基于纳米Zr3Y2O9交叉敏感的苯和三甲胺传感器

周考文等

1 引 言

苯是一种无色易挥发且有特殊芳香性气味的液体，已被世界卫生组织确定为强烈致癌物质。含苯的空气对皮肤、眼睛和上呼吸道都有刺激作用，长期吸入这种空气能导致再生障碍性贫血[1]。三甲胺（TMA）是一种恶臭污染物，有鱼的腥臭味。三甲胺的存在及其浓度指标是评估肉类和鱼类食品质量的重要标准， 是表征某些代谢缺陷疾病的气味标识，是环境恶臭污染控制的主要对象，是某些工农业生产质量控制的关键参数[2]。

苯或三甲胺的测定方法主要有色谱法[3，4]、色质联用法[5]和荧光法[6]等，由于这些方法都需要预先富集和适当处理后才能完成测定，因此耗时长，不易现场实现。苯可以从装修材料中散发，三甲胺是鱼虾新鲜度的重要检测指标，这两种分子在大型冷藏库、商场冷藏柜和居民厨房常常同时存在，因此，研究同时快速准确测定空气中苯和三甲胺的方法具有一定的现实意义。

催化发光（Cataluminescence， CTL）是在固体敏感材料表面发生催化反应时产生的激发态产物返回基态时放射出的残余能量，不同反应的催化发光光谱轮廓有差异，因此可以作为分析依据。催化发光具有不需要发光试剂、气敏材料寿命长、光信号便于处理和易于小型化等优点，被认为是一种十分理想的气体传感机制，从1976年Breysse等[7]首先观察到这种现象至今，已经得到了人们的广泛关注和应用[8～20]。

3.9 小结

研究了两种分子同时在纳米材料表面的催化发光响应关系，利用苯和三甲胺的交叉敏感特性，建立了基于纳米Zr3Y2O9复合氧化物催化发光的苯和三甲胺传感模式，可以实现大气中微量苯和三甲胺的在线监测。本研究不同于利用多个气体传感器组成阵列监测多组分气体的识别模式[14，17～19]， 为复杂气体传感技术研究提供了一条新思路。

References

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18 Li B， Liu J F， Shi G L， Liu J. Sens. Actuators B， 2013， 177： 1167-1172

19 Li S F， Zheng J Z， Zhang W X， Cao J， Li S X， Rao Z M. Analyst， 2013， 138（3）： 916-920

20 Li B， Zhang Y， Liu J， Xie X， Zou D， Li M， Liu J. Luminescence， 2013， doi： 10.1002/bio.2548

21 GB/T 117371989， Standard Method for Hygienic Examination of Benzene， Toluene and Xylene in Air of Residential AreasGas Chromatography. National Standard of the People′s Republic of China.

居住区大气中苯、甲苯和二甲苯卫生检验标准方法——气相色谱法. 中华人民共和国国家标准. GB/T 117371989

22 GB/T 146761993， Air Quality Determination of TrimethylamineGas Chromatography. National Standard of the People′s Republic of China.

空气质量三甲胺的测定——气相色谱法. 中华人民共和国国家标准. GB/T 146761993

A Gaseous Benzene and Trimethylamine Sensor Based on

Cross Sensitivity on NanoZr3Y2O9

ZHOU KaoWen*， YANG HongWei， GU ChunXiu， CHENG YanLing， LI WenZong

（College of Biochemical Engineering， Beijing Union University， Beijing 100023， China）

Abstract A novel method based on cross sensitivity of cataluminescence （CTL） generated on the surface of a nanometer composite oxide was proposed for simultaneous determination of benzene and trimethylamine （TMA） in air. A variety of nanometer composite oxides based on Y2O3 that showed catalytic activity to many gas molecules were synthesized. For the fabrication of the detector， nanometer composite oxide was directly coated on the ceramic rod to form a 0.1-0.15 mm thick layer. The ceramic rod with nanometer composite oxide was inserted into a quartz tube with an inner diameter of 10 mm. The temperature of nanometer composite oxide was controlled by the digital heater. When gas samples passed through the nanometer composite oxide in the quartz tube by the air flow， the CTL was generated during the catalytic oxidation on the surface of the nanometer composite oxide. The CTL signals were respectively recorded by two ultra weak chemiluminescence analyzers. The CTL intensity and selectivity for the determination of benzene and TMA on nano Zr3Y2O9 which was characterized by TEM were bigger and better than those on other nanosized composite oxides. The optimum experimental conditions were tested. Selective determination was achieved at a wavelength of 440 nm for benzene and 540 nm for TMA. The surface temperature of the nanometer materials was about 313 ℃. The flow rate of air carrier was about 140 mL/min. The limit of detection of this method was 0.30 mg/m3 for benzene at 440 nm and 0.70 mg/m3 for TMA at 540 nm. The linear range of CTL intensity versus concentration of benzene at 440 nm was 0.8-105.0 mg/m3， benzene at 540 nm was 3.0-130.0 mg/m3， TMA at 440 nm was 2.5-232.0 mg/m3 and TMA at 540 nm was 1.2-156.0 mg/m3. The recovery of 5 testing standard samples by this method was 96.8%-102.3% for benzene and 97.6%-103.4% for TMA. Common coexistence matters， such as formaldehyde， ethanol， acetone， ammonia， sulfur dioxide and carbon dioxide， did not disturb the determination. The relative standard deviation （RSD） of CTL signals of a continuous 200 h detection of gas mixture of 50 mg/m3 benzene and 50 mg/m3 TMA was 2.0%， which demonstrated the longevity and steady performance of nanoZr3Y2O9 to benzene and TMA under this experimental conditions.

Keywords Benzene； Trimethylamine； Cross sensitivity； Nanometer composite oxide； Gas sensor

（Received 4 November 2013； accepted 12 March 2014）

18 Li B， Liu J F， Shi G L， Liu J. Sens. Actuators B， 2013， 177： 1167-1172

19 Li S F， Zheng J Z， Zhang W X， Cao J， Li S X， Rao Z M. Analyst， 2013， 138（3）： 916-920

20 Li B， Zhang Y， Liu J， Xie X， Zou D， Li M， Liu J. Luminescence， 2013， doi： 10.1002/bio.2548

21 GB/T 117371989， Standard Method for Hygienic Examination of Benzene， Toluene and Xylene in Air of Residential AreasGas Chromatography. National Standard of the People′s Republic of China.

居住区大气中苯、甲苯和二甲苯卫生检验标准方法——气相色谱法. 中华人民共和国国家标准. GB/T 117371989

22 GB/T 146761993， Air Quality Determination of TrimethylamineGas Chromatography. National Standard of the People′s Republic of China.

空气质量三甲胺的测定——气相色谱法. 中华人民共和国国家标准. GB/T 146761993

A Gaseous Benzene and Trimethylamine Sensor Based on

Cross Sensitivity on NanoZr3Y2O9

ZHOU KaoWen*， YANG HongWei， GU ChunXiu， CHENG YanLing， LI WenZong

（College of Biochemical Engineering， Beijing Union University， Beijing 100023， China）

Abstract A novel method based on cross sensitivity of cataluminescence （CTL） generated on the surface of a nanometer composite oxide was proposed for simultaneous determination of benzene and trimethylamine （TMA） in air. A variety of nanometer composite oxides based on Y2O3 that showed catalytic activity to many gas molecules were synthesized. For the fabrication of the detector， nanometer composite oxide was directly coated on the ceramic rod to form a 0.1-0.15 mm thick layer. The ceramic rod with nanometer composite oxide was inserted into a quartz tube with an inner diameter of 10 mm. The temperature of nanometer composite oxide was controlled by the digital heater. When gas samples passed through the nanometer composite oxide in the quartz tube by the air flow， the CTL was generated during the catalytic oxidation on the surface of the nanometer composite oxide. The CTL signals were respectively recorded by two ultra weak chemiluminescence analyzers. The CTL intensity and selectivity for the determination of benzene and TMA on nano Zr3Y2O9 which was characterized by TEM were bigger and better than those on other nanosized composite oxides. The optimum experimental conditions were tested. Selective determination was achieved at a wavelength of 440 nm for benzene and 540 nm for TMA. The surface temperature of the nanometer materials was about 313 ℃. The flow rate of air carrier was about 140 mL/min. The limit of detection of this method was 0.30 mg/m3 for benzene at 440 nm and 0.70 mg/m3 for TMA at 540 nm. The linear range of CTL intensity versus concentration of benzene at 440 nm was 0.8-105.0 mg/m3， benzene at 540 nm was 3.0-130.0 mg/m3， TMA at 440 nm was 2.5-232.0 mg/m3 and TMA at 540 nm was 1.2-156.0 mg/m3. The recovery of 5 testing standard samples by this method was 96.8%-102.3% for benzene and 97.6%-103.4% for TMA. Common coexistence matters， such as formaldehyde， ethanol， acetone， ammonia， sulfur dioxide and carbon dioxide， did not disturb the determination. The relative standard deviation （RSD） of CTL signals of a continuous 200 h detection of gas mixture of 50 mg/m3 benzene and 50 mg/m3 TMA was 2.0%， which demonstrated the longevity and steady performance of nanoZr3Y2O9 to benzene and TMA under this experimental conditions.

Keywords Benzene； Trimethylamine； Cross sensitivity； Nanometer composite oxide； Gas sensor

（Received 4 November 2013； accepted 12 March 2014）

18 Li B， Liu J F， Shi G L， Liu J. Sens. Actuators B， 2013， 177： 1167-1172

19 Li S F， Zheng J Z， Zhang W X， Cao J， Li S X， Rao Z M. Analyst， 2013， 138（3）： 916-920

20 Li B， Zhang Y， Liu J， Xie X， Zou D， Li M， Liu J. Luminescence， 2013， doi： 10.1002/bio.2548

21 GB/T 117371989， Standard Method for Hygienic Examination of Benzene， Toluene and Xylene in Air of Residential AreasGas Chromatography. National Standard of the People′s Republic of China.

居住区大气中苯、甲苯和二甲苯卫生检验标准方法——气相色谱法. 中华人民共和国国家标准. GB/T 117371989

22 GB/T 146761993， Air Quality Determination of TrimethylamineGas Chromatography. National Standard of the People′s Republic of China.

空气质量三甲胺的测定——气相色谱法. 中华人民共和国国家标准. GB/T 146761993

A Gaseous Benzene and Trimethylamine Sensor Based on

Cross Sensitivity on NanoZr3Y2O9

ZHOU KaoWen*， YANG HongWei， GU ChunXiu， CHENG YanLing， LI WenZong

（College of Biochemical Engineering， Beijing Union University， Beijing 100023， China）

Abstract A novel method based on cross sensitivity of cataluminescence （CTL） generated on the surface of a nanometer composite oxide was proposed for simultaneous determination of benzene and trimethylamine （TMA） in air. A variety of nanometer composite oxides based on Y2O3 that showed catalytic activity to many gas molecules were synthesized. For the fabrication of the detector， nanometer composite oxide was directly coated on the ceramic rod to form a 0.1-0.15 mm thick layer. The ceramic rod with nanometer composite oxide was inserted into a quartz tube with an inner diameter of 10 mm. The temperature of nanometer composite oxide was controlled by the digital heater. When gas samples passed through the nanometer composite oxide in the quartz tube by the air flow， the CTL was generated during the catalytic oxidation on the surface of the nanometer composite oxide. The CTL signals were respectively recorded by two ultra weak chemiluminescence analyzers. The CTL intensity and selectivity for the determination of benzene and TMA on nano Zr3Y2O9 which was characterized by TEM were bigger and better than those on other nanosized composite oxides. The optimum experimental conditions were tested. Selective determination was achieved at a wavelength of 440 nm for benzene and 540 nm for TMA. The surface temperature of the nanometer materials was about 313 ℃. The flow rate of air carrier was about 140 mL/min. The limit of detection of this method was 0.30 mg/m3 for benzene at 440 nm and 0.70 mg/m3 for TMA at 540 nm. The linear range of CTL intensity versus concentration of benzene at 440 nm was 0.8-105.0 mg/m3， benzene at 540 nm was 3.0-130.0 mg/m3， TMA at 440 nm was 2.5-232.0 mg/m3 and TMA at 540 nm was 1.2-156.0 mg/m3. The recovery of 5 testing standard samples by this method was 96.8%-102.3% for benzene and 97.6%-103.4% for TMA. Common coexistence matters， such as formaldehyde， ethanol， acetone， ammonia， sulfur dioxide and carbon dioxide， did not disturb the determination. The relative standard deviation （RSD） of CTL signals of a continuous 200 h detection of gas mixture of 50 mg/m3 benzene and 50 mg/m3 TMA was 2.0%， which demonstrated the longevity and steady performance of nanoZr3Y2O9 to benzene and TMA under this experimental conditions.

Keywords Benzene； Trimethylamine； Cross sensitivity； Nanometer composite oxide； Gas sensor

（Received 4 November 2013； accepted 12 March 2014）