新型室温硫化氢纳米传感器的制备及性能

doi:10.7503/cjcu20131161

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (6): 1175.doi: 10.7503/cjcu20131161

新型室温硫化氢纳米传感器的制备及性能

黄晓玮, 邹小波(), 赵杰文, 石吉勇, 李志华

江苏大学食品与生物工程学院, 镇江 212013

收稿日期:2013-11-27 出版日期:2014-06-10 发布日期:2014-04-29
作者简介:联系人简介: 邹小波, 男, 博士, 教授, 博士生导师, 主要从事农产品和食品品质无损检测研究. E-mail:zou_xiaobo@ujs.edu.cn
基金资助:
国家“八六三”计划项目(批准号: 2011AA100807)、江苏省杰出青年基金(批准号: BK20130010)、教育部新世纪优秀人才支持计划项目(批准号: NCET-11-0986)、江苏特聘教授、全国优秀博士基金(批准号: 200968)、国家自然科学基金(批准号: 61301239)、江苏省自然科学基金(批准号: BK20130505)、中国博士后科学基金(批准号: 2013M540422)、江苏省博士后科研资助计划(批准号: 1301051C)、江苏省普通高校研究生科研创新计划项目(批准号: CXZZ13_0697)、镇江市科技支撑计划(批准号: NY2011026)和江苏大学高级专业人才科研启动基金(批准号: 13JDG039)资助

Fabrication and Characteristics Investigation of a Novel Nanosensor for Sulfuretted Hydrogen Operating at Room Temperature^†

HUANG Xiaowei, ZOU Xiaobo^*(), ZHAO Jiewen, SHI Jiyong, LI Zhihua

College of Food and Biological Engineering, Jiangsu University, Zhenjiang 212013, China

Received:2013-11-27 Online:2014-06-10 Published:2014-04-29
Contact: ZOU Xiaobo E-mail:zou_xiaobo@ujs.edu.cn
Supported by:
† Support by the National High-tech R & D Program of China(No.2011AA108007), the Jiangsu Provincal Science Fund for Distinguished Young Scholars, China(No.BK20130010), the New Century Excellent Talents in University, China(No.NCET-11-0986), the Specially-Appoin-ted Professors by Universities in Jiangsu Province, the Foundation of Chinese Top 100 Doctoral Dissertation(No.200968), the National Natural Science Foundation of China(No.61301239), the Natural Science Foundation of Jiangsu Province, China(No.BK20130505), the China Postdoctoral Science Foundation(No.2013M540422), Science Foundation for Postdoctoral in Jiangsu Province, China(No.2013M540422), the Scienpngic Innovation Research of College Graduate in Jiangsu Province, China(No.CXZZ13_0697), the Science and Technology Support Program of Zhenjiang, China(No.NY2011026) and the Research Foundation for Advanced Talents in Jiangsu University, China(No.13JDG039)

摘要/Abstract

摘要：

采用溶胶-凝胶法在叉指金电极表面制备纳米二氧化钛(TiO₂)多孔薄膜, 并用浓度为2.5×10⁴ mol/L的花青素对其进行敏化, 制备了一种能在室温条件下检测硫化氢(H₂S)的高灵敏度传感器. 从材料的光谱特性、微观结构和传感器的灵敏度等方面对该传感器的性能进行了评价, 并讨论了传感器的响应机理以及温度和湿度对灵敏度的影响. 结果表明, 材料表面的可见吸收光谱比花青素红移了约50 nm, 吸收能力有所提高; 纳米TiO₂颗粒呈层状堆积排列, 颗粒之间具有较多缝隙, 比表面积大. 在室温下, 该气体传感器对浓度为5~50 mL/m³的H₂S具有良好的敏感特性, 传感器灵敏度与H₂S浓度呈线性相关, 相关系数为0.939, 响应时间为50~70 s, 恢复时间为160~180 s. 计算和测试结果表明, 环境湿度约为50%时传感器的灵敏度最佳; 在10~50 ℃范围内, 温度与传感器的灵敏度存在负相关性. 该方法为简单、经济制备室温条件下工作的气体传感器提供了新思路和新方法.

关键词: 硫化氢, 二氧化钛, 花青素, 溶胶-凝胶, 气体传感器

Abstract:

A sulfuretted hydrogen sensor operating at room temperature based on pigment-sensitized TiO₂ films was fabricated. TiO₂ was prepared by sol-gel method and deposited on glass slides containing gold electrodes. The film was then immersed in a 2.5×10^-4 mol/L ethanol solution of cyanidin to absorb the pigment. For characterization of texture, UV-Vis diffuse reflectance spectra, field emission scanning electron microscopy, sulfuretted hydrogen adsorption-desorption measurements and temperature, humidity measurements were adop-ted. The results demonstrate that the sol-gel layers show a high porosity, a slightly more compact material close to the substrate. The cyanidin-sensitized TiO₂ nanosheets exhibit a clear red shift(50 nm) compared with cyanidin. The hybrid organic-inorganic formed film can detect sulfuretted hydrogen reversibly at room temperature. The sensitivity of the films increased almost linearly with increasing the concentrations of sulfuretted hydrogen(R²=0.939). The response time to increasing concentrations of the sulfuretted hydrogen is about 50~70 s, and the corresponding values for decreasing concentrations 160~180 s. At low humidity, sulfuretted hydrogen could be ionized by the cyanidin on the TiO₂ film and thereby decrease in the proton concentration at the surface. The resistance response to sulfuretted hydrogen of the sensors was nearly independent on temperature from 10 ℃ to 50 ℃. This preliminary work proposes simpler and cheaper processes to fabricate gas sensor for room temperature applications.

Key words: Sulfuretted hydrogen, Titanium dioxide, Cyanidin, Sol-gel, Gas sensor

中图分类号:

O657.11

TrendMD:

黄晓玮, 邹小波, 赵杰文, 石吉勇, 李志华. 新型室温硫化氢纳米传感器的制备及性能. 高等学校化学学报, 2014, 35(6): 1175.

HUANG Xiaowei, ZOU Xiaobo, ZHAO Jiewen, SHI Jiyong, LI Zhihua. Fabrication and Characteristics Investigation of a Novel Nanosensor for Sulfuretted Hydrogen Operating at Room Temperature^†. Chem. J. Chinese Universities, 2014, 35(6): 1175.

图/表 8

Fig.1 Schematic diagram of the sensor measurement

Fig.2 Absorption spectra of TiO2 treated with cyaniding(a) and an aqueous solution of cyaniding(b)

Fig.3 Molecular structure of cyanidin anion(A) and mechanism of surface complexation of cyanidin and TiO2(B)

Fig.4 Surface(A) and cross(B) SEM micrographs of a sol-gel TiO2 layer

Fig.5 Response of the flexible assembled pigment-sensitized TiO2 film sensors to various concentrations of H2S vapors……Concentration of H2S/(mL·m-3): 1. 5; 2. 10; 3. 20; 4. 30; 5. 40; 6. 50.

Fig.6 Resistance of 5 sensors on relative H2S concentrations(A) and the sensitivity of pigment-sensitized TiO2 film sensors(B)

Fig.7 Reaction of sulfuretted hydrogen(H2S) and cyanidin sensitized TiO2 film for the lower humidity condition

Fig.8 Dependence of the resistance response to 40 mL/m3 H2S gas(S40, a) and the clean air resistance(R0, b)…… (A) Relative humidity in air at the ambient temperature[(25±1) ℃]; (B) relative temperature in the ambient humidity air(40%).

参考文献 14

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新型室温硫化氢纳米传感器的制备及性能

Fabrication and Characteristics Investigation of a Novel Nanosensor for Sulfuretted Hydrogen Operating at Room Temperature^†

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新型室温硫化氢纳米传感器的制备及性能

Fabrication and Characteristics Investigation of a Novel Nanosensor for Sulfuretted Hydrogen Operating at Room Temperature†

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Fabrication and Characteristics Investigation of a Novel Nanosensor for Sulfuretted Hydrogen Operating at Room Temperature^†