Gas sensing performance and preparation of WO3 nanosheets decorated by ZIF-67
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摘要: 金属氧化物半导体气敏传感器在有毒有害气体检测领域逐渐表现出巨大的应用前景，但是金属氧化物半导体传感器通常在检测时受环境湿度影响较大，这极大地限制了其应用。本文采用水热法成功在陶瓷管表面原位生长WO3纳米片，并以此为基底，在其表面生长ZIF-67多孔材料，通过调控W和Co的比例制备了不同比例的ZIF-67/WO3复合材料，利用XRD、SEM、FTIR和比表面积测试仪(BET)等方法对所制备的材料进行物相和形貌表征。针对其不同比例的复合材料的气敏性能进行了研究。结果表明：W∶Co摩尔比为 1∶1的ZIF-67/WO3(1∶1)复合材料性能最好，在220℃对三乙胺表现出优异的选择性，对体积分数为100×10−6的三乙胺的响应值可达140.34，响应和恢复时间分别为9 s和7 s。研究了空气相对湿度(RH)对ZIF-67/WO3(1∶1)传感器的影响，结果表明，在高达75%RH环境下该材料仍能保持较好的响应值，相对于纯WO3气敏材料具有较好的抗湿性能。Abstract: Metal oxide semiconductor gas sensors are exhibiting great application prospects in the field of toxic and hazardous gas detection gradually, but metal oxide semiconductor sensors are commonly affected by ambient humidity during detection, which significantly limits their applications. In this paper, WO3 nanosheets were successfully in situ grown on the surface of ceramic tubes by hydrothermal method, and ZIF-67 porous materials were grown on the surface of ceramic tubes using it as substrate. Different ZIF-67/WO3 composites were prepared by adjusting the proportion of W and Co. The structures and morphologies of different ZIF-67/WO3 composites were analyzed via XRD, SEM, FTIR and BET techniques. The gas sensing properties of the pristine and different ZIF-67/WO3 composites are investigated. The results indicate that the ZIF-67/WO3(1∶1) composite which W∶Co molar ratio is 1∶1 has the best performance with excellent selectivity to trimethylamine (TEA) at 220℃, and high response of 140.34 to TEA gas with volume fraction of 100×10−6. The response/recovery time is 9 s and 7 s, respectively. The effect of air relative humidity (RH) on the sensors has also studied. The results show that the ZIF-67/WO3(1∶1) sensor can maintain a good response value in an environment humidity up to 75%RH and has a good moisture resistance compared with the pristine WO3 gas sensing material.
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Key words:
- WO3 /
- ZIF-67 /
- composites /
- in situ /
- trimethylamine /
- humidity resistance /
- gas sensing
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图 1 ZIF-67、WO3及ZIF-67/WO3复合材料的XRD图谱
Figure 1. XRD patterns of ZIF-67, WO3 and different ZIF-67/WO3 composites
图 2 WO3、ZIF-67、ZIF-67/WO3(1∶1)复合材料的 SEM图像
Figure 2. SEM images of WO3, ZIF-67 and ZIF-67/WO3(1∶1) composite
图 3 ZIF-67、WO3及ZIF-67/WO3复合材料的FTIR图谱
Figure 3. FTIR spectra of ZIF-67, WO3 and different ZIF-67/WO3 composites
图 4 不同ZIF-67/WO3复合材料的气敏性能：(a)对三乙胺的温度-灵敏度曲线；(b)对多种气体的选择性
TEA—Triethylamine; Ra, Rg—Resistance of the sensor in air and target gas, respectively
Figure 4. Gas sensing properties of different ZIF-67/WO3 composites: (a) Temperature-sensitivity curves to triethylamine; (b) Response to various gases
图 5 (a) ZIF-67/WO3(1∶1)元件对100×10−6三乙胺的响应曲线；(b)不同元件在220℃对三乙胺的响应恢复时间
Tres and Trec—Response and recovery time, respectively, which defined as the time required to reaching 90% of the total resistance change after exposure to the target gas and air, respectively
Figure 5. (a) Response curve of the ZIF-67/WO3(1∶1) sensor to 100×10−6 triethylamine; (b) Response/recovery time of different sensors to triethylamine at 220℃
图 6 (a) ZIF-67/WO3(1∶1)元件在220℃对不同浓度三乙胺的动态响应曲线(插图为低浓度的放大图)；(b) 体积分数1×10−6~50×10−6的响应线性关系
R2—Linearly dependent coefficient
Figure 6. (a) Dynamic response curves of the ZIF-67/WO3(1∶1) sensor to different concentrations of triethylamine at 220℃ (Inset is an enlarged view of low concentration); (b) Linear relation of volume fraction 1×10−6-50×10−6
图 7 ZIF-67/WO3(1∶1)传感器的长期稳定性测试
Figure 7. Long-term stability tests of the ZIF-67/WO3(1∶1) sensor
图 8 ZIF-67/WO3(1∶1)和纯WO3元件在220℃对100×10−6三乙胺的湿度稳定性曲线
Figure 8. Humidity stability curves of the ZIF-67/WO3(1∶1) sensor and pure WO3 sensor to 100×10−6 triethylamine at 220℃
图 9 ZIF-67/WO3异质结在空气和三乙胺中的传感机制示意图
Eg—Band gap; Ec—Conduction energy; Ev—Valence band energy; Ef—Fermi level
Figure 9. Schematic diagram of sensing mechanism for ZIF-67/WO3 composites in air and TEA
表 1 ZIF-67/WO3复合材料的原料配比
Table 1. Raw material ratios of ZIF-67/WO3 composites
Sample Molar ratio n(W)∶n(Co) ZIF-67/WO3(5∶1) 5∶1 ZIF-67/WO3(1∶1) 1∶1 ZIF-67/WO3(1∶5) 1∶5 
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表 2 不同敏感材料对于三乙胺气敏性能对比
Table 2. Compared TEA sensing performance of different sensing materials
Material Volume fraction/10−6 Response (Ra/Rg) Temperature
/℃Tres/Trec/s Ref. ZnO 50 83.00 280 8/23 [30] WO3/h-BN-5 500 390.60 260 8/60 [31] WO3 50 16.00 220 1.5/22 [32] Pd NPs-In2O3 50 47.56 220 4/17 [33] SnO2/SiO2 50 8.27 280 –/– [34] SnO2 50 54.90 235 26/13 [1] 2%Ga-doped Co3O4 50 108.00 180 3/15 [35] ZIF-67/WO3(1∶1) 50 118.08 220 9/7 This work Notes: h-BN—Hexagonal boron nitride; NPs—Nanoparticles.
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