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

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

* Corresponding authors.
E-mail addresses: [email protected] (F. Liu), [email protected] (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. 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
Fig. 1. Diagram of material preparation process.

SEM (JEOL JSM-7500 F), TEM and HRTEM (JEOL JSM-2100 F) were
2. Experimental section used to analyze morphology and microstructure of samples. EDS
elemental mapping measurements were carried out to investigate
2.1. Synthesis of ZIF-67 and Pd@ZIF-67 elemental distribution. XRD (Rigaku D/MAX-2550, Cu-Kα radiation,
λ = 1.5418 Å) was applied to examine the crystal structure. The chem­
As shown in Fig. 1, ZIF-67 was prepared by static precipitation [12]. ical binding energy of samples was investigated by X-ray photoelectron
0.01 mol Co(NO3)2⋅6 H2O and 0.079 mol 2-Methylimidazole (C4H6N2) spectroscopy (XPS, ThermoFischer ESCALAB 250Xi). Inductively
were dissolved in 200 mL methanol, respectively. Then, the above so­ Coupled Plasma-Atomic Emission Spectrometry (ICP-AES, Perkin Elmer
lutions were mixed and stirred for 6 h. Let the mixture sit overnight and Optima 8000) was used to analyze element content.
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. 2.4. Fabrication and gas measurement
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 The fabrication and gas measurement of the sensor were similar to
NaBH4 solution was then slowly added into the solution. The products the previous work [15]. The prepared material was mixed with ethanol
were centrifuged with DI water and ethanol for several times. Finally, to form a paste so that it was uniformly covered on the gold electrode of
Pd@ZIF-67 was dispersed in 4 mL ethanol for storage. 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
2.2. Synthesis of PdO-Co3O4-SnO2 composite materials 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
Pd@ZIF-67 was added to the precursor and PdO-Co3O4-SnO2 nano­ resistance of the sensor was stabilized in the air chamber, it was trans­
fibers (NFs) was synthesized by electrospinning and calcination [13]. ferred to the TEA chamber. Then, the sensor was moved to the air
Above 80 μL Pd@ZIF-67 dispersion solution, the mixed solution of chamber again. HCHO atmosphere was obtained from 40% aqueous

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.

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

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 diameter was 332 nm. Due to the small size of Pd@ZIF-67, they may be
analytical grade liquid reagents using microsyringes. The humidity was evenly embedded in composite NFs. After calcination, the organic
about 20% RH and set at 25 ◦ C. During the test, the response is S = Ra/ compounds were broken down to form nanofibers with average diam­
Rg, where Ra and Rg indicated the resistance of the sensor when stabi­ eter of 183 nm, which composed of PdO, Co3O4 and SnO2 nanoparticles.
lized in air and TEA, respectively. In addition, the response time (tres) is As shown in Fig. 3c, the XRD patterns of pure SnO2, PdO-SnO2, Co3O4-
defined as the time required for the sensor resistance to change by 90%, SnO2 and PdO-Co3O4-SnO2-n (n = 1, 2, 3, 4) corresponded to the stan­
and the recovery time (trecov) is the time required for the resistance to dard card (PDF #41–1445). Because the content of PdO and Co3O4 were
return to 90% of the initial resistance. 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
3. Results and discussion pure SnO2. The reason for this phenomenon may be that during calci­
nation, cobalt ions were released from ZIF-67 and incorporated into the
3.1. Characterization of ZIF-67 and Pd@ZIF-67 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)
As shown in Fig. 2a, ZIF-67 nanoparticle was a dodecahedron planes were 13 and 13.9 nm, respectively, which were calculated by
structure with an edge length of about 200 nm. XRD patterns of ZIF-67 Scherrer equation. The TEM image in Fig. 3d showed PdO-Co3O4-SnO2-2
could correspond to those previously reported (Fig. 2b) [16]. After Pd2+ was a solid nanofiber composed of nanoparticles, corresponding to SEM
entered the ZIF-67 cavity and was reduced to Pd nanoparticles, the images. As shown in HRTEM image (Fig. 3e), the pink spacing was
surface morphology had been changed. From the SEM image of Fig. 2c measured at an average of 0.335 nm, consistent with the (110) plane of
and TEM image of Fig. 2d, it showed the structure of Pd@ZIF-67 was still SnO2. The interplanar spacing of green was about 0.243 and 0.284 nm,
dodecahedron, but the surface had changed from the original smooth to which matched (311) and (220) crystal planes of Co3O4, respectively.
wrinkled. This phenomenon may be due to corrosion of ZIF-67 during There was no crystal plane of PdO observed due to the too low content.
the reduction process. Similar results have been reported in the litera­ Fig. 3 f showed the EDS elemental mapping images, which contained
ture [17]. As shown in Fig. 2e, the area to the left of the purple line was four elements of Sn, O, Co and Pd. It demonstrated that all elements were
ZIF-67. The lattice spacing of nanoparticle in the circle was about evenly distributed on the nanofibers and the size of the nanoparticles
0.226 nm, which corresponded to (111) lattice plane of Pd. And its was small. The results further indicated that PdO-Co3O4-SnO2 NFs was
particle size was about 4.14 nm. EDS elemental mapping images of successfully prepared.
Pd@ZIF-67 was shown in Fig. 2f. The results further indicated that As shown in Fig. S1, there were the peaks of Sn, O and Co elements in
Pd@ZIF-67 was successfully prepared and Pd NPs was uniformly the survey spectrum. However, no peak of Pd was observed due to its
dispersed on ZIF-67. In addition, the mass ratio of Pd and Co was 14:86 low content. Fig. 4 showed the XPS spectra of samples. Sn 3d spectrum
measured by ICP-AES. 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
3.2. Characterization of PdO-Co3O4-SnO2 composite materials 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
Since there was no significant difference in the morphology of PdO-Co3O4-SnO2-2 could be classified into three peaks, corresponding
composites with different proportions, PdO-Co3O4-SnO2-2 was used as to lattice oxygen (Olat), oxygen vacancy defects (Odef) and chemisorbed
the representative to describe the morphology. As shown in Fig. 3a and oxygen (Oads). The proportion of oxygen species was calculated by peak
b, Pd@ZIF-67/PVP/Sn exhibited a smooth 1D structure, which average

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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.

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

Table 2 PdO-Co3O4-SnO2-2 was more disturbed by humidity than PdO-Co3O4-

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

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.

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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.

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Catalyst Functionalized Co3O4 Hollow Nanocages Using MOF Templates for
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