基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器

doi:10.7503/cjcu20150669

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (3): 460.doi: 10.7503/cjcu20150669

基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器

周煦成, 李志华, 邹小波(), 石吉勇, 黄晓玮, 胡雪桃

江苏大学食品与生物工程学院, 镇江 212013

收稿日期:2015-08-21 出版日期:2016-03-10 发布日期:2015-12-26
基金资助:
国家自然科学基金(批准号: 61301239)、国家科技支撑计划项目(批准号: 2015BAD19B03, 2015BAD19B04)、中国博士后科学基金(批准号: 2013M540422, 2014T70483)、江苏省博士后科研资助计划(批准号: 1301051C)、国家“八六三”计划项目(批准号: 2011AA108007)、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)和江苏省自然科学基金(批准号: BK20130505)资助

Gas Sensor Based on Porous Film of Polyaniline/sulfonated Nickel Phthalocyanine Composites for the Detection of Ammonia^†

ZHOU Xucheng, LI Zhihua, ZOU Xiaobo^*(), SHI Jiyong, HUANG Xiaowei, HU Xuetao

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

Received:2015-08-21 Online:2016-03-10 Published:2015-12-26
Contact: ZOU Xiaobo E-mail:zou_xiaobo@ujs.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.61301239), the National Science and Technology Support Program of China(Nos.2015BAD19B03, 2015BAD19B04), the Postdoctoral Science Foundation of China(Nos.2013M540422, 2014T70483), the Science Foundation for Postdoctoral in Jiangsu Province, China(No.1301051C), the National High-tech Research and Development Program of China(No.2011AA108007), the Jiangsu Provincial Science Fund for Distinguished Young Scholars of China(No.BK20130010), the New Century Excellent Talents in University, China(No.NCET-11-0986) and the Natural Science Foundation of Jiangsu Province, China(No.BK20130505)

摘要/Abstract

摘要：

利用磺化镍酞菁(NiTSPc)对苯胺(PANI)聚合的催化作用, 通过简单的电聚合方法在叉指金电极(IAE)表面合成了PANI/NiTSPc多孔渗透膜. 利用扫描电子显微镜(SEM)、原子力显微镜(AFM)、能量色散图谱(EDS)和拉曼光谱对PANI/NiTSPc多孔膜进行表征. 在室温下, 采用基于PANI/NiTSPc多孔膜制备的传感器对不同浓度(3.8~1900 mg/m³)的NH₃进行了检测. 结果表明, 对于76 mg/m³的NH₃, 传感器的灵敏度为2.75, 响应时间为10 s, 且该传感器具有恢复时间短、重复性及稳定性良好等优点. 所制备的PANI/NiTSPc薄膜传感器在NH₃检测及电子鼻的应用中具有巨大潜力.

关键词: 磺化镍酞菁, 聚苯胺, 氨气, 气体传感器

Abstract:

By utilizing the significant catalytic effect of sulfonated nickel phthalocyanine(NiTSPc) on the anilinepolymerization, a porous thin film of polyaniline(PANI) and sulfonated nickel phthalocyanine(PANI/NiTSPc) composite was deposited across the gaps of an interdigitated Au electrode(IAE) by a simple electrochemical polymerization method. The PANI/NiTSPc porous thin film was characterized by means of scanning electron microscopy(SEM), atomic force microscopy(AFM), energy dispersive spectrum(EDS) and Raman spectrum. At room temperature, the ammonia sensing properties of the PANI/NiTSPc porous thin film prepared at optimum conditions were studied. The sensitivity of the film to 76 mg/m³ NH₃ was up to 2.75 with response time as short as 10 s. In addition, rather fast recovery rate, good reproducibility and long-term stability were also observed in a wide concentration range from 3.8 to 1900 mg/m³. Therefore, the proposed PANI/NiTSPc nanocomposite thin film sensors are highly potential candidates in the field of NH₃ detection and electronic nose application in further work.

Key words: Sulfonated nickel phthalocyanine, Polyaniline, Ammonia, Gas sensor

中图分类号:

O657

TrendMD:

周煦成, 李志华, 邹小波, 石吉勇, 黄晓玮, 胡雪桃. 基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器. 高等学校化学学报, 2016, 37(3): 460.

ZHOU Xucheng, LI Zhihua, ZOU Xiaobo, SHI Jiyong, HUANG Xiaowei, HU Xuetao. Gas Sensor Based on Porous Film of Polyaniline/sulfonated Nickel Phthalocyanine Composites for the Detection of Ammonia^†. Chem. J. Chinese Universities, 2016, 37(3): 460.

图/表 10

Fig.1 Schematic and photo of the interdigitated Au electrode

Fig.2 Schematic diagram of the experimental setup

Fig.3 Comparison of CV curves of aniline electropolymerization in the absence(a) and presence(b) of NiTSPc(A) and continuous CV curves of aniline electropolymerization in the presence of NiTSPc for 5 cycles(B) Electrolyte: 0.5 mol/L H2SO4+0.05 mol/L aniline+2×10-3 mol/L NiTSPc. Inset of (B) is enlarge curves in the range of 0.14—0.20 V.

Fig.4 SEM images of the porous PANI/NiTSPc film deposited on IAE scanned for 1 cycle(A) and the details of the porous film(B), SEM images of the PANI/NiTSPc film(C) and pure PANI on IAE scanned for 5 cycles(D), AFM images of PANI/NiTSPc films scanned for 1 cycle(E) and 5 cycles(F) and EDS(G) and Raman spectra(H) of the PANI/NiTSPc composites

Fig.5 Dynamic response of the sensor prepared in electrolyte containing 5×10-4(A), 2×10-3(B) and 4×10-3 mol/L of NiTSPc(C) toward 760 mg/m3 NH3 and dependence of the resistance and response(D), response time and recovery time(E) on NiTSPc concentration

Fig.6 Dependence of sensitivity and Ra of the prepared sensors on the applied potential limit(A) and scan rate(B)

Fig.7 Response transients(A, B) and relative response values(C, D) of PANI/NiTSPc thin films exposed to NH3 of different concentrations(B) enlarged response transients of in the aoncentration range of 3.8—190 mg/m3; (D) dependence of relative response on NH3 concentration ranging from 3.8 mg/m3 to 76 mg/m3)

Table 1 Comparison of the analytical performance of the proposed ammonia sensor with previously reported ammonia sensors

Sensing material	Linear range/(mg·m^-3)	Response time/s	Recovery time/s	Reference
ZnO		160	660	[10]
PANI		122	180	[18]
Graphene/PANI	0.76—4864	50	23	[24]
CSA-PANI/SnO₂		46	3245	[44]
PANI/MSSA		25	274	[45]
MWCNTs/PANI	0—76			[46]
PANI/PTSA		270	210	[47]
PANI/HCL/PTSA		240	240	[47]
CNFL/SnO₂		100	120	[48]
PANI/NiTSPc	3.8—1900	10	25	This work

Fig.8 Comparison of the response of the proposed sensor to different gases

Fig.9 Dynamic response transients of the sensor toward 760 mg/m3 NH3 for 3 times

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基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器

Gas Sensor Based on Porous Film of Polyaniline/sulfonated Nickel Phthalocyanine Composites for the Detection of Ammonia^†

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基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器

Gas Sensor Based on Porous Film of Polyaniline/sulfonated Nickel Phthalocyanine Composites for the Detection of Ammonia†

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Gas Sensor Based on Porous Film of Polyaniline/sulfonated Nickel Phthalocyanine Composites for the Detection of Ammonia^†