基于納米Zr3Y2O9交叉敏感的苯和三甲胺傳感器

周考文等

1 引 言

苯是一種無(wú)色易揮發(fā)且有特殊芳香性氣味的液體，已被世界衛(wèi)生組織確定為強(qiáng)烈致癌物質(zhì)。含苯的空氣對(duì)皮膚、眼睛和上呼吸道都有刺激作用，長(zhǎng)期吸入這種空氣能導(dǎo)致再生障礙性貧血[1]。三甲胺（TMA）是一種惡臭污染物，有魚的腥臭味。三甲胺的存在及其濃度指標(biāo)是評(píng)估肉類和魚類食品質(zhì)量的重要標(biāo)準(zhǔn)， 是表征某些代謝缺陷疾病的氣味標(biāo)識(shí)，是環(huán)境惡臭污染控制的主要對(duì)象，是某些工農(nóng)業(yè)生產(chǎn)質(zhì)量控制的關(guān)鍵參數(shù)[2]。

苯或三甲胺的測(cè)定方法主要有色譜法[3，4]、色質(zhì)聯(lián)用法[5]和熒光法[6]等，由于這些方法都需要預(yù)先富集和適當(dāng)處理后才能完成測(cè)定，因此耗時(shí)長(zhǎng)，不易現(xiàn)場(chǎng)實(shí)現(xiàn)。苯可以從裝修材料中散發(fā)，三甲胺是魚蝦新鮮度的重要檢測(cè)指標(biāo)，這兩種分子在大型冷藏庫(kù)、商場(chǎng)冷藏柜和居民廚房常常同時(shí)存在，因此，研究同時(shí)快速準(zhǔn)確測(cè)定空氣中苯和三甲胺的方法具有一定的現(xiàn)實(shí)意義。

催化發(fā)光（Cataluminescence， CTL）是在固體敏感材料表面發(fā)生催化反應(yīng)時(shí)產(chǎn)生的激發(fā)態(tài)產(chǎn)物返回基態(tài)時(shí)放射出的殘余能量，不同反應(yīng)的催化發(fā)光光譜輪廓有差異，因此可以作為分析依據(jù)。催化發(fā)光具有不需要發(fā)光試劑、氣敏材料壽命長(zhǎng)、光信號(hào)便于處理和易于小型化等優(yōu)點(diǎn)，被認(rèn)為是一種十分理想的氣體傳感機(jī)制，從1976年Breysse等[7]首先觀察到這種現(xiàn)象至今，已經(jīng)得到了人們的廣泛關(guān)注和應(yīng)用[8～20]。

3.9 小結(jié)

研究了兩種分子同時(shí)在納米材料表面的催化發(fā)光響應(yīng)關(guān)系，利用苯和三甲胺的交叉敏感特性，建立了基于納米Zr3Y2O9復(fù)合氧化物催化發(fā)光的苯和三甲胺傳感模式，可以實(shí)現(xiàn)大氣中微量苯和三甲胺的在線監(jiān)測(cè)。本研究不同于利用多個(gè)氣體傳感器組成陣列監(jiān)測(cè)多組分氣體的識(shí)別模式[14，17～19]， 為復(fù)雜氣體傳感技術(shù)研究提供了一條新思路。

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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.

居住區(qū)大氣中苯、甲苯和二甲苯衛(wèi)生檢驗(yàn)標(biāo)準(zhǔn)方法——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). GB/T 117371989

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

空氣質(zhì)量三甲胺的測(cè)定——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). 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.

居住區(qū)大氣中苯、甲苯和二甲苯衛(wèi)生檢驗(yàn)標(biāo)準(zhǔn)方法——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). GB/T 117371989

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

空氣質(zhì)量三甲胺的測(cè)定——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). 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.

居住區(qū)大氣中苯、甲苯和二甲苯衛(wèi)生檢驗(yàn)標(biāo)準(zhǔn)方法——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). GB/T 117371989

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

空氣質(zhì)量三甲胺的測(cè)定——?dú)庀嗌V法. 中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn). 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）