二氧化锡中空微球用于快速灵敏检测硫化氢

doi:10.7503/cjcu20170219

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (11): 1953.doi: 10.7503/cjcu20170219

二氧化锡中空微球用于快速灵敏检测硫化氢

李光耀¹, 王煜¹, 曹尹亮¹, 肖忠良¹(), 黄颖¹, 冯泽猛², 印遇龙², 曹忠¹()

1. 长沙理工大学化学与生物工程学院, 电力与交通材料保护湖南省重点实验室,微纳生物传感与食品安全检测协同创新中心, 长沙 410114
2. 中国科学院亚热带农业生态研究所, 长沙 410125

收稿日期:2017-04-11 出版日期:2017-11-10 发布日期:2017-10-30
作者简介:联系人简介: 曹忠, 男, 博士, 教授, 主要从事纳米生物传感、环境与食品安全检测方面的研究. E-mail: zhongcao2004@163.com。肖忠良, 男, 博士, 教授, 主要从事环境检测与传感器件及装置方面的研究. E-mail: xiaozhongliang@163.com
基金资助:
中国科学院科技服务网络(STS)计划项目(批准号: KFJ-SW-STS-173)和国家自然科学基金(批准号: 31527803)资助

SnO₂ Hollow Microspheres Used for Rapid and Sensitive Detection of Hydrogen Sulfide^†

LI Guangyao¹, WANG Yu¹, CAO Yinliang¹, XIAO Zhongliang^1,^*(), HUANG Ying¹, FENG Zemeng², YIN Yulong², CAO Zhong^1,^*()

1. Collaborative Innovation Center of Miro/nano Bio-sensing and Food Safety Inspection, Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering,Changsha University of Science and Technology, Changsha 410114, China
2. Institute of Subtropical Agriculture, Chinese Academy of Sciences, Changsha 410125, China

Received:2017-04-11 Online:2017-11-10 Published:2017-10-30
Contact: XIAO Zhongliang,CAO Zhong E-mail:xiaozhongliang@163.com;zhongcao2004@163.com
Supported by:
† Supported by the Projects of Science and Technology Service-net(STS) Program of the Chinese Academy of Sciences, China(No.KFJ-SW-STS-173) and the National Natural Science Foundation of China(No.31527803)

摘要/Abstract

摘要：

以氨基酚醛树脂球作模板, 通过一种简单的模板法制备了具有中空微球(HMS)结构的二氧化锡; 将其涂覆于氧化铝陶瓷管金电极表面, 制得一种新型薄膜式硫化氢传感器. 采用X射线衍射(XRD)及透射电子显微镜(TEM)表征了材料的微观结构和形貌, 并考察了二氧化锡中空微球(SnO₂ HMS)的气敏性能. 结果表明, 二氧化锡中空微球对硫化氢气体表现出良好的气敏特性. 在最佳工作温度(200 ℃)下, 所制作的传感器对142.6 mg/m³硫化氢的响应值高达97.13%, 响应时间为22 s. 该传感器对硫化氢的响应线性范围为0.2852~142.6 mg/m³, 相关系数为0.9931, 检出限达到0.1549 mg/m³, 且几乎不受环境湿度和温度的影响, 具有良好的重现性和选择性. 对养殖场中硫化氢气体连续监测10个月后, 传感器响应信号衰减了5.4%, 表明该传感器具有长期稳定的使用寿命, 可实现远程监测的实际应用.

关键词: 二氧化锡中空微球, 硫化氢, 气体传感器, 氨基酚醛树脂球

Abstract:

Tin dioxide hollow microspheres(Sn $O 2$ HMS) were prepared using amino-phenol/formaldehyde resin spheres(APF) as templates. A novel thin-film type hydrogen sulfide(H₂S) gas sensor was constructed by coating SnO₂ HMS onto an alumina ceramic tube based Au electrode. The crystalline phase and microstructure of different nano-materials were characterized by means of X-ray diffraction(XRD) and transmission electron microscopy(TEM), and the gas sensing properties of SnO₂ HMS were studied in detail. The experimental results showed that SnO₂ HMS had good sensing properties for H₂S. At the optimum operating temperature of 200 ℃, the response signal of the prepared sensor to 142.6 mg/m³ H₂S was as high as 97.13%, and the response time was very short, i.e. 22 s. The response linear range to H₂S was from 0.2852 mg/m³ to 142.6 mg/m³, with a detection limit of 0.1549 mg/m³, and the correlation coefficient was 0.9931. Almost no effects on the sensor were observed from the environmental humidity and temperature. Also, the sensor possessed good reproducibility and selectivity. The sensor response signal reduced by 5.4% after 10 months of continuous monitoring of H₂S gas in a pig farm, indicating that the sensor has a long-term stable lifetime with valuable application for remote monitoring in practice.

Key words: SnO2 hollow microspheres, Hydrogen sulfide, Gas sensor, Aminophenol/formaldehyde resin sphere

中图分类号:

O659.36

TrendMD:

李光耀, 王煜, 曹尹亮, 肖忠良, 黄颖, 冯泽猛, 印遇龙, 曹忠. 二氧化锡中空微球用于快速灵敏检测硫化氢. 高等学校化学学报, 2017, 38(11): 1953.

LI Guangyao, WANG Yu, CAO Yinliang, XIAO Zhongliang, HUANG Ying, FENG Zemeng, YIN Yulong, CAO Zhong. SnO₂ Hollow Microspheres Used for Rapid and Sensitive Detection of Hydrogen Sulfide^†. Chem. J. Chinese Universities, 2017, 38(11): 1953.

图/表 14

Scheme 1 Schematic diagram for construction of SnO2 HMS gas sensor

Scheme 2 Schematic diagram of the device for gas detection1. AC power source; 2.sample injector; 3. thermohygrometer; 4. temperature and humidity probe; 5. detection cell;6. thermostatic water bath; 7. SnO2 HMS gas sensor; 8. digital multimeter; 9. DC power supply.

Fig.1 XRD patterns of APF(a), APF@SnO2 CSMS(b), SnO2 HMS(c) and tetragonal rutile SnO2(d)

Fig.2 TEM images of different nano-materials(A) APF; (B) APF@SnO2 CSMS; (C) SnO2 HMS; (D) high-magnification image of shell edge of SnO2 HMS particles;(E) HRTEM of SnO2; (F) selected area electron diffraction pattern of SnO2 HMS.

Fig.3 N2 adsorption-desorption isotherms of SnO2 HMS before(A) and after(B) calcination at 400 ℃ for 1 hThe insets show the corresponding pore size distributions obtained from the adsorption curves.

Fig.4 Response of SnO2 HMS sensor to 142.6 mg/m3 H2S at different temperatures

Fig.5 Response behaviors of SnO2 HMS sensor to 142.6 mg/m3 H2S at different ambient relative humidity(RH)(A) and ambient temperatures(B)

Fig.6 Dynamic response curves of SnO2 HMS sensor to different concentrations of H2S(A) and their relation curve of response value vs. concentration(B) Inset of (B) is a linear working curve of response value vs. logarithmic value of concentration.

Fig.7 Continuous response-recovery curve of SnO2 HMS sensor to 142.6 mg/m3 H2S(A) and the corresponding response time curve[B, dotted line of (A)] at operating temperature of 200 ℃

Fig.8 Reproducibility of six SnO2 HMS sensors responding to 142.6 mg/m3 H2S

Fig.9 Histogram of SnO2 HMS sensor responding to 142.6 mg/m3 of different gases

Fig.10 Application of SnO2 HMS sensor for remote monitoring of H2S in pig farm(A) Photograph of SnO2 HMS gas sensor hanging in pig farm; (B) photograph of signal acquisition module of gas sensor.

Fig.11 Long-term stability curve of SnO2 HMS sensor

Fig.12 Schematic diagram of response mechanism of the SnO2 HMS gas sensor to H2S

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二氧化锡中空微球用于快速灵敏检测硫化氢

SnO₂ Hollow Microspheres Used for Rapid and Sensitive Detection of Hydrogen Sulfide^†

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二氧化锡中空微球用于快速灵敏检测硫化氢

SnO2 Hollow Microspheres Used for Rapid and Sensitive Detection of Hydrogen Sulfide†

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SnO₂ Hollow Microspheres Used for Rapid and Sensitive Detection of Hydrogen Sulfide^†