重金属离子选择传感器及其在海水分析中应用的研究
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摘要
随着工业化大规模的发展,重金属广泛分布于各种水体,通过饮水、食物链以及生物富集等方式正在严重危害人体健康。重金属的监测迫在眉睫。中国海域海水水质污染加剧,特别是近岸海域污染严重,海洋生态系统继续恶化,因此,在“十五”期间国家提出了建立国家海洋生态环境现场快速监测示范系统的计划,通过海上实时采样、检测和分析来监测海洋水质的状况,从而能够快速做出决策以防止和制止污染的扩散。另一方面,重金属传感器的研究及其实时检测技术也是目前国际上一个重要的前沿研究课题。基于上述原因,本论文以重金属离子选择传感器及其在海水分析中的应用作力主要研究内容,该研究得到了国家863高技术项目、国家自然科学基金委国际合作中俄专项基金以及浙江省国际合作重点项目的资助。
本文所作的主要工作如下:
1) 提出了一种光寻址电位传感器(Light-Addressable Potenntiometric Sensor, LAPS)等效电路模型,对模型中各参数的影响进行了评估分析,把电化学动力学理论与半导体能带理论相结合,对LAPS的原理进行了新的阐述,指出静电电位(外置偏压和电解质溶液离子强度引起的静电吸附电位)会改变LAPS的Fermi能级,影响空间电荷区的厚度,从而影响光生电流;离子交换产生的特性吸附会影响LAPS的平带电位,从而改变空间电荷区电容,导致影响光生电流。最后,基于等效电路模型和LAPS原理,对重金属薄膜LAPS传感器进行了优化设计。
2) 首次研制出了基于LAPS和脉冲激光沉积(Pulsed Laser Deposition, PLD)技术的一种玻璃态结构的Fe离子选择薄膜传感器。合成了一种Fe离子选择电极(Fe—ISE),并对其性能进行了研究。以该电极为PLD的靶材,在LAPS上制备了一种玻璃态结构的Fe薄膜传感器(Fe-LAPS)。该传感器的线性区间为10~(-2)～10~(-5) mol/L,标准曲线的斜率为435nA/decade,检测下限为6.31×10~(-6)mol/L,适宜pH范围0～2,在浓度高于10~(-4) mol/L时,响应时间少于30 s,低于此浓度时,响应时间不超过2 min,标准曲线在8周内基本是可重复的。Fe—LAPS的分辨率和灵敏度比Fe—ISE提高了7.69倍。
3) 首次研制出了基于LAPS和PLD技术的一种晶体态结构的Hg离子选择薄膜传
With the extensive development of industrialization, heavy metals distributing comprehensively various waters are severely endangering human health by drinking water, food chain, and biogenic enrichment modes etc. It is urgent to detect heavy metals. The water pollution is aggravating in Chinese sea area, especially in neritic area. Marine ecosystems continue worsening. So the plan to establish national marine ecological environment monitor typical system in-situ was proposed during the Tenth Five-Year Plan. By means of real-time sampling, analysis and detection, seawater quality is monitoring, accordingly the decisions and measures to prevent pollution diffusion are able to be taken in time. On the other hand, heavy metal sensors and detection techniques are also foreland topics to research in the world. Based on the reasons above-mentioned, the researches on heavy metal ion selective sensors and the application in seawater analysis are as major tasks in the thesis and financed by Nation 863 High-tech Project Fund, China-Russia Special Fund in International Cooperation at Nation Nature Science Fund (NSFC) and Zhejiang Province International Cooperation Major Fund.The major contents of this thesis are given in the following aspects.1. A kind of equivalent circuit model on light-addressable potentiometric sensor (LAPS) is proposed and the effects of parameters in the LAPS model are evaluated and anaylzed. By combining electrochemical kinetics theory into semiconductor energy band theory, LAPS theory is reformulated. The results are described, that electrostatic potential including bias voltage in external circuit and electrostatic adherence caused by electrolyte solution ions can change the Fermi energy level of LAPS, thus thickness of space-charge region is changed and photo-induced current is affected, and that specific adsorption caused by ionic exchange can affect the flat band voltage of LAPS, space-charge region and photo-induced current. At last heavy metal thin film LAPS is optimized to design based on the equivalent model and LAPS theory.2. Based on LAPS and pulsed laser deposition (PLD) technique, a kind of iron (III) ion selective thin film sensor with glass state structure has been developed for the first
time. A kind of ion selective electrode (Fe —ISE) sensitive to iron (III) ion synthesized was studied on it's characteristic and used as a target of PLD device, correspondingly thin film sensor (Fe—LAPS) with glass state structure sensitive to iron (III) ion was prepared on the surface of LAPS. The Fe—LAPS has a good linearity range of 10~(-2)~10~-(5) mol/L, the slope of calibration curve is 435nA/decade, the limit of determination 6.31X10~(-6) mol/L, suitable pH range 0 to 2. While the concentration of Fe (III) ion is more than 10~(-4) mol/L, the response time is less than 30 s, and the concentration less than 10~(-4) mol/L, no more than 2 min. The calibration curve has good repetitiveness in 8 weeks. The resolution and sensitivity of Fe— LAPS improve 7.69 times than Fe—ISE's.3. Based on LAPS and PLD technique, a kind of mercury (II) ion selective thin film sensor with crystal state structure had been developed for the first time. A kind of ion selective electrode (Hg—ISE) sensitive to mercury (II) ion synthesized was studied on it's characteristic and used as a target of PLD device, correspondingly thin film sensor (Hg—LAPS) with crystal state structure was prepared on the surface of LAPS. The Hg—LAPS has a good linearity range of 10~(-3)~10~(-6) mol/L, the slope of calibration curve is 46.5 nA/decade, the limit of determination 3.44x10~(-7) mol/L, suitable pH range 1 to 3. While the concentration of Hg (II) ion is more than 10~(-5) mol/L, the response time is less than 40 s, and the concentration less than 10~(-5) mol/L, no more than 2 min. The calibration curve has good repetitiveness in 2 weeks. The resolution and sensitivity of Hg—LAPS improve 1.53 times than Hg—ISE's.4. Based on LAPS and PLD technique, a kind of chromium (VI) ion selective thin film sensor with glass state struct
本文所作的主要工作如下:
1) 提出了一种光寻址电位传感器(Light-Addressable Potenntiometric Sensor, LAPS)等效电路模型,对模型中各参数的影响进行了评估分析,把电化学动力学理论与半导体能带理论相结合,对LAPS的原理进行了新的阐述,指出静电电位(外置偏压和电解质溶液离子强度引起的静电吸附电位)会改变LAPS的Fermi能级,影响空间电荷区的厚度,从而影响光生电流;离子交换产生的特性吸附会影响LAPS的平带电位,从而改变空间电荷区电容,导致影响光生电流。最后,基于等效电路模型和LAPS原理,对重金属薄膜LAPS传感器进行了优化设计。
2) 首次研制出了基于LAPS和脉冲激光沉积(Pulsed Laser Deposition, PLD)技术的一种玻璃态结构的Fe离子选择薄膜传感器。合成了一种Fe离子选择电极(Fe—ISE),并对其性能进行了研究。以该电极为PLD的靶材,在LAPS上制备了一种玻璃态结构的Fe薄膜传感器(Fe-LAPS)。该传感器的线性区间为10~(-2)～10~(-5) mol/L,标准曲线的斜率为435nA/decade,检测下限为6.31×10~(-6)mol/L,适宜pH范围0～2,在浓度高于10~(-4) mol/L时,响应时间少于30 s,低于此浓度时,响应时间不超过2 min,标准曲线在8周内基本是可重复的。Fe—LAPS的分辨率和灵敏度比Fe—ISE提高了7.69倍。
3) 首次研制出了基于LAPS和PLD技术的一种晶体态结构的Hg离子选择薄膜传
With the extensive development of industrialization, heavy metals distributing comprehensively various waters are severely endangering human health by drinking water, food chain, and biogenic enrichment modes etc. It is urgent to detect heavy metals. The water pollution is aggravating in Chinese sea area, especially in neritic area. Marine ecosystems continue worsening. So the plan to establish national marine ecological environment monitor typical system in-situ was proposed during the Tenth Five-Year Plan. By means of real-time sampling, analysis and detection, seawater quality is monitoring, accordingly the decisions and measures to prevent pollution diffusion are able to be taken in time. On the other hand, heavy metal sensors and detection techniques are also foreland topics to research in the world. Based on the reasons above-mentioned, the researches on heavy metal ion selective sensors and the application in seawater analysis are as major tasks in the thesis and financed by Nation 863 High-tech Project Fund, China-Russia Special Fund in International Cooperation at Nation Nature Science Fund (NSFC) and Zhejiang Province International Cooperation Major Fund.The major contents of this thesis are given in the following aspects.1. A kind of equivalent circuit model on light-addressable potentiometric sensor (LAPS) is proposed and the effects of parameters in the LAPS model are evaluated and anaylzed. By combining electrochemical kinetics theory into semiconductor energy band theory, LAPS theory is reformulated. The results are described, that electrostatic potential including bias voltage in external circuit and electrostatic adherence caused by electrolyte solution ions can change the Fermi energy level of LAPS, thus thickness of space-charge region is changed and photo-induced current is affected, and that specific adsorption caused by ionic exchange can affect the flat band voltage of LAPS, space-charge region and photo-induced current. At last heavy metal thin film LAPS is optimized to design based on the equivalent model and LAPS theory.2. Based on LAPS and pulsed laser deposition (PLD) technique, a kind of iron (III) ion selective thin film sensor with glass state structure has been developed for the first
time. A kind of ion selective electrode (Fe —ISE) sensitive to iron (III) ion synthesized was studied on it's characteristic and used as a target of PLD device, correspondingly thin film sensor (Fe—LAPS) with glass state structure sensitive to iron (III) ion was prepared on the surface of LAPS. The Fe—LAPS has a good linearity range of 10~(-2)~10~-(5) mol/L, the slope of calibration curve is 435nA/decade, the limit of determination 6.31X10~(-6) mol/L, suitable pH range 0 to 2. While the concentration of Fe (III) ion is more than 10~(-4) mol/L, the response time is less than 30 s, and the concentration less than 10~(-4) mol/L, no more than 2 min. The calibration curve has good repetitiveness in 8 weeks. The resolution and sensitivity of Fe— LAPS improve 7.69 times than Fe—ISE's.3. Based on LAPS and PLD technique, a kind of mercury (II) ion selective thin film sensor with crystal state structure had been developed for the first time. A kind of ion selective electrode (Hg—ISE) sensitive to mercury (II) ion synthesized was studied on it's characteristic and used as a target of PLD device, correspondingly thin film sensor (Hg—LAPS) with crystal state structure was prepared on the surface of LAPS. The Hg—LAPS has a good linearity range of 10~(-3)~10~(-6) mol/L, the slope of calibration curve is 46.5 nA/decade, the limit of determination 3.44x10~(-7) mol/L, suitable pH range 1 to 3. While the concentration of Hg (II) ion is more than 10~(-5) mol/L, the response time is less than 40 s, and the concentration less than 10~(-5) mol/L, no more than 2 min. The calibration curve has good repetitiveness in 2 weeks. The resolution and sensitivity of Hg—LAPS improve 1.53 times than Hg—ISE's.4. Based on LAPS and PLD technique, a kind of chromium (VI) ion selective thin film sensor with glass state struct
引文
1. A. Guessous, P. Paper, J. Sarradin, M. Ribes. Thin films of chalcogenide glass as sensitive membranes for the detection of mercuric ions in solution. Sensors and Actuators B, 24-25 (1995) 296-299
2. A. Guessous, J. Sarradin, P. Papet, K. Elkacemi, S. Belcadi, A. Pradel, M. Ribes. Chemical microsensors based on chalcogenide glass for the detection of cadmium ions in solution. Sensors and Actuators B, 53 (1998) 13-18
3. A.R. Curtis. Mutation in the gene encoding ferritin light polypeptide causes dominant adult-onset basal ganglia disease. Nature Genet, 28 (2001) 350-354
4. B. Zhou. A novel pantothenate kinase gene (PANK2) is defective in Hallervorden-Spatz syndrome. Nature Genet, 28 (2001) 345-349
5. E.A. Bychkov, M. Bruns, H. Klewe-Nebenius, G. Pfennig, W. Hoffmann, H.J. Ache. Cu~(2+)-selective thin films for chemical microsensors based on sputtered copper-arsenic-selenium glass. Sensors and Actuators B, 24-25 (1995) 733-736
6. J. Mortensen, A.V. Legin, A. Ipatov, A. Rudnitskaya, Yu. Vlasov, K. Hjuler. A flow injection system based on chalcogenide glass sensors for the determination of heavy metals. Analytica Chimica Acta, 403 (2000) 273-277
7. J. Schubert, M.J. SchSning, Yu.G. Mourzina, A.V. Legin, Yu.G. Vlasov, W. Zander, H. Luth. Multicomponent thin films for electrochemical sensor applications prepared by pulsed laser deposition. Sensors and Actuators B, 76 (2001) 327-330
8. M.J. Schoing, C. Schmidt, J. Schubert, W. Zangder, S. Mesters, P. Kordos, H. L uth, A. Legin, B. Seleznev, Yu.G. Vlasov. Thin film sensors on the basis of chalcogenide glass materials prepared by pulsed laser deposition technique. Sensors and Actuators B, 68 (2000) 254-259
9. M.J. Schoning, Yu.G. Mourzina, J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, H. Luth. Can pulsed laser deposition serve as an advanced technique in fabricating chemical sensors? Sensors and Actua.tors B, 78 (2001) 273-278
10. R. Tomova, G. Spasov, R. Stoycheva-Topalova, A. Buroff. Copper-doped vacuum evaporated chalcogenide layers as sensitive ion-selective membranes. Journals of Non-Crystalline Solids, 266-269 (2000) 985-988
11. T.A. Rouault. Iron on the brain. Nature Genet, 28 (2001) 299-300
12. Yu.G. Mourzina, M. J. Schoning, J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, H. Luth. Copper, cadmium and thallium thin film sensors based on chalcogenide glass. Analytica Chimica Acta, 433 (2001) 103-110
13. Yu.G. Vlasov, E.A. Bychkov. Ion-Selective Electrode Rev., 9 (1987)5
14. Yu. Mourzina, M.J. Schoning J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, P. Kordos, H. Luth. A new thin-film Pb microsensor based on chalcogenide glass. Sensors and Actuators B, 71 (2000) 13-18
15. Y. Mourzina, T. Yoshinobu, J. Schubert, H. Luth, H. Iwasaki, M.J. SchSning. Ion-selective light-addressable potentiometric sensor (LAPS) with chalcogenide thin film prepared by pulsed laser deposition. Sensors and Actuators B, 80 (2001) 136-140
16.A.R. Date, A.L. Gray.李金英等译.电感耦合等离子质谱分析的应用.北京:原子能出版社,1998年4月
17.陈怀满.土壤—植物系统中的重金属污染.北京:科学出版社,1996年9月
18.陈集,饶小桐.仪器分析.重庆:重庆大学出版社,2002年2月
19.陈静生,周家义.中国水环境重金属研究.北京:中国环境科学出版社,1992年6月
20.陈立春.仪器分析.北京:中国轻工业出版社,2002年3月
21.邓延倬,何金兰.高效毛细管电泳.北京:科学出版社出版,1996年7月
22.杜宝中.环境监测中的电化学分析法.北京:化学工业出版社,2003年5月
23.方惠群,于俊生,史坚.仪器分析.北京:科学出版社,2002年2月
24.黄德培,沈子琛.离子选择电极的原理及应用.北京:新时代出版社,1982年5月
25.廖自基.环境中微量重金属元素的污染危害及迁徙.北京:科学出版社,1989年2月
26.林炳承.毛细管电泳导论.北京:科学出版社,1996年11月
27.门洪,刘大龙,韩清鹏,徐丹,王平.Hg~(2+)离子传感器的最新研究进展.传感技术学报,16(3)(2003)
28.彭图治,王国顺.分析化学手册(第四分册:电分析化学).北京:化学工业出版社,1999年8月
29.汪尔康.分析化学.北京:北京理工大学出版社,2002年9月
30.王绍文,姜凤有.重金属废水治理技术.北京:冶金工业出版社,1993年1月
31.王世平,王静,仇厚援.现代仪器分析原理与技术.哈尔滨:哈尔滨工程大学出版社,1999年1月
32.谢声洛.离子选择电极分析技术.北京:化学工业出版社,1985年12月
33.杨根元,金瑞祥,应武林.实用仪器分析.北京:北京大学出版社,1997年9月
2. A. Guessous, J. Sarradin, P. Papet, K. Elkacemi, S. Belcadi, A. Pradel, M. Ribes. Chemical microsensors based on chalcogenide glass for the detection of cadmium ions in solution. Sensors and Actuators B, 53 (1998) 13-18
3. A.R. Curtis. Mutation in the gene encoding ferritin light polypeptide causes dominant adult-onset basal ganglia disease. Nature Genet, 28 (2001) 350-354
4. B. Zhou. A novel pantothenate kinase gene (PANK2) is defective in Hallervorden-Spatz syndrome. Nature Genet, 28 (2001) 345-349
5. E.A. Bychkov, M. Bruns, H. Klewe-Nebenius, G. Pfennig, W. Hoffmann, H.J. Ache. Cu~(2+)-selective thin films for chemical microsensors based on sputtered copper-arsenic-selenium glass. Sensors and Actuators B, 24-25 (1995) 733-736
6. J. Mortensen, A.V. Legin, A. Ipatov, A. Rudnitskaya, Yu. Vlasov, K. Hjuler. A flow injection system based on chalcogenide glass sensors for the determination of heavy metals. Analytica Chimica Acta, 403 (2000) 273-277
7. J. Schubert, M.J. SchSning, Yu.G. Mourzina, A.V. Legin, Yu.G. Vlasov, W. Zander, H. Luth. Multicomponent thin films for electrochemical sensor applications prepared by pulsed laser deposition. Sensors and Actuators B, 76 (2001) 327-330
8. M.J. Schoing, C. Schmidt, J. Schubert, W. Zangder, S. Mesters, P. Kordos, H. L uth, A. Legin, B. Seleznev, Yu.G. Vlasov. Thin film sensors on the basis of chalcogenide glass materials prepared by pulsed laser deposition technique. Sensors and Actuators B, 68 (2000) 254-259
9. M.J. Schoning, Yu.G. Mourzina, J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, H. Luth. Can pulsed laser deposition serve as an advanced technique in fabricating chemical sensors? Sensors and Actua.tors B, 78 (2001) 273-278
10. R. Tomova, G. Spasov, R. Stoycheva-Topalova, A. Buroff. Copper-doped vacuum evaporated chalcogenide layers as sensitive ion-selective membranes. Journals of Non-Crystalline Solids, 266-269 (2000) 985-988
11. T.A. Rouault. Iron on the brain. Nature Genet, 28 (2001) 299-300
12. Yu.G. Mourzina, M. J. Schoning, J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, H. Luth. Copper, cadmium and thallium thin film sensors based on chalcogenide glass. Analytica Chimica Acta, 433 (2001) 103-110
13. Yu.G. Vlasov, E.A. Bychkov. Ion-Selective Electrode Rev., 9 (1987)5
14. Yu. Mourzina, M.J. Schoning J. Schubert, W. Zander, A.V. Legin, Yu.G. Vlasov, P. Kordos, H. Luth. A new thin-film Pb microsensor based on chalcogenide glass. Sensors and Actuators B, 71 (2000) 13-18
15. Y. Mourzina, T. Yoshinobu, J. Schubert, H. Luth, H. Iwasaki, M.J. SchSning. Ion-selective light-addressable potentiometric sensor (LAPS) with chalcogenide thin film prepared by pulsed laser deposition. Sensors and Actuators B, 80 (2001) 136-140
16.A.R. Date, A.L. Gray.李金英等译.电感耦合等离子质谱分析的应用.北京:原子能出版社,1998年4月
17.陈怀满.土壤—植物系统中的重金属污染.北京:科学出版社,1996年9月
18.陈集,饶小桐.仪器分析.重庆:重庆大学出版社,2002年2月
19.陈静生,周家义.中国水环境重金属研究.北京:中国环境科学出版社,1992年6月
20.陈立春.仪器分析.北京:中国轻工业出版社,2002年3月
21.邓延倬,何金兰.高效毛细管电泳.北京:科学出版社出版,1996年7月
22.杜宝中.环境监测中的电化学分析法.北京:化学工业出版社,2003年5月
23.方惠群,于俊生,史坚.仪器分析.北京:科学出版社,2002年2月
24.黄德培,沈子琛.离子选择电极的原理及应用.北京:新时代出版社,1982年5月
25.廖自基.环境中微量重金属元素的污染危害及迁徙.北京:科学出版社,1989年2月
26.林炳承.毛细管电泳导论.北京:科学出版社,1996年11月
27.门洪,刘大龙,韩清鹏,徐丹,王平.Hg~(2+)离子传感器的最新研究进展.传感技术学报,16(3)(2003)
28.彭图治,王国顺.分析化学手册(第四分册:电分析化学).北京:化学工业出版社,1999年8月
29.汪尔康.分析化学.北京:北京理工大学出版社,2002年9月
30.王绍文,姜凤有.重金属废水治理技术.北京:冶金工业出版社,1993年1月
31.王世平,王静,仇厚援.现代仪器分析原理与技术.哈尔滨:哈尔滨工程大学出版社,1999年1月
32.谢声洛.离子选择电极分析技术.北京:化学工业出版社,1985年12月
33.杨根元,金瑞祥,应武林.实用仪器分析.北京:北京大学出版社,1997年9月