Preparation and H2S sensing performance of Co(CO3)0.5(OH)·0.11H2O/WO3 nanomaterials
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摘要: 近年来，H2S作为哮喘和慢阻肺的新型生物标志物对人体健康监测具有重要意义，因此人们对低功耗、高选择性、低检出限和高稳定性H2S传感器的研究显得十分迫切。通过两步原位生长的方式合成了Co(CO3)0.5(OH)·0.11H2O/WO3纳米材料。以原位水热法合成的WO3纳米片为基底，通过调控水浴反应时间，在WO3纳米片上原位生长了不同的Co(CO3)0.5(OH)·0.11H2O/WO3纳米材料。利用FE-SEM、FTIR、XRD和TG等方法对复合材料进行表征和气敏性能测试。结果表明：反应20 min所制得的Co(CO3)0.5(OH)·0.11H2O/WO3复合材料具有最优异的气敏性能，在最佳工作温度(90℃)下对浓度为50×10−6 H2S气体的响应值高达109，响应和恢复时间分别为130 s和182 s，对H2S气体表现出优异的选择性。该复合材料在低浓度H2S (3×10−6) 氛围中，仍具有良好的响应恢复曲线。在一个月内进行的3次重复测试中，表现出较好的重复性和长期稳定性。Co(CO3)0.5(OH)·0.11H2O/WO3气敏材料的原位制备及气敏性能研究为气敏传感器器件的制备提供了新思路，为气敏材料的多样性提供了新途径。在环境检测和智能医疗方面有着潜在的应用价值。Abstract: In recent years, H2S as a novel biomarker for asthma and chronic obstructive pulmonary disease is of great significance to human health monitoring, so it is urgent to study H2S sensors with low power consumption, high selectivity, low detection limit and high stability. Co(CO3)0.5(OH)·0.11H2O/WO3 nanomaterials were synthesized by a two-step in situ growth method. Different Co(CO3)0.5(OH)·0.11H2O/WO3 nanomaterials were grown in situ on WO3 nanosheets by regulating the water bath reaction time using WO3 nanosheets as a substrate synthesized by in situ hydrothermal method. The composites were characterized by FE-SEM, FTIR, XRD and TG, and then tested for gas sensing performance. The results show that the Co(CO3)0.5(OH)·0.11H2O/WO3 composite prepared after 20 min reaction has the best gas-sensitive property, and the response value to 50×10−6 H2S gas at the optimal working temperature (90℃) is as high as 109. The response and recovery time are 130 s and 182 s respectively, showing excellent selectivity for H2S gas. The composite still has a good response/recovery curve in low concentration H2S (3×10−6) atmosphere. In three repeated tests conducted in one month, it showed good repeatability and long-term stability. The in-situ preparation of Co(CO3)0.5(OH)·0.11H2O/WO3 gas sensing materials and the study of gas sensing properties provide a new idea for the preparation of gas sensing devices and a new way for the diversity of gas sensing materials. It has potential application value in environmental detection and intelligent medical treatment.
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Key words:
- nanomaterials /
- WO3 /
- Co(CO3)0.5(OH)·0.11H2O /
- H2S /
- composites /
- in situ /
- gas sensing
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图 1 Co(CO3)0.5(OH)·0.11H2O/WO3复合材料的制备过程示意图
Figure 1. Schematic diagram of the preparation process for Co(CO3)0.5(OH)·0.11H2O/WO3 composites
图 2 WO3和Co(CO3)0.5(OH)·0.11H2O/WO3复合材料的FE-SEM图像
Figure 2. FE-SEM images of WO3 and Co(CO3)0.5(OH)·0.11H2O/WO3 composites
图 3 WO3、Co(CO3)0.5(OH)·0.11H2O/WO3和Co(CO3)0.5(OH)·0.11H2O的FTIR图谱
Figure 3. FTIR spectra of WO3, Co(CO3)0.5(OH)·0.11H2O/WO3 and Co(CO3)0.5(OH)·0.11H2O
图 4 Al2O3基底、WO3、Co(CO3)0.5(OH)·0.11H2O/WO3-20和Co(CO3)0.5(OH)·0.11H2O的XRD图谱
Figure 4. XRD patterns of Al2O3 substrate, WO3, Co(CO3)0.5(OH)·0.11H2O/WO3-20 and Co(CO3)0.5(OH)·0.11H2O
图 6 WO3和Co(CO3)0.5(OH)·0.11H2O/WO3复合材料的气敏性能：(a) 对H2S气体的温度-灵敏度曲线；(b) 对多种气体的选择性
Ra—Resistance in air atmosphere; Rg—Resistance in the target gas atmosphere
Figure 6. Gas sensing performance of WO3 and Co(CO3)0.5(OH)·0.11H2O/WO3 composites: (a) Temperature-sensitivity curves to H2S; (b) Response to various gases
图 7 (a) Co(CO3)0.5(OH)·0.11H2O/WO3-20元件对50×10−6 H2S气体的响应恢复曲线；(b) 长期稳定性曲线
Tres—Response time; Trec—Recovery time
Figure 7. (a) Response recovery curve of Co(CO3)0.5(OH)·0.11H2O/WO3-20 sensor to 50×10−6 H2S; (b) Long-term stability curves
图 8 (a) Co(CO3)0.5(OH)·0.11H2O/WO3-20元件对不同浓度H2S气体的灵敏度曲线；(b) 体积分数3×10−6~50×10−6的响应线性关系
R2—Coefficient of determination
Figure 8. (a) Sensitivity curve of Co(CO3)0.5(OH)·0.11H2O/WO3-20 sensor to different concentrations of H2S gas; (b) Linear relation of volume fraction 3×10−6-50×10−6
图 9 WO3和Co(CO3)0.5(OH)·0.11H2O/WO3元件在气敏测试过程中的电阻变化曲线
Figure 9. Resistance change curves of WO3 and Co(CO3)0.5(OH)·0.11H2O/WO3 sensors during gas sensing test
图 10 Co(CO3)0.5(OH)·0.11H2O/WO3-20元件在90℃对50×10−6 H2S的湿度稳定性曲线
Figure 10. Humidity stability curve of Co(CO3)0.5(OH)·0.11H2O/WO3-20 sensor at 90℃ to 50×10−6 H2S
图 11 Co(CO3)0.5(OH)·0.11H2O/WO3在空气(a)和H2S (b)中的传感机制图
Eg—Energy gap
Figure 11. Sensing mechanism of Co(CO3)0.5(OH)·0.11H2O/WO3 in air (a) and H2S (b)
表 1 不同复合材料的命名
Table 1. Naming of different composites
Sample Reaction time/min Co(CO3)0.5(OH)·0.11H2O/WO3-10 10 Co(CO3)0.5(OH)·0.11H2O/WO3-20 20 Co(CO3)0.5(OH)·0.11H2O/WO3-30 30 
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表 2 不同H2S气敏传感器的气敏性能对比
Table 2. Comparison of gas sensing performance of different H2S gas sensors
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