Surfaces and Interfaces 24 (2021) 101110

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Surfaces and Interfaces

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A gas sensor based on Ag-modified ZnO flower-like microspheres:

Temperature-modulated dual selectivity to CO and CH4
Yan Wang a, Yuanyuan Cui a, Xiaoning Meng a, Zhanying Zhang a, Jianliang Cao b, *
a
State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, State Key Laboratory Cultivation Bases for Gas Geology and Gas Control,
College of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, PR China
b
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, PR China

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

Keywords: The detection of carbon monoxide (CO) and methane (CH4) is crucial given that CH4 explosions and CO
Ag/ZnO microspheres poisoning are two major gas accidents that seriously restrict coal mining safety. In this study, Ag-modified ZnO
Gas sensor flower-like microspheres are prepared by a solvothermal method combined with an impregnation route. The
Dual selectivity
techniques of X-ray diffraction characterize the crystallographic information, morphology and surface compo­
Methane
Carbon monoxide
sition of the samples, field emission scanning electron microscopy, transmission electron microscopy and X-ray
photoelectron spectroscopy. The gas sensing measurement results show that a sensor based on 1.5 at.% Ag/ZnO
microspheres exhibits temperature-modulated dual selectivity detection for CO at 130◦ C and CH4 at 200◦ C.
Furthermore, the sensor possesses satisfactory sensing performance with high response, fast response/recovery
rate, low detection limit and excellent selectivity. The enhanced sensing properties of ZnO microspheres
modified with Ag nanoparticles are mainly attributed to the chemical sensitization of Ag nanoparticles, the
formation Schottky barrier between semiconducting ZnO and the noble metal Ag and the p-n heterojunction
between Ag2O and ZnO. Our experimental results indicate that the obtained sensor is based on 1.5 at.% Ag/ZnO
microspheres have broad application prospects in the detection of coal mine gases.

1. Introduction Therefore, semiconducting metal oxides are promising sensing materials

for detecting various toxic and harmful gases [8].
Gas is a mixture of gases produced during coal mining, since its main Currently, metal oxide semiconductor sensing materials, such as
component is the explosive gas methane (CH4), which accounts for SnO2 [9], ZnO [10], TiO2 [11], Fe2O3 [12], and NiO [13], have been
~83–89%, in addition to the asphyxiating gas carbon monoxide (CO) as considered as promising matrix materials, owing to their stable physi­
a trace component. In the process of coal mining, CH4 explosions and CO cochemical properties. Among these metal oxide semiconducting ma­
poisoning are two common gas disasters, which severely restrict the terials, n-type ZnO has been widely used to detect a variety of harmful
safety production of coal mines [1]. Therefore, accurately identifying gases, including H2S [14], NO2 [15], H2 [16], and CO [17]. However,
and measuring gas concentrations and taking precautionary measures in pure ZnO suffers from some drawbacks, such as low sensitivity, slow
advance is key to preventing gas disasters. Moreover, the lower explo­ response/recovery rate and poor selectivity. Noble metals possess strong
sion limit of CH4 is 4.9% and the permissible exposure limit of CO is catalytic activity, which can effectively reduce the target gas’s chemical
0.0024%, according to Safety Regulations of Coal Mines of China. Thus, adsorption energy and play active catalytic centers. Besides, a Schottky
the detection of CH4 and CO is necessary to guarantee coal mine safety barrier will be formed at the interface of semiconductors and noble
and miner security. Various types of sensing devices have been used to metals, which can be used as an electron trap to capture free electrons
monitor CH4 concentrations, including non-dispersive infrared adsorp­ and further improve the surface activity of metal oxide semiconductors
tion spectroscopy [2], catalytic combustion [3], surface acoustic wave improve their gas sensing performance. As the cheapest noble metal, Ag
[4] and metal oxide semiconductor sensors [5–7]. Among these detec­ is usually used as a sensitizer to upgrade metal oxide semiconductors’
tion technologies, metal oxide semiconductor gas sensors possess the sensing capability. For instance, Zhang et al. [18] reported that the
advantages of an excellent response, good stability and easy integration. Ag-Zn2SnO4/SnO2 hollow nanospheres were prepared by a one-step

* Corresponding author.
E-mail address: caojianliang@hpu.edu.cn (J. Cao).

https://doi.org/10.1016/j.surfin.2021.101110
Received 9 November 2020; Received in revised form 16 March 2021; Accepted 23 March 2021
Available online 29 March 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
Y. Wang et al. Surfaces and Interfaces 24 (2021) 101110

hydrothermal method exhibited better performance to 50 ppm formal­ processes of pure ZnO and Ag/ZnO microspheres is displayed in Fig. 1.
dehyde compared with pure Zn2SnO4/SnO2. Yang et al. [19] reported According to Ag to Zn’s atomic number ratios,the synthesized samples
that Ag@TiO2 nanowires exhibited an excellent response to ammonia, were labeled as ZnO, 1.0 at.% Ag/ZnO, 1.5 at.% Ag/ZnO and 2.0 at.%
owing to forming a Schottky barrier between Ag and TiO2. Ding et al. Ag/ZnO.
[20] reported that Ag-doped hollow urchin-like In2O3 spheres could
enhance the response of NO2, owing to the catalytic activity of the Ag 2.4. Characterization
nanoparticles. The method of coating new materials on the substrate can
significantly improve the various properties of the materials. For X-ray diffraction (XRD) patterns were recorded on a Bruker AXS D8-
instance, Lin et al. [21] reported that Systematic studies for the novel Advance diffractometer (40 kV, 25 mA, Cu-Kα radiation and 10◦ min-1
synthesis of nano-structured lanthanide flfluorides. Liu et al. [22] re­ from 10◦ to 80◦ ). Field emission scanning electron microscopy (FESEM)
ported that Reinforcing effects of waterproof substrate on the photo-, images and EDS elemental maps were obtained using a Hitachi SU8220
thermal and pH stabilities of perovskite nanocrystals. Therefore, Ag SEM equipped with a Bruler Quantax Flat QUAD energy dispersive
nanoparticles modification on metal oxide semiconductor surfaces is spectrometer at 10 kV. Transmission electron microscopy (TEM) images
expected to show satisfactory sensing properties. were collected on a JEOL JEM-2100 TEM at 200 kV. X-ray photoelectron
This study synthesized ZnO flower-like microspheres via a sol­ spectroscopy (XPS) analysis was carried out on a Thermo Fisher ESCA­
vothermal method and then decorated them with Ag nanoparticles on LAB 250Xi (Al-Kα radiation, hv = 1486.6 eV and C 1s peak at 284.4 eV).
the ZnO surface by a facile impregnation method. The gas sensing per­ The specific surface area of the prepared samples was measured on a
formance of the Ag/ZnO microspheres was systematically investigated. Quantachrome Autosorb-iQ sorption analyzer by using the Brunauer-
The gas sensing measurement results showed that a sensor based on 1.5 Emmett-Teller (BET) method. The pore size distribution was derived
at.% Ag/ZnO exhibited dual selectivity detection for CO at 130◦ C and from the adsorption branch of the adsorption-desorption isotherms
CH4 at 200◦ C. Considering the spillover effect of Ag nanoparticles, the using the Discrete Fourier Transform (DFT) method. The samples were
formation of the Schottky barrier between ZnO and Ag, and the p-n analyzed by thermogravimetric analysis using a German Netzsch
heterojunction between ZnO and Ag2O, the sensing mechanisms are STA449C TG-DSC analyzer (heating rate of 10◦ C•min− 1, a temperature
discussed detail. range of room temperature to 800◦ C) and the TG-DSC charts were
drawn.
2. Experimental section
2.5. Fabrication and measurement of gas sensors
2.1. Materials
The fabrication process of the gas sensor has been discussed in our
Zinc nitrate hexahydrate (Zn(NO3)2•6H2O, 99.0%) and urea previous reports [23,24]. The as-prepared samples and DI water were
(CH4N2O,99.0%) was purchased from Tianjin Kemiou Chemical Reagent mixed to form a paste by grinding. Subsequently, this paste was brushed
Co., Ltd. China. Ethanol (CH3CH2OH, 99.7%) was purchased from on the surface of interdigital electrodes on a ceramic substrate to form
Shanxi Tongjie Chemical Reagent Co., Ltd., China. Silver nitrate the sensing film. Finally, the as-obtained gas sensor was naturally dried
(AgNO3, 99.9%) was purchased from the Shanghai Institute of Fine in the shade and then aged at 150◦ C for 16 h to improve its stability.
Chemicals, China. Glycol (HOCH2CH2OH, 98.0%) was purchased from The gas sensing performances were measured using the intelligent
Luoyang Chemical Reagent Factory, China. All of the chemical raw re­ gas sensing analysis system of a hazardous gas sensor (CGS-4TPs, Beijing
agents used in the experiment were analytical-grade purity and directly Elite Tech Co., Ltd., Beijing, China) at 30–35◦ C and relative humidity of
used without further purification. Distilled water was used in the whole 40–45% by a static gas distribution method (Fig. 2). The gas sensor was
experiment process. put on the heating stage of a closed test chamber and the probe gas was
then injected into the gas chamber (1.8 L) with a syringe when the
2.2. Preparation of ZnO flower-like microspheres resistance value of the measuring element in the air was stable. Subse­
quently, the gas chamber was opened after the sensor was exposed to
The ZnO flower-like microspheres were obtained via a simple sol­ test gas for a while. In this study, the response was defined as the gas
vothermal route with Zn(NO3)2•6H2O as the Zn source, urea as the sensor’s resistance ratio before and after exposure to reducing gas (Ra/
precipitant and ethylene glycol as the solvent. In brief, 1.19 g of Zn Rg), where Ra and Rg are the resistances in the air and probe gas,
(NO3)2•6H2O and 1.00 g of urea were dissolved into a solution of 20 mL respectively. The response time (τres) was defined as the time required
of ethylene glycol and 20 mL of deionized (DI) water. The above solution for the gas sensor to reach 90% of the stable resistance value from
was then stirred for 30 min at room temperature and transferred to a 50 contacting the probe gas. The recovery time (τrec) was defined as the
mL Teflon-lined stainless steel autoclave, sealed and heated at 100◦ C for time required for the gas sensor to recover 90% of the resistance value in
12 h. After the autoclave was cooled to room temperature naturally, the clean air from missing the target gas.
precipitates were collected by centrifugation and washed with DI water
several times until the supernatant’s pH was neutral. Finally, the ZnO 3. Results and discussion
microspheres were obtained by dried at 60◦ C for 6 h and annealing at
400◦ C for 1 h. 3.1. Materials characterization

2.3. Preparation of Ag-modified ZnO flower-like microspheres The crystal structures of Ag/ZnO nanomaterials with different con­
tents of Ag were investigated by XRD characterization. From Fig. 3, all
The Ag-modified ZnO microspheres were synthesized via an the as-prepared samples exhibit three main diffraction peaks at
impregnation method. ZnO microspheres (162.76 mg) were dispersed in diffraction angles of 36.21◦ , 31.74◦ , and 34.38◦ corresponding to the
20 mL of DI water with magnetic stirring for several minutes. An (101), (100) and (002) crystal planes of the wurtzite structure of ZnO
appropriate amount of AgNO3 aqueous solution (0.015 M) was dropped (JCPDS: 89-1397), respectively. In general, the peak intensity of Ag is
into the above solution and gently stirred for 4 h. The products were weak and almost invisible, which may be attributed to the extremely low
then washed with DI water and absolute ethanol in turn and the pre­ Ag content and homogeneous loading distribution of Ag nanoparticles in
cipitates obtained by centrifugation were dried in an oven at 60◦ C for 6 ZnO. However, the existence of Ag can be demonstrated by EDS, HR-
h. Finally, the Ag/ZnO flower-like microspheres were obtained by TEM and XPS characterization, as discussed later. Furthermore, no im­
annealing at 350◦ C for 1 h. A schematic illustration of the synthesis purity peaks exist in the XRD patterns, confirming that the samples are

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Fig. 1. Schematic illustration for the synthesis processes of pure ZnO and Ag/ZnO flower-like microspheres.

Fig. 2. Schematic diagram of sensing test device, the inset is the planar type gas sensor.

successfully prepared by the hydrothermal method. From the high-

magnification SEM images, the porous nanosheets have a thickness of
~20 nm. This three-dimensional porous structure is beneficial to gas
diffusion due to its high surface area and pores that can be used as
transport channels for gas molecules. The morphology of the ZnO mi­
crospheres remains unchanged after Ag loading; its structure is stable
and does not break into dispersed nanosheets even after 4 h of vigorous
stirring. The EDS elemental mapping (Figs. 4e–h) displays the existence
of Zn, O and Ag, with Zn and O originating from ZnO. Moreover, Fig. 4h
demonstrates the even distribution of Ag on the ZnO surface. Figs. 4i–j
show the flower-like microsphere structure of 1.0 at.% Ag/ZnO and 2.0
at.% Ag/ZnO, and we can see from these images that ZnO’s morphology
and size are not affected by the different doping content of Ag. Further
structure analysis was performed by using the techniques of TEM and
HR-TEM. From Figs. 5a and c, many pores exist in the nanosheets, which
is consistent with the FESEM results. In addition, the red rectangular
section in Fig. 5c is characterized by HR-TEM to determine the
composition of the black spot. The obtained HR-TEM image in Fig. 5d
Fig. 3. XRD patterns of (a) ZnO, (b) 1.0 at.% Ag/ZnO, (c) 1.5 at.% Ag/ZnO and presents interplanar spacings of 0.23 and 0.25 nm for the (111) crystal
(d) 2.0 at.% Ag/ZnO. plane of Ag and (101) crystal plane of ZnO, respectively.
The surface elemental composition and valence states of 1.5 at.% Ag/
of high purity. ZnO microspheres were studied by XPS. From Fig. 6a, C, Zn and O ele­
Fig. 4 displays the FESEM images of bare ZnO and Ag/ZnO. The ments are observed, in which Zn and O are from ZnO, whereas C is
FESEM images show that the flower-like microsphere structure with a introduced from the adventitious carbon-based additives. Fig. 6b show
diameter of ~10 μm composed of thousands of 1.5–3.0 μm nanosheets is two peaks at binding energies of 1021.6 and 1044.6 eV in 1.5 at.% Ag/

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Fig. 4. FESEM images of (a-b) pure ZnO and (c-d) Ag/ZnO flower-like microspheres; (e-h) SEM image and corresponding EDS images of Ag/ZnO flower-like mi­
crospheres; (i) 1.0 at.% Ag/ZnO flower-like microspheres; (j) 2.0 at.% Ag/ZnO flower-like microspheres.

ZnO, corresponding to Zn 2p3/2 and Zn 2p1/2, respectively, and the gap The N2 adsorption-desorption isotherms and pore size distribution of
of splitting energy levels is 23 eV, which reveals that Zn exists in the ZnO and 1.5 at.% Ag/ZnO are illustrated in Fig. 7. It can be seen from
form of Zn2+ [25]. Fig. 6c displays two peaks centered at binding en­ Fig. 7a that the N2 adsorption-desorption isotherms exhibit a type IV
ergies of 530.1 and 531.7 eV, which represent the lattice oxygen O2− curves with a type H3 hysteresis loops, indicating the presence of mes­
(OL) and surface adsorbed oxygen O−X (OC), respectively. It is known that oporous structure in the sample. The BET surface areas of ZnO and 1.5
only O−X can react with reducing gas to improve sensing performance. at.% Ag/ZnO samples were calculated to be 22.64 m2•g− 1 and 28.01
From Fig. 6d, the peaks at binding energies of 367.5 and 373.5 eV are m2•g− 1, respectively. The corresponding pore size distribution is in
ascribed to Ag 3d5/2 and Ag 3d3/2, respectively. Two Gaussian peaks of multimodal forms with multiple peaks as shown in Fig. 7b. The corre­
Ag 3d5/2 are centered at 367.5 and 368.2 eV, while the peaks of Ag 3d3/2 sponding pore size distribution presents a multi-peak shape and the peak
are located at 373.5 and 374.2 eV. Moreover, the peaks at 367.5 and value of 1.5 at.% Ag/ZnO is higher than that of pure ZnO, as shown in
373.5 eV with a splitting distance of 6 eV correspond to the Ago state Fig. 7b. The results showed that the specific surface area and nanopore
[26], whereas the peaks at 368.2 and 374.2 eV can be attributed to Ag+ size of Ag/ZnO modified by Ag increased, which is advantageous for
[27], which confirms that Ag2O exists in the 1.5 at.% Ag/ZnO increasing the surface oxygen content, improving the surface adsorption
microspheres. capacity, and thereby improving the gas sensing performance of the

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Fig. 5. (a) TEM and (b) high-resolution TEM images of ZnO flower-like microspheres; (c) TEM and (d) high-resolution TEM images of Ag/ZnO flower-like
microspheres.

Fig. 6. XPS spectrum of 1.5 at.% Ag/ZnO flower-like microspheres: (a) survey spectra, (b) Zn 2p spectra, (c) O 1s spectra and (d) Ag 3d spectra.

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Fig. 7. (a) N2 adsorption-desorption isotherms and (b) corresponding pore size distribution curves of pure ZnO and 1.5 at.% Ag/ZnO nanocomposite.

materials. The pore size distribution image further indicates the meso­ increasing Ag loading, where 1.5 at.% is the optimal Ag content. When
porous structure of the synthesized material, which is beneficial to the the loading concentration is less than 1.5 at.%, the enhanced response is
gas transmission and enhances the reaction between the gas to be limited due to the catalytic effect not making the target gas contact with
measured and the oxygen anion, thereby improving the gas sensing all the sensing film’s surface. When the loading concentration exceeds
performance the material to the gas. 1.5 at.%, the response is decreased due to the desorption process of the
The TG-DSC analysis of 1.5 at.% Ag/ZnO was performed to study its target gas being enhanced [28]. In addition, Fig. 9b shows the responses
stability, as shown in Fig. 8. According to the comprehensive analysis of of all the sensors to 5000 ppm CH4 in the temperature range from 140 to
TG-DSC, 1.5 at.% Ag/ZnO exists two stages of weight loss in the picture, 260◦ C. As shown, all the samples reach the highest response value to
the first phase at room temperature to 250◦ C slow weight loss is due to 5000 ppm CH4 at 200◦ C, were 1.5 at.% Ag/ZnO exhibits the maximal
the adsorption and desorption of gas molecules. The second phase in response value of 20.15. Therefore, the 1.5 at.% Ag/ZnO gas sensor
250◦ C -800◦ C, in addition to the weight loss is the primary solvent. displays temperature-modulated double selectivity for CO sensing at
Therefore, the results show that the 1.5 at.% Ag/ZnO does not decom­ 130◦ C and CH4 sensing at 200◦ C.
pose under 250◦ C, and the stability of the as-synthesized sample is good. Figs. 10a and c show the dynamic response curves of as-prepared
bare ZnO and 1.5 at.% Ag/ZnO to 1–100 ppm CO and 10–5000 ppm
CH4 at their optimal working temperature. A stepwise distribution of the
3.2. Gas sensing properties
gas response upon exposing the sensors to various concentrations of CO
and CH4 can be observed. Both sensors exhibit outstanding response and
The working temperature is a vital influencing factor for metal oxide
recovery characteristics for CO sensing. In addition, Fig. 10b shows the
semiconductor resistance gas sensors. Fig. 9a shows all as-prepared
linear relationships between the response and CO gas concentration: y =
samples’ responses to 100 ppm CO in the working temperature range
2.22539 + 0.21844x for 1.5 at.% Ag/ZnO sensor and y = 2.20681 +
from 30 to 210◦ C. The responses of all the samples display a bell curve
0.04333x for the bare ZnO sensor, where y is the gas response and x is
variation with increasing temperature. This experimental phenomenon
the concentration of the target gas concentration. Fig. 10d shows a rapid
is mainly attributed to the balance between chemical reaction dynamics
linear increase in the low CH4 concentration region (10–100 ppm),
and the adsorption/desorption of gas molecules [19]. Ag loading
followed by a gentle increase in the high CH4 concentration region
effectively lowers the optimal operating temperature since the sensor
(100–3000 ppm). In contrast, a saturation trend in the gas response is
based on bare ZnO shows its maximal response to 100 ppm CO at 150◦ C.
observed when the CH4 concentration is higher than 3000 ppm. The
In contrast, all the Ag/ZnO samples’ optimal operating temperature is
linear relationships between response and 10–100 ppm CH4 are y =
reduced from 150 to 130◦ C. The optimal temperature of Ag/ZnO has a
3.04183 + 0.05833x for the 1.5 at.% Ag/ZnO sensor and y = 1.28882 +
shift to lower temperature compared to bare ZnO, which can be ascribed
0.02532x for the bare ZnO sensor. Such excellent linearity can reduce
to the fact that the loading of Ag decreases the activation energy.
the measurement error in the whole concentration range.
Moreover, the responses exhibit a volcanic change tendency with
The limit of detection (LoD) of the sensors is calculated by [29]:
Noiserms
LoD = 3 (1)
Slope
Where, Noiserms is the gas sensor noise, which is calculated as the
variation of gas response at 30 points of baseline by using root-mean-
square deviation and Slope is the slope value of the linear fitting
curves. The LoD values for CO and CH4 with 1.5 at.% Ag/ZnO are 44 and
166 ppb, respectively.The LoD values for CO and CH4 with bare ZnO are
284 and 407 ppb, respectively. The detection limits of 1.5 at.% Ag/ZnO
for CO and CH4 are lower than that of bare ZnO. As shown in Fig. 11, the
transient response curves display response/recovery times for 1.5 at.%
Ag/ZnO and ZnO to 100 ppm CO at 130◦ C of 1/23 and 2/25 s, respec­
tively. Moreover, the response/recovery times of 1.5 at.% Ag/ZnO and
ZnO to 5000 ppm CH4 at 200◦ C are 118/119 and 252/346 s, respec­
tively. Obviously, Ag-modified ZnO shows a faster response/recovery
rate than that of bare ZnO. This fast response/recovery characteristic is
mainly ascribed to Ag’s catalytic effect that reduces the activation
Fig. 8. TG-DSC profiles of 1.5 at.% Ag/ZnO composite from 40◦ C up to 800◦ C.

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Fig. 9. Response versus working temperature of all as-prepared samples to (a) 100 ppm CO and (b) 5000 ppm CH4.

Fig. 10. (a) Dynamic response curves of as-prepared ZnO and 1.5 at.% Ag/ZnO to 1–100 ppm CO at 130◦ C, and (b) their corresponding fitting curves; (c) the
dynamic response curves of ZnO and 1.5 at.% Ag/ZnO to various concentrations of CH4 at 200◦ C, and (d) their corresponding fitting curves.

energy of the surface reaction and thus accelerates the redox reaction permitted contents of CO and NH3 are 0.0024% (24 ppm) and 0.004%
process. The specific porous structure can accelerate the diffusion of gas (40 ppm), respectively. Besides, the concentrations of other VOCs in the
molecules into the interior of the materials. In addition, the resistance of environment are less than 1 ppm. Thus 5000 ppm CH4, 24 ppm CO, 40
ZnO displays a dramatic increase after Ag loading; the reason is mainly ppm NH3 and 1 ppm VOCs are complete to satisfy practical applications’
due to the noble metals being able to form a Schottky barrier at the demands. As shown in Fig. 12, both sensors exhibit excellent selectivity
interface of semiconductors, which can effectively act as an electron in monitoring CO at 130◦ C and CH4 at 200◦ C. Obviously, the selectivity
trap. of the 1.5 at.% Ag/ZnO sensor is increased dramatically compared to the
Selectivity is a critical parameter that reflects a gas sensor’s recog­ bare ZnO sensor. The selectivity coefficients (K = SCO/SCH4) of the 1.5 at.
nition ability to a target gas and an interference gas’s inhibition ability. % Ag/ZnO and pure ZnO sensors at 130◦ C are 6.28 and 2.92, respec­
Furthermore, the selectivity is usually expressed by the selectivity co­ tively, while the other selectivity coefficients (K = SCO/SNH3) are 3.39
efficient K, which is calculated as follows [30]: and 1.78, respectively. Furthermore, the selectivity coefficients (K =
SCH4/SCO) of the 1.5 at.% Ag/ZnO and pure ZnO sensors at 200◦ C are
STarget gas
K= (2) 9.08 and 6.64, respectively, while the other selectivity coefficients (K =
SInterference gas
SCH4/SNH3) are 4.75 and 4.33, respectively. These results indicate that
It is generally known that coal mine gas contains many CH4, small the sensor is based on 1.5 at.% Ag/ZnO can be used for the dual-selective
amounts of CO and NH3, and trace amounts of volatile organic com­ detection of CH4 and CO through control of the working temperature.
pounds (VOCs). The Safety Regulations of Coal Mine of China set the Repeatability and stability are critical parameters of
alarm concentration of CH4 at 0.5–1.5% (5000–15000 ppm).The semiconducting-type gas sensors in practical applications. Fig. 13

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Fig. 11. Response/recovery times of (a) 1.5 at.% Ag/ZnO and (b) pure ZnO toward 100 ppm CO at 130◦ C. Response/recovery times of (c) 1.5 at.% Ag/ZnO and (d)
pure ZnO toward 5000 ppm CH4 at 200◦ C.

Fig. 12. Selectivity histogram of 1.5 at.% Ag/ZnO and bare ZnO at the working temperature of (a) 130 and (b) 200◦ C.

displays the gas sensing measurement results of 1.5 at.% Ag/ZnO to 100 considers the variation of charge carrier concentration before and after
ppm CO at 130◦ C and 500 ppm CH4 at 200◦ C. The response values do not exposure to the target gas. When n-type ZnO is put in a clean air at­
show a significant fluctuation. The sensor’s attenuation to CO and CH4 mosphere, oxygen molecules will be chemisorbed on the ZnO surface to
in one month is only 8.28% and 1.33%, respectively. Thus, the sensor is form chemisorbed oxygen species by capturing electrons from the ZnO
based on 1.5 at.% Ag/ZnO exhibits excellent repeatability and stability. conduction band (O−2 , T < 100◦ C; O− , 100 < T < 300◦ C; O2− ,T > 300◦ C),
Table 1 lists the gas sensing properties of various semiconducting leading to the formation of an electron depletion layer and a decrease in
metal oxide gas sensors toward CO and CH4. The 1.5 at.% Ag/ZnO electron carrier concentration [38]. Once the sensing materials are
sensor possesses an outstanding CO sensing ability concerning the high exposed to the reducing gas (CO and CH4), the chemisorbed oxygen
response value and fast response/recovery rate. Furthermore, the 1.5 at. species (the chemisorbed oxygen ions is mainly O− due to the optimal
% Ag/ZnO sensor exhibits a high response to CH4 at a relatively low working temperatures of 130 and 200◦ C, respectively) react with the
working temperature. Based on the above test results, the 1.5 at.% Ag/ target gas and electrons are released back into the ZnO conduction band,
ZnO sensor exhibits excellent sensing properties to CO at 130◦ C and CH4 leading to the decease of the electron depletion layer width and the
at 200◦ C, which confirms that the sensor with temperature-modulated increase of electron carrier concentration. The redox reactions occurring
double selectivity to CO and CH4 possesses excellent application on the ZnO surface can be described as follows [24,39]:
prospects.
CO(ads) + O− (ads) →CO2(gas) + e− (3)

3.3. Gas sensing mechanism CH4(ads) + 4O− (ads) →2H2 O(gas) + CO2(gas) + 4e− (4)

Generally, the working principle of a semiconducting metal oxide

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Fig. 13. (a) Repeatability and (b) stability of 1.5 at.% Ag/ZnO to 100 ppm CO at 130◦ C; (c) repeatability and (d) stability of 1.5 at.% Ag/ZnO to 500 ppm CH4
at 200◦ C.

the 1.5 at.% Ag/ZnO sensor has no obvious response toward CH4 when
Table 1
the temperature is lower than 140◦ C. Then with the temperature in­
Comparison of gas sensing properties of various semiconducting gas sensors
creases, CH4 will be activated by Ag due to enough thermal energy to
toward CO and CH4.
overcome the barrier, leading to the increase in response. Thus, the 1.5
Sensing Gas Temp. Conc. Res. τres/τrec Ref.
at.% Ag/ZnO sensor displays temperature-modulated double selectivity
materials (◦ C) (ppm)
to CO at 130◦ C and CH4 at 200◦ C.
Pd/SnO2 CO 400 400 6.80a 5/40 s [31]
Ag-ZnO/ CO RT 100 5.08%b 45/40 s [32]
3.3.2. Sensitizing mechanism
MoS2
2 at.% Ga- CO 150 1000 25.00%b 40/30 s [33] In terms of the Ag/ZnO flower-like microspheres, the enhanced
ZnO sensing properties after modification by Ag could be attributed to the
Pd/ZnO CO 220 20 5.50a 25/17 s [34] following reasons. The noble metal exhibits a strong catalytic activity,
1.5 at.% Ag/ CO 130 100 24.17a 1/23 s This
effectively reducing gas molecules’ chemical adsorption energy and
ZnO work
20 mol.% Pt- CH4 350 1000 4.48a 24/141 [9]
accelerating gas molecules’ dissociation [42]. Ag can promote the
SnO2 s dissociation of O2 into O, as well as CH4 into CH3 and H via the catalytic
Pd-SnO2/rGO CH4 RT 12000 9.50% b
5/7 [35] effect, and then these dissociated species spillovers to the surface of ZnO
min and participate in the redox reactions Eqs. (5)–((8)). Compared with the
ZnO CH4 300 500 1.70a 1/2–3 [36]
pure ZnO microspheres, the above processes increase the magnitude of
min
Pd-Ag/ZnO/ CH4 220 10000 3.85a 5/16 s [37] adsorption and reduction/oxidation processes on the Ag/ZnO surface.
Zn The corresponding chemical sensitization sensing mechanism diagrams
a
1.5 at.% Ag/ CH4 200 5000 20.15 118/ This are shown in Figs. 14a–c.
ZnO 119 s work
(5)
Ag
Note: aThe response is defined as Ra/Rg. b(Ra -Rg)/Ra × 100%. O2(ads) → O(ads) + O(ads)

O(ads) + e− →O− (6)

3.3.1. Discussion of dual selectivity (ads)

The dual selectivity detection for CH4 and CO of 1.5 at.% Ag/ZnO
(7)
Ag
through control of the working temperature can be attributed to the CH4(ads) → CH3(ads) + H(ads)
catalytic discrepancy between the sensing materials and target gases. Yu ) )
et al. [40] reported that the ignition temperature and complete con­ CH3(ads) + 4H(ads) + 4O− (ads →CO2(gas) + 2H2 O(gas + 4e− (8)
version temperature of CH4 on the catalyst are much higher than that of
Owing to the work function of ZnO (4.45 eV) being lower than that of
CO. The sensor is based on 1.5 at.% Ag/ZnO in this work uses this
Ag (5.1 eV) [43,44], the electrons will transfer from ZnO to Ag, leading
temperature difference to realize the selectivity reaction and detection
to the band bending near the interface region and thus forming the
of CO and CH4. Though the noble metal Ag exhibits a strong catalytic
Schottky barrier (Fig. 14e). Furthermore, Ag2O as a p-type semi­
capability for the oxidation of CO at a low temperature region [41], CH4
conductor with a high work function of 5.3 eV [45] will form the p-n
oxidation is highly difficult to achieve at low temperature because CH4 is
heterojunction with ZnO and result in the electrons transfer from ZnO to
a sp3-hybrid nonpolar molecule that is thermodynamically stable. Thus,
Ag2O (Fig. 14f). The formation of the Schottky barrier and p-n

9
Y. Wang et al. Surfaces and Interfaces 24 (2021) 101110

Fig. 14. (a-c) Gas sensing mechanism diagrams of Ag/ZnO exposed to air, CO and CH4, respectively (EDL - electron depletion layer); (d) energy band diagram of Ag
and ZnO; Plots of surface band bending when ZnO contacts with (e) Ag and (f) Ag2O (EC - energy of conduction band minimum; EV - energy of valence band
maximum; χ - electron affinity of the semiconductor; Wm - metal work function; Ws - semiconductor work function; Ef - Fermi level).

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