天然矿泉水中溴酸盐快速检测方法的研究
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摘要
溴酸盐是2B级潜在致癌物,主要存在于天然矿泉水和面制品中。目前采用的检测方法都是离子色谱法,仪器昂贵,不适合普遍推广使用,无法满足实时在线检测。因此,研究和建立一种方便、安全和快速的检测方法具有重要意义。化学修饰电极是通过化学修饰的方法在电极表面进行分子设计,将具有优良物理化学性质的分子、离子、聚合物固定在电极表面,从而具有某种特定的化学和物理性质的一类电极。其应用已涉及到化学、生命科学、医学、环境、食品和军事等诸多领域。本论文主要内容包括利用电化学的特性,制备新型快速灵敏的溴酸盐电化学传感器,建立溴酸盐快速检测方法,并对实际样品进行测定。具体研究结果如下:
采用电聚合的方法制备GC/Ppy/PMo_(12)纳米复合修饰电极,通过循环伏安法(CV)对电极化学性质进行表征,发现Ppy大大的改善PMo_(12)的化学性质和对BrO_3~-的电催化还原效应。该修饰电极在0.5 mol/L H_2SO_4中有着良好的电化学行为。在﹣0.06 V的检测电位下,采用I—T曲线法,发现该修饰电极在溴酸盐浓度为0.005-0.1 mmol/L的范围内有着良好的线性关系,相关系数为0.998,响应时间为1.87 s,最低检测限为2μmol/L,灵敏度为46.86μA·mmol~(-1)·L·cm~(-2)。
基于层层组装法,将带正电荷的PDDA和带负电荷的功能化的MWNTs通过静电吸引力的作用构筑{MWNTs/PDDA}n/PMo_(12)修饰电极。通过SEM、UV-Vis技术对该修饰电极的微观形貌进行表征。通过电化学方法研究表明该电极对溴酸盐有着良好的电催化性能。优化组装层数、溶液pH值以及PMo_(12)的使用量。在最佳的实验条件下,检测电位为﹣0.09 V,{MWNTs/PDDA}_5/PMo_(12)修饰电极在溴酸盐浓度为0.05-0.4μmol/L的范围内有着良好的线性关系,相关系数为0.99,响应时间为1.53 s,最低检测限为0.02μmol/L,灵敏度为966.9μA·mmol~(-1)·L·cm~(-2)。结果表明,该修饰电极的BrO_3~-传感器表现出较Gc/Ppy/PMo_(12)修饰电极卓越的性能。
使用{MWNTs/PDDA}_5/PMo_(12)修饰电极对实际样品进行检测,结果表明该电极具有良好的重现性和稳定性。
Bromates are 2B-class potential carcinogens, which are mainly found in natural mineral water and flour goods. Tranditional Method currently used to detect bromates is ion chromatography. Due to the expensive cost of equipments, it cannot be widely applied in real-time detection. Therefore, it is meaningful to establish a convenient, safe and rapid detection method for bromates. Owing to their present particular physical and chemical properties via surface bonding of certain molecules, ions or polymers, chemically modified electrodes have been widely employed in many fields such as chemistry, biology, medicine, environment, food and military. The aim of present research is to prepare new bromate electrochemical sensors with fast and accurate responses. The main research contents are as follows:
Gc/Ppy/PMo_(12) modified electrodes were prepared using electropolymerization. On the bais of cyclic voltammetry (CV) experimental results, it was found that Ppy significantly improved chemical properties of PMo_(12) and its electro-catalytic reducibility to BrO_3~-. In 0.5 mol/L H2SO4 solution, the modified electrode presented good electrochemical behavior.Under the detecting potential -0.05 V.,using I-T surve method, in the concentration range of 0.005-0.1 mmol/L ,the linear correlation coefficient was 0.998, the response time was 1.87 s, its detection limit on bromate was 2μmol/L, and sensitivity was 46.86μA·mmol~(-1)·L·cm~(-2).
In this chapter , layer-by-layer{MWNTs/PDDA}n/PMo_(12) films assembled by altematead sorption of positively charged PDDA and negatively charged funditional MWNTs onto a glassy carbon electrode.The micorstructure of modified electrode were characterized by SEM and UV-Vis. Electric properties of the modified electrode were investigated by CV method and displayed a good electrocatalytic activity to the reduction of broamte . Lay numbers , pH and the concentration of PMo_(12) were optimized. At -0.09V, in the range of 0.05-0.4μmol/L, the linear correlation coefficient was 0.99, the response time was 1.53 s, its detection limit on BrO_3~- was 0.02μmol/L, and the sensitivity was 966.9μA·mmol~(-1)·L·cm~(-2). The result displayed that the electrode prepared by this method had a superior performance than that of Gc/Ppy/PMo_(12).
The experimental resulted on commercial goods using {MWNTs/PDDA}_5/PMo_(12) modified electrode indicated that the modified electrode had good reproducibility and stability.
采用电聚合的方法制备GC/Ppy/PMo_(12)纳米复合修饰电极,通过循环伏安法(CV)对电极化学性质进行表征,发现Ppy大大的改善PMo_(12)的化学性质和对BrO_3~-的电催化还原效应。该修饰电极在0.5 mol/L H_2SO_4中有着良好的电化学行为。在﹣0.06 V的检测电位下,采用I—T曲线法,发现该修饰电极在溴酸盐浓度为0.005-0.1 mmol/L的范围内有着良好的线性关系,相关系数为0.998,响应时间为1.87 s,最低检测限为2μmol/L,灵敏度为46.86μA·mmol~(-1)·L·cm~(-2)。
基于层层组装法,将带正电荷的PDDA和带负电荷的功能化的MWNTs通过静电吸引力的作用构筑{MWNTs/PDDA}n/PMo_(12)修饰电极。通过SEM、UV-Vis技术对该修饰电极的微观形貌进行表征。通过电化学方法研究表明该电极对溴酸盐有着良好的电催化性能。优化组装层数、溶液pH值以及PMo_(12)的使用量。在最佳的实验条件下,检测电位为﹣0.09 V,{MWNTs/PDDA}_5/PMo_(12)修饰电极在溴酸盐浓度为0.05-0.4μmol/L的范围内有着良好的线性关系,相关系数为0.99,响应时间为1.53 s,最低检测限为0.02μmol/L,灵敏度为966.9μA·mmol~(-1)·L·cm~(-2)。结果表明,该修饰电极的BrO_3~-传感器表现出较Gc/Ppy/PMo_(12)修饰电极卓越的性能。
使用{MWNTs/PDDA}_5/PMo_(12)修饰电极对实际样品进行检测,结果表明该电极具有良好的重现性和稳定性。
Bromates are 2B-class potential carcinogens, which are mainly found in natural mineral water and flour goods. Tranditional Method currently used to detect bromates is ion chromatography. Due to the expensive cost of equipments, it cannot be widely applied in real-time detection. Therefore, it is meaningful to establish a convenient, safe and rapid detection method for bromates. Owing to their present particular physical and chemical properties via surface bonding of certain molecules, ions or polymers, chemically modified electrodes have been widely employed in many fields such as chemistry, biology, medicine, environment, food and military. The aim of present research is to prepare new bromate electrochemical sensors with fast and accurate responses. The main research contents are as follows:
Gc/Ppy/PMo_(12) modified electrodes were prepared using electropolymerization. On the bais of cyclic voltammetry (CV) experimental results, it was found that Ppy significantly improved chemical properties of PMo_(12) and its electro-catalytic reducibility to BrO_3~-. In 0.5 mol/L H2SO4 solution, the modified electrode presented good electrochemical behavior.Under the detecting potential -0.05 V.,using I-T surve method, in the concentration range of 0.005-0.1 mmol/L ,the linear correlation coefficient was 0.998, the response time was 1.87 s, its detection limit on bromate was 2μmol/L, and sensitivity was 46.86μA·mmol~(-1)·L·cm~(-2).
In this chapter , layer-by-layer{MWNTs/PDDA}n/PMo_(12) films assembled by altematead sorption of positively charged PDDA and negatively charged funditional MWNTs onto a glassy carbon electrode.The micorstructure of modified electrode were characterized by SEM and UV-Vis. Electric properties of the modified electrode were investigated by CV method and displayed a good electrocatalytic activity to the reduction of broamte . Lay numbers , pH and the concentration of PMo_(12) were optimized. At -0.09V, in the range of 0.05-0.4μmol/L, the linear correlation coefficient was 0.99, the response time was 1.53 s, its detection limit on BrO_3~- was 0.02μmol/L, and the sensitivity was 966.9μA·mmol~(-1)·L·cm~(-2). The result displayed that the electrode prepared by this method had a superior performance than that of Gc/Ppy/PMo_(12).
The experimental resulted on commercial goods using {MWNTs/PDDA}_5/PMo_(12) modified electrode indicated that the modified electrode had good reproducibility and stability.
引文
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2.刘勇建,牟世芬.离子色谱法在测定饮用水中痕量溴酸盐标准方法中的应用[J].环境化学,2002,21(2):203-204
3. USEPA. List of drinking water contaminants and MCLs, Current drinking water standards, EPA. 816-F-02-013[S]. 2002
4. Council Directive 98/83/EC on the quality of water intended for human consumption[S]. 1998
5. Haag. W, R. Hoign. Ozonation of Bromide Containing Waters:Kinetics of Formation of Hypobromous Acid and Bromate[J]. Environ. Sci.Tech.,1983(17):261
6. Urs Von Gunten. Ozonation of drinking water: Part II. Disinfection and by -product formation in presence of bromide,iodide or chlorine[J]. Water Research, 2003(37):1469-1487
7.何星存.萃取浮光度法间接测定微量溴酸根离子[J].化学试剂,1992,14(4):249
8.吕庆淮,韩长秀.褪色光度法测定微量溴酸根[J].理化检验-化学分册,2005,41:434
9.刘文明,马卫兴.褪色光度法测定微量溴酸根离子[J].化学试剂,1999,21(3):164
10.姜华.褪色光度法测定微量溴酸根[J].分析实验室,2001,20(2):89
11.冠宗燕,王安平,赵心伟,等.用DSPCF光度法测定微量XO3-离子的研究[J].化学试剂,1988,10(5):291
12. USEPA.Determination of inorganic anions in drinking water by ion chromatography[S].Method, 300.1
13.陆洋,林奇.离子色谱法测定水中微量卤化物及卤素含氧酸盐[J].净水技术,2002,21(2):41-43
14.臧道德,童俊,冯菊丽,等.淋洗液在线离子色谱法测定水中的溴酸盐[J].中国给水排水,2006,22(18): 83-85
15.董绍俊,车广礼,谢远武.化学修饰电极[M].北京:科学出版社,1995
16.金利通,仝威等.化学修饰电极[M].上海:华东师范大学出版社,1992
17. B.Keita,L.Nadjo. New aspects of the electrochemistry of heteropolyacids: Part II. Coupled electron and proton transfers in the reduction of silicoungstic species[J].J.Electroanal.Chem..1987(217):287
18.奚晓丹,刘绍琴,王恩波.吸附杂多化合物对亚硝酸根的电催化还原[J].分析化学,1998(6): 719
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