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Progress in Chemistry 2020, Vol. 32 Issue (2/3): 344-360 DOI: 10.7536/PC190628 Previous Articles   

Applications of Electrospun One-Dimensional Nanomaterials in Gas Sensors

Lei Zhu1,2, Jianan Wang1,3,**(), Jianwei Liu1, Ling Wang1, Wei Yan1,**()   

  1. 1. Department of Environmental Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China;
    2. School of Mathematics and Physics, Weinan Normal University, Weinan 714099, China
    3. Department of Applied Chemistry, School of Science, Xi’an Jiaotong University, Xi’an 710049, China;
  • Received: Online: Published:
  • Contact: Jianan Wang, Wei Yan
  • About author:
    ** e-mail: (Jianan Wang);
    (Wei Yan)
  • Supported by:
    Natural Science Foundation of China(51803164); China Postdoctoral Science Foundation(2018M643635); Natural Science Foundation of Shaanxi Province(2019JQ-126); Natural Science Research Project of Shaanxi Provincial Education Department(19JK0293)
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Electrospun 1D nanomaterials have the advantages of such as large specific surface area, high porosity, and superior electrochemical properties, which can significantly improve the sensitivity of gas sensors, making them the most widely used materials in the gas sensor field. In this review, the classification of gas sensor, the principle of electrospinning technology and the sensing mechanism of semiconductor metal oxide gas sensor is highlighted. And the research status of different sensing materials, including semiconductor metal oxide, doped semiconducting metal oxide, polymer-metal oxide, graphene-metal oxide composite material that are prepared by electrospinning and applied in gas sensors is reviewed in detail. Finally, the research prospect in this field is presented.

Key words: electrospinning, gas sensor, sensing mechanism, one-dimensional nanomaterials, semiconductor metal oxides
Fig.1 Different morphologies of electrospun fibers (a) beaded[14]; (b) smooth[15];(c) ribbon[16]; (d) multichannel tubular[17]; (e)hollow[18];(f) nanowire-in-microtube[19];(g)brush-like[20];(h)chain-like[21] and (i)nano-net[22]
Fig.2 Smplified gas sensing mechanism of space charged model of (a)n type and(b)p type semiconductor metal oxide[24]
Fig.3 Schematic diagram of the proposed bifunctional sensing mechanism: reducing gas (H2) effect at SnO2 homointerfaces[25]
Table 1 Summary of sensing properties of semiconducting metal oxide nanostructures
Material Structure Treatment Average
Diameter		 Target gas Concentration Response T response/T recovery Temperature(℃) Limit of detection ref
TiO2 Nanorods Calcined at 650 ℃ for 4 h 500 nm Acetone 1‰ 20 14/8 s 500 0.01‰ 26
TiO2 Nanofibers Annealing at 550 ℃ 60 nm Ethanol 0.05‰ 4.5 - 450 0.002‰ 48
SnO2 Nanofibers Calcined at 500 ℃ for 2 h - Ethanol 0.1‰ 7.6 7/22 s 250 - 49
ZnO Nanorods Calcined at 873 K for 6 h - Ethanol 0.1‰ 23 26/43 s RT ~0.001‰ 50
ZnO Nanowires Calcined at 873 K for 3 h - Ethanol 0.1‰ 78 9/12 s RT ~0.001‰ 51
In2O3 Nanotubes Annealed at 600 ℃ for 3 h 80 nm H2S 0.02‰ 166.6 287/636 s RT ~0.001‰ 52
WO3 Nanofibers Calcined at 500 ℃ and etched with HF - Acetone 0.05‰ 22.1 24/27 s 300 0.005‰ 53
Fig.4 (a) Schematic illustration of synthetic process of PdO@ZnO-SnO2 NTs; (b) SEM image of as-spun Pd@ZIF-8/PVP/Sn composite NFs;(c) TEM image of as-spun Pd@ZIF-8/PVP/Sn composite NFs;(d) SEM image of PdO@ZnO-SnO2 NTs;(e) Dynamic acetone response transition in the concentration range of 0.0001‰~0.005‰ at 400 ℃; (f) selective sensing characteristics of PdO@ZnO-SnO2 NTs toward 0.001‰ of various analytes at 400 ℃ [85]
Table 2 Summary of sensors made of metal ion doped semiconducting metal oxide nanostructures and their sensing properties
Material Structure Treatment Diameter of
nanoparticles		 Target gas Concentration Response T respose/T recovery Temperature(℃) Limit of detection ref
Au-In2O3 Nanofibers Annealed at 500 ℃
for 2 h		 30~50 nm Ethanol 0.1‰ 116.13 2/152 s 175 ~0.001‰ 88
Pt-In2O3 Nanofibers Reduction method 50~100 nm NO2 0.01‰ 23.9 -/358 s RT 0.00001‰ 89
Eu-SnO2 Nanofibers Calcined at 600 ℃
for 5 h		 10 nm Acetone 0.1‰ 32.2 4/3 s 280 0.0003‰ 90
Rh-SnO2 Nanofibers Calcined at 500 ℃
for 2 h		 150 nm Acetone 0.05‰ 60.6 2/64 s 200 0.001‰ 59
Cr-WO3 Nanofibers Calcined at 500 ℃
for 2 h		 - Xylene 0.1‰ 35.04 1/2 s 255 0.002‰ 91
Pd-WO3/Pt-WO3 Nanotubes Calcined at 500 ℃
for 1 h		 - Toluene 0.005‰ 2.35/2.24 - 400 0.001‰ 83
Ni-ZnO Nanofibers Calcined at 500 ℃
for 4 h		 45 nm HCHO 0.1‰ 532.7% - RT 0.005‰ 92
Fig.5 TEM images of the BW/TiO2 HNFs and dynamic ethanol response-recovery curves of the BW/TiO2 HNFs-based flexible sensing devices under different bent state[104]
Table 3 Sensing properties of composites of semiconducting metal oxide nanostructures
Material Structure Average
Diameter		 Target gas Concentration Response T response/T recovery Temperature(℃) Limit of detection ref
WO3-SnO2 Core-shell 220~240 nm Ethanol 0.01‰ 5.09 18.5/282 s 280 - 107
ZnO@In2O3 Core@shell 60 nm Ethanol 0.1‰ 31.87 52/3.7 s 225 ~0.005‰ 108
SnO2-ZnO Nanofibers 100 nm H2 0.00005‰ 50.1 - 300 0.00005‰ 97
SnO2/TiO2 Nanofibers 100~200 nm Ethanol 0.1‰ 9.58 8/10 s 240 0.005‰ 109
TiO2-SnO2 Core-shell - Acetone 0.1‰ 13.7 2/60 s 280 0.01‰ 110
WO3-CuO Hollow-core 50 nm DMMP 0.01‰ 19.3 9.2/15.5 s 25 0.0005‰ 111
Co3O4-ZnO Core-shell 200 nm HCHO 0.1‰ 5 6/9 s 220 0.01‰ 112
α-Fe2O3@NiO Core-shell 90~180 nm HCHO 0.05‰ 12.8 2/9 s 240 0.001‰ 113
Table 4 Sensing properties of composites of conductive polymer and semiconductor metal oxide nanostructures
Material Structure Average
Diameter		 Target gas Concentration Response T response/
T recovery 		Temperature(℃) Limit of detection ref
PPy-PAN Nanofibers Yarn 406 nm Ammonia 2‰ 1.5 1 s RT 0.25‰ 119
PANI/CNF/PVA Nanofibers 350 nm Ammonia 0.1‰ 83 41/46 s RT 0.02‰ 120
PANI Nanofiber membrane 300 nm CO 0.000125‰ 37 20/50 s RT 0.00025‰ 121
PVP Nanofibers - Ethanol 0.005‰ 680 Hz 500/2700 s RT 0.005‰ 122
Al-SnO2/PANI Nanofibers 200 nm Hydrogen 0.1‰ 3.7 2/2 s 48 - 123
Cellulose/TiO2/PANI Nanofibers - Ammonia 0.25‰ 6.335 - RT 0.010‰ 117
Table 5 Sensing properties of composites of graphene and semiconductor metal oxide nanostructures
Material Structure Treatment Average
Diameter		 Target gas Concentration Response T response/
T recovery 		Temperature(℃) Limit of detection ref
CuO-RGO Nanofibers Calcined at 600 ℃ for 2 h ~50 nm H2S 0.01‰ 11.2 - 300 0.001‰ 131
GO-WO3 Nanofibers Calcined at 500 ℃ for 2 h 100 nm Acetone 0.1‰ 35.9 4/11 s 375 0.02‰ 132
rGO-In2O3 Nanofibers Calcined at 450 ℃ for 3 h - NO2 0.005‰ 42 261/698 s 50 0.001‰ 133
rGO-Co3O4 Nanofibers Calcined at 550 ℃ for 3 h in N2 - Ammonia 0.05‰ 53.6% 4 s/5 min RT 0.005‰ 134
Au-rGO/ZnO Nanofibers Calcined at 600 ℃ - CO 0.005‰ 35.8 177.3/76.1 s 400 0.001‰ 135
Pd-rGO/ZnO Nanofibers for 3 min - C6H6 0.005‰ 23 110.3/318.2 s
rGO/α-Fe2O3 Nanofibers Calcined at 500 ℃ for 2 h 100 nm Acetone 0.1‰ 8.9 25/30 s 375 0.005‰ 136
Table 6 The advantages and disadvantages of gas sensor prepared with different materials
Materials Advantage Disadvantage ref
Pure SMOs minimal response/recovery time minimal sensitivity, high operating
temperature, low detection limit		 137~140
Doped SMOs high sensitivity, lower detection limit, short response/recovery time slightly lower operating temperature 78,80
SMOs-SMOs composites enhanced selectivity, short response/recovery time, improved operating temperature slightly improved response, slightly improved detection limit 95
Conjugated polymer-conjugated
polymer composites orconjugated polymer/non-conjugated polymer-SMOs composites		 low operating temperature, high selectivity, minimal detection limit, minimal response/recovery time minimal response 115,141
Graphene-SMOs composites lower operating temperature, minimal
response/recovery time, minimal detection
limit		 minimal response 142~144
Table 7 Summary of different gas sensors prepared by electrospinning
Gas species Materials Response Response time Recovery time ref
Sensitivity Concentration Temperature(℃)
Ethanol Pd/SnO2 1020.6 0.1‰ 330 <10 s 9.6 s 67
Sn/SnO2/C 46.15 1‰ 220 - - 145
SnO2/ZnO - 0.0272‰ 360 14 s 2 s 146
ZnO/TiO2 50.6 0.5‰ 320 5 s 10 s 21
NH3 SiO2/PANI 0.88 0.4‰ RT - - 147
Ce/TiO2/PANI 3.5 0.1‰ RT 83 s 130 s 117
rGO/Co3O4 53.6 0.05‰ RT 4 s 300 s 134
NO2 Ag/WO3 90.3 0.005‰ 225 6 s 18 s 148
rGO/In2O3 42 0.005‰ 50 261 s 698 s 132
Formaldehyde NiO/SnO2 - 0.01‰ 200 50 s 80 s 94
Nd/In2O3 44.6 0.1‰ 240 15 s 50 s 149
PEI/PS 5 0.003‰ RT - - 15
CO SnO2/CuO 95 0.01‰ 235 37 s - 150
In2O3 - 0.1‰ 300 - - 151
Acetone GO/WO3 35.9 0.1‰ 375 4 s 11 s 131
Ca2+/Au-SnO2 62 0.1‰ 180 8 s 5 s 57
In2O3/WO3 12.9 0.05‰ 275 6 s 64 s 152
Triethylamine ZnO-In2O3 119.4 0.005‰ 375 - - 153
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