高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (6): 1166.doi: 10.7503/cjcu20140098
收稿日期:
2014-01-29
出版日期:
2014-06-10
发布日期:
2014-04-29
作者简介:
联系人简介: 曹小安, 女, 教授, 主要从事基于纳米材料的催化发光传感器研究. E-mail:基金资助:
CHEN Jinglin, CAO Xiaoan*(), LIU Yonghui, ZENG Jiayi, REN Keke
Received:
2014-01-29
Online:
2014-06-10
Published:
2014-04-29
Contact:
CAO Xiaoan
E-mail:caoxiaoan2003@aliyun.com
Supported by:
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.
中图分类号:
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.
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 |
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.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
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 |
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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