Preparation of WO3@PANI composite nanofibers and their sensing properties towards triethylamine at room temperature
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摘要: 随着工业生产的日益发展，对气体传感器的需求不断增长。鉴于三乙胺对人体容易造成危害，开发可以有效检测三乙胺的气体传感器具有重要意义。针对目前常见气体传感器存在工作温度高、耗能高的特性，本文制备了一种可以在室温条件下快速检测三乙胺的气体传感器材料。采用静电纺丝技术、高温热处理及原位化学氧化聚合相结合的方法，成功合成了组分含量可控的WO3@聚苯胺(PANI)无机有机复合纤维材料。利用扫描电子显微镜、X射线衍射仪、能量色散X射线光谱仪和傅里叶变换红外光谱对所制备的样品形貌结构、元素含量及官能团进行表征。所制备的复合材料整体呈现纤维形貌，PANI均匀分布在WO3纳米纤维表面，形成WO3@PANI核壳结构。WO3@PANI复合纳米纤维在室温工作条件下对三乙胺表现出良好的传感性能。此外，还实现了优异的三乙胺选择性、高湿度检测、高浓度检测范围(50~5000 μg/g三乙胺)及良好的响应恢复特性。相比于PANI和WO3纳米纤维纯相材料，WO3@PANI复合纳米纤维的传感性能增强主要归因于WO3和PANI之间形成的p-n异质结。Abstract: With the increasing development of industrial production, the demand for gas sensors is growing. Given that triethylamine is easily harmful to the human body, it is important to develop a gas sensor that can effectively detect triethylamine. Considering the shortcomings of common gas sensors with high working temperature and high energy consumption, a gas sensing material that can quickly detect triethylamine at room temperature was proposed in this paper. Through the combination of electrospinning, heat treatment and in-situ chemical oxidation polymerization, the inorganic-organic composite, WO3@polyaniline (PANI) nanofibers, was successfully synthesized with controllable component content. Scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectrometer and Fourier transform infrared spectroscopy were used to characterize the morphology, element content and functional groups of the as-prepared samples. The composite demonstrates fibrous morphology with PANI uniformly distributed on the surface of WO3 nanofibers, forming WO3@PANI core-shell structure. The WO3@PANI composite nanofibers show good sensing performance to triethylamine at room temperature. In addition, excellent sensing properties are also achieved, such as excellent triethylamine selectivity, stable response under high humidity condition, wide concentration detection range (50-5000 μg/g triethylamine) and good response-recovery characteristics. Compared with sensing performance of pristine PANI and WO3 nanofibers, the enhanced sensing response of WO3@PANI composite nanofibers is mainly attributed to the p-n heterojunction formed between WO3 and PANI.
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Key words:
- electrospinning /
- tungsten trioxide /
- polyaniline /
- triethylamine /
- gas sensitivity at room temperature
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图 1 WO3@聚苯胺(PANI)制备流程示意图
Figure 1. Schematic diagram of the WO3@polyaniline (PANI) preparation flow
图 2 (a)静电纺丝后前驱体纳米纤维的SEM图像；500℃ (b)、600℃ (c)、700℃ (d)煅烧后的WO3纳米纤维的SEM图像；PANI (e)、WO3@PANI复合纳米纤维(f)的SEM图像；WO3纳米纤维(g)、WO3@PANI复合纳米纤维(h)的EDS图谱
Figure 2. (a) SEM image of electrospinning post-precursor nanofibers; SEM images of 500℃ (b), 600℃ (c), 700℃ (d) calcined WO3 nanofibers; SEM images of PANI (e), WO3@PANI composite nanofibers (f); EDS map of WO3 nanofibers (g), WO3@PANI composite nanofibers (h)
图 3 PANI、WO3纳米纤维和WO3@PANI 复合纳米纤维的FTIR图谱
Figure 3. FTIR spectra of the PANI, WO3 nanofibers and WO3@PANI composite nanofibers
图 4 WO3纳米纤维和WO3@PANI复合纳米纤维的XRD图谱
Figure 4. XRD patterns of the WO3 nanofibers and WO3@PANI composite nanofibers
图 5 室温条件下不同掺杂量WO3@PANI复合纳米纤维的气敏特性：(a)在空气中的电阻(Ra)；(b)对三乙胺的响应灵敏度(气体浓度：100 μg/g)
Rg—Resistance in target gas
Figure 5. Sensing property of WO3@PANI composite nanofiber with different WO3 doping amount at room temperature: (a) Resistance in air (Ra); (b) Response sensitivity to triethylamine (Gas concentration: 100 μg/g)
图 6 室温条件下WO3@PANI-4复合纳米纤维对三乙胺的气体传感特性：(a)对不同测试气体的响应灵敏度(气体浓度：100 μg/g)；(b)对不同浓度三乙胺气体的响应灵敏度；(c)对三乙胺气体的响应恢复曲线；(d)在不同湿度下对三乙胺气体的响应灵敏度(气体浓度：100 μg/g)
TEA—Triethylamine
Figure 6. Gas sensing properties of WO3@PANI-4 composite nanofibers to triethylamine at room temperature: (a) Response sensitivity to different test gases (Gas concentration: 100 μg/g); (b) Response sensitivity to different concentrations of triethylamine gas; (c) Response recovery curve to triethylamine gas; (d) Response sensitivity to triethylamine gas at different humidity (Gas concentration: 100 μg/g)
图 7 室温条件下WO3@PANI-4复合纳米纤维对三乙胺的重复性传感测试(a)和长期稳定性传感测试(b) (气体浓度：100 μg/g)
Figure 7. Repeatability sensing test (a) and long-term stability sensing test (b) of WO3@PANI-4 composite nanofibers on triethylamine at room temperature (Gas concentration: 100 μg/g)
图 8 WO3@PANI异质结的能带结构示意图
LUMO—Lowest unoccupied molecular orbital; HOMO—Highest occupied molecular orbital; EC—Bottom of conduction band; EF—Fermi level; EV—Top of valence band
Figure 8. Schematic diagram of the band structure of the WO3@PANI heterojunction
表 1 WO3和WO3@PANI主要制备参数
Table 1. Preparation parameters of WO3 and WO3@PANI
Fiber type Sample Calcination temperature/℃ Aniline dosage/μL WO3-600℃dosage/g WO3 nanofibers WO3-500℃ 500 — — WO3-600℃ 600 — — WO3-700℃ 700 — — WO3@PANI composite nanofibers WO3@PANI-1 — 35 0.03 WO3@PANI-2 — 35 0.10 WO3@PANI-3 — 35 0.15 WO3@PANI-4 — 35 0.20 WO3@PANI-5 — 35 0.30 
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