提取多维催化发光信号鉴别有害气体的传感器

doi:10.7503/cjcu20140098

摘要/Abstract

摘要：

基于2种催化敏感材料, 设计了通过提取多维发光信号鉴别有害气体的催化发光(CTL)传感器. 在最佳检测条件下, 18种有害气体依次经过纳米Al₂O₃(或MgO)表面进行CTL反应, 产生的CTL 响应信号组成其特征图谱. 通过主成分分析法(PCA)鉴别了各种气体. 采用线性判别分析(LDA)对浓度分别为100, 300及500 mL/m³的18种气体的识别正确率均为100%. 该传感器可以同时测量气体的浓度, 检出限均低于我国工作场所有害因素职业接触限值(GBZ2.1-2007), 空气中几种常见的污染物共存不影响这些有害气体的检测. 该传感器具有传感元件少、稳定性好、操作方便、信息丰富和识别能力强等优点, 可用于发展微型实用的传感器.

关键词: 多维信号, 催化发光, 化学发光, 传感器, 有害气体

Abstract:

A sensor system for idenpngying toxic gas was fabricated by extracting multidimensional cataluminescence(CTL) signal based on two kinds of catalytic sensitive materials. Under the optimal conditions of wavelength of 440 nm, temperature of 247 ℃ and flow rate of 240 mL/min, eighteen kinds of volatile organic compounds respectively generated CTL signal I₁(the first order reaction signal) when each vapor passed through nano-Al₂O₃ or MgO, then residual gas from first reaction was regarded as a new reactant and continued to be oxidized on nano-Al₂O₃ or MgO, generating new CTL signal I₂(the second order reaction signal). Moreover, for each organic gas, eight CTL signals could be obtained by changing the direction of the gas flowing through Al₂O₃-MgO, which formed the characteristic spectrum for each toxic compound. Different gases could be scienpngically and objectively idenpngied based on the principal component analysis(PCA). In addition, linear discriminant analysis(LDA) was utilized to idenpngy eighteen kinds of organic gas in different concentration(100, 300 and 500 mL/m³) with an accuracy of 100%. Furthermore, the sensor could achieve quantitative analysis with the detection limits below the occupational exposure limit of workplace(GBZ2.1-2007). Several kinds of common pollutants in the air had no interference on the detection of chosen toxic gases. Therefore, the sensor system may be capable to develop a micro-sensor with less sensing elements, good stability, conve-nient operation, rich information and strong recognition ability in real-life application.

Key words: Multidimensional signal, Cataluminescence, Chemiluminiscence, Sensor, Toxic gas

中图分类号:

O657

TrendMD:

陈景林, 曹小安, 刘永慧, 曾嘉仪, 任柯柯. 提取多维催化发光信号鉴别有害气体的传感器. 高等学校化学学报, 2014, 35(6): 1166.

CHEN Jinglin, CAO Xiaoan, LIU Yonghui, ZENG Jiayi, REN Keke. Sensor Based on Extracting Multidimensional Cataluminescence Signals for Idenpngying Toxic Gas^†. Chem. J. Chinese Universities, 2014, 35(6): 1166.

图/表 12

Fig.1 Schematic diagram of CTL detection system by simultaneous detection of I1 and I2PMT: photomultiplier.

Table 1 Experimental materials and reagents

Material or reagent	Molecular Formula	Purity(%)	Source
MgO(50 nm)	MgO	≥99.99	Beijing Nachen Scienpngic Trading Co., Ltd.
Al₂O₃(≤10 nm)	Al₂O₃	≥99.99	Shanghai Zhuerna High-tech Powder Material Co., Ltd.
Formaldehyde	HCHO	40.0	Guangzhou Chemical Company
Acetaldehyde	CH₃CHO	40.0	Tianjin Fuchen Chemical Co., Ltd.
n-Propionaldehyde	CH₃CH₂CHO	97.0	Aladdin Reagent(Shanghai) Co., Ltd.
n-Butanal	CH₃(CH₂)₂CHO	99.8	Najing Haizhilan Chemical Co., Ltd.
Acetone	CH₃COCH₃	99.8	Shanghai Shenxiang Chemical Co., Ltd.
Butanone	CH₃CH₂COCH₃	≥99.5	Guangzhou Chemical Company
2-Pentanone	CH₃CO(CH₂)₂CH₃	99.0	Aladdin Reagent(Shanghai) Co., Ltd.
3-Pentanone	CH₃(CH₂)₂COCH₃	98.0	Aladdin Reagent(Shanghai) Co., Ltd.
Cyclopentanone	C₅H₈O	99.5	Aladdin Reagent(Shanghai) Co., Ltd.
Cyclohexanone	C₆H₁₀O	≥99.5	Tianjin Damao Chemical Co., Ltd.
Methyl alcohol	CH₃OH	≥99.5	Tianjin Damao Chemical Co., Ltd.
Ethanol	CH₃CH₂OH	≥99.7	Tianjin Damao Chemical Co., Ltd.
Isopropyl alcohol	CH₃CH(OH)CH₃	≥99.0	Tianjin Damao Chemical Co., Ltd.
n-Butyl alcohol	CH₃(CH₂)₃OH	≥99.0	Guangzhou Chemical Company
Ethyl acetate	CH₃COOC₂H₅	≥99.5	Tianjin Fuyu Chemical Co., Ltd.
Propyl acetate	CH₃COOC₃H₇	99.0	Aladdin Reagent(Shanghai) Co., Ltd.
Butyl acetate	CH₃COOC₄H₉	≥99.0	Tianjin Fuyu Chemical Co., Ltd.
Amyl acetate	CH₃COOC₅H₁₁	98.5	Aladdin Reagent(Shanghai) Co., Ltd.
Benzene	C₆H₆	≥99.8	Tianjin Kemi'ou Chemical Reagents Development Center
Toluene	C₇H₈	≥99.8	Tianjin Kemi'ou Chemical Reagents Development Center
Ammonia	NH₃·H₂O	25.0—28.0	Guangzhou Chemical Company

Fig.2 Optimization of luminescence conditions of acetone vapor on nano-Al2O3-Al2O3■ S1; □ S2; ▲ S1/N; △ S2/N.

Fig.3 CTL intensities for 18 kinds of vapors(300 mL/m3) detected by Al2O3-Al2O3( I1, I2), Al2O3-MgO( I1, I2), MgO-MgO( I1, I2) and MgO-Al2O3( I1, I2) sensor system with an average of five parallel testa. Formaldehyde; b. acetaldehyde; c. n-propionaldehyde; d. n-butanal; e. acetone; f. butanone; g. 2-pentanone; h. 3-pentanone; i. cyclopentanone; j. cyclohexanone; k. methyl alcohol; l. ethanol; m. isopropyl alcohol; n. n-butyl alcohol; o. ethyl acetate; p. propyl acetate; q. butyl acetate; r. amyl acetate.

Fig.4 PCA score plot from an average of five parallelmeasurements of 18 kinds of vapors(300 mL/m3)1. Formaldehyde; 2. acetaldehyde; 3. n-propionaldehyde; 4. n-butanal; 5. acetone; 6. butanone; 7. 2-pentanone; 8. 3-pentanone; 9. cyclopentanone; 10. cyclohexanone; 11. methyl alcohol; 12. ethanol; 13. isopropyl alcohol; 14. n-butyl alcohol; 15. ethyl acetate; 16. propyl acetate; 17. butyl acetate; 18. amyl acetate.

Fig.5 Canonical score plots by LDA for discriminationof 18 kinds of vapors at 100 mL/m3(A), 300 mL/m3(B) and 500 mL/m3(C)1. Formaldehyde; 2. acetaldehyde; 3. n-propionaldehyde; 4. n-butanal; 5. acetone; 6. butanone; 7. 2-pentanone; 8. 3-pentanone; 9. cyclopentanone; 10. cyclohexanone; 11. methyl alcohol; 12. ethanol; 13. isopropyl alcohol; 14. n-butyl alcohol; 15. ethyl acetate; 16. propyl acetate; 17. butyl acetate; 18. amyl acetate.

Fig.6 Calibration curves between I1(a) or I2(b) intensity and concentrations of n-propionaldehyde(A), acetone(B), methyl alcohol(C) and ethyl acetate(D) vapor detected by Al2O3-Al2O3sensor system

Fig.7 Calibration curve between I1(a) or I2(b) intensity and concentration of n-propionaldehyde(A), acetone(B), methyl alcohol(C) and ethyl acetate(D) vapor detected using MgO-Al2O3 sensor system

Fig.8 Effects of humidity on CTL intensity of acetone vapors(100 mL/m3)

Fig.9 Reproducibility of I1 and I2 of acetone vapor(100 mL/m3)

Table 2 Analysis of arpngicial samples of acetone, n-propionaldehyde, ethyl acetate and methyl alcohol vapor with benzene, toluene, ammonia as interfering substance

No.	Composition	c(Actual)/(mL·m^-3)	c(Average)/(mL·m^-3)(n=3)	RSD(%, n=3)	Recovery(%)
1	Acetone	50	53	1.2	106
	Benzene	100
	Toluene	100
	Ammonia	100
2	n-Propionaldehyde	100	108	1.6	108
	Benzene	100
	Toluene	100
	Ammonia	100
3	Ethyl acetate	500	521	3.7	104
	Benzene	200
	Toluene	200
	Ammonia	200
4	Methyl alcohol	600	584	2.1	97
	Benzene	100
	Toluene	100
	Ammonia	100

Fig.10 GC/MS chromatograms from the first order catllytic oxidation product(A) and the second order catllytic oxidation product(B) of butanone vapor on Al2O3-Al2O3 surface

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