. Her cur­
rent research mainly focus on scanning electron microscope.
Xishuang Liang received the B. Eng. Degree in Department of Electronic Science and
Technology in 2004. He received his Doctor’s degree in College of Electronic Science and
Engineering at Jilin University in 2009. Now he is a professor of Jilin University, China.
His current research is solid electrolyte gas sensor.
Fengmin Liu received the BE degree in Department of Electronic Science and Technology
in 2000. She received his Doctor’s degree in College of Electronic Science and Engineering
at Jilin University in 2005. Now she is a professor in Jilin University, China. Her current
research is preparation and application of semiconductor oxide, especial in gas sensor and
solar cell.
Geyu Lu received the B.Sci. degree in Electronic Sciences in 1985 and the M.Sci. degree in
1988 from Jilin University in China and the Dr.Eng. degree in 1998 from Kyushu Uni­
versity in Japan. Now he is a professor of Jilin University, China. His current research
interests include the development of chemical sensors and the application of the function
materials.