CN103499629A - Electrochemical method for detecting explosive HMX - Google Patents
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Abstract
本发明公开了一种检测炸药HMX的电化学方法。所述方法是将制备好的硼掺杂石墨烯超声分散在N,N-二甲基甲酰胺中，把分散液直接滴涂到玻碳电极表面，自然晾干制得所需电化学修饰电极。本发明构建的硼掺杂石墨烯修饰玻碳电极对HMX具有良好的电催化性能、快速的电流响应、高的灵敏度、宽的线性范围、低的检测限、良好的重现性和稳定性等特点，而且制备成本低廉、操作简易、选择性强和环境友好等优点。制备的硼掺杂石墨烯修饰电极在环境污染检测领域具有良好的应用前景和潜在应用价值。
The invention discloses an electrochemical method for detecting explosive HMX. The method is to ultrasonically disperse the prepared boron-doped graphene in N,N-dimethylformamide, directly drop-coat the dispersion onto the surface of a glassy carbon electrode, and dry it naturally to obtain the required electrochemically modified electrode . The boron-doped graphene-modified glassy carbon electrode constructed in the present invention has good electrocatalytic performance, fast current response, high sensitivity, wide linear range, low detection limit, good reproducibility and stability for HMX, etc. It has the advantages of low preparation cost, simple operation, strong selectivity and environmental friendliness. The prepared boron-doped graphene modified electrode has good application prospects and potential application value in the field of environmental pollution detection.
Description
技术领域 technical field
本发明属于电化学分析检测技术领域，涉及一种检测对环境有害炸药HMX的电化学方法。 The invention belongs to the technical field of electrochemical analysis and detection, and relates to an electrochemical method for detecting the environmentally harmful explosive HMX.
背景技术 Background technique
HMX中文名奥克托今，化学名称为1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷或环四亚甲基四硝胺，是一种高熔点的炸药,有毒性，容易起爆，安定性较好，可能导致基因突变。炸药和相关化合物对土壤和地下水的污染是一个重大的全球问题，考虑到国家安全和环境应用等问题，对它们的检测已经得到重视。目前, 测定HMX残留的方法有气相色谱法、高效液相色谱法、毛细管电泳法和离子迁移色谱法等。但是这些方法具有成本较高、操作复杂等缺点。因此，开发快速、简便、灵敏的方法检测炸药HMX非常必要而且具有挑战性。 The Chinese name of HMX is Octojin, and its chemical name is 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane or cyclotetramethylenetetranitroamine. Explosives with a high melting point are toxic, easy to detonate, have good stability, and may cause genetic mutations. Contamination of soil and groundwater by explosives and related compounds is a major global problem, and their detection has received attention considering issues such as national security and environmental applications. Currently, methods for the determination of HMX residues include gas chromatography, high performance liquid chromatography, capillary electrophoresis, and ion mobility chromatography. However, these methods have disadvantages such as high cost and complicated operation. Therefore, it is necessary and challenging to develop a fast, easy and sensitive method to detect explosive HMX.
石墨烯是碳原子以sp2 杂化呈蜂巢晶格排列构成的单层二维晶体， 其表现出优异的电学、光学、热和机械性能通过化学或者物理方法。将石墨烯进行修饰或改性可以改善石墨烯的性质,拓宽石墨烯的应用领域，其中化学掺杂是调整和研究石墨烯性质的一种非常重要且有效的途径。石墨烯掺杂其它化学元素可以调整其电子学性能和拓宽能隙，其中硼(B)和氮(N)是研究最多的碳材料的掺杂元素，分别为p 型和n 型掺杂。掺杂的B原子会影响C 原子的自旋密度和电荷分布， 导致石墨烯表面产生“活性位点”，这些活性位点可以直接参与催化反应。掺杂B原子的石墨烯还具有石墨烯的一些特性，例如大的比表面积、传递电子速率快和良好的机械性能等，使得B原子掺杂石墨烯在电化学电容器和电化学传感器方面得到了广泛的应用。 Graphene is a single-layer two-dimensional crystal composed of carbon atoms arranged in sp2 hybridized honeycomb lattice, which exhibits excellent electrical, optical, thermal and mechanical properties through chemical or physical methods. Modification or modification of graphene can improve the properties of graphene and broaden the application fields of graphene, among which chemical doping is a very important and effective way to adjust and study the properties of graphene. Doping graphene with other chemical elements can adjust its electronic properties and widen the energy gap, among which boron (B) and nitrogen (N) are the most studied doping elements of carbon materials, which are p-type and n-type doping respectively. The doped B atoms will affect the spin density and charge distribution of C atoms, leading to the generation of "active sites" on the graphene surface, which can directly participate in catalytic reactions. Graphene doped with B atoms also has some characteristics of graphene, such as large specific surface area, fast electron transfer rate and good mechanical properties, etc., making B atom-doped graphene obtained in electrochemical capacitors and electrochemical sensors. Wide range of applications.
电化学方法(尤其是结合化学修饰电极)具有灵敏度高、响应速度快、线性范围宽、仪器低廉、操作简便和成本低廉的特点，已经成为一种重要的分析手段。电化学方法检测HMX早有报道，N. Pon Saravanan等人（Voltammetric determination of nitroaromatic and nitramine explosives contamination in soil，Talanta 69 (2006) 656–662）研究了HMX在玻碳电极上的循环伏安行为，结果表明，HMX在玻碳电极上的电化学还原机理为不可逆过程。在电位-1.0 V处可见明显的还原峰, 其峰电流值与HMX浓度在42~ 182 μmol /L之间呈线性关系，最低检出限为1.0μmol /L，该修饰电极成功用于土壤中残留HMX的电化学检测。 Electrochemical methods (especially combined with chemically modified electrodes) have the characteristics of high sensitivity, fast response, wide linear range, low-cost instruments, easy operation and low cost, and have become an important analytical method. Electrochemical detection of HMX has been reported for a long time. N. Pon Saravanan et al. (Voltammetric determination of nitroaromatic and nitramine explosives contamination in soil, Talanta 69 (2006) 656–662) studied the cyclic voltammetry behavior of HMX on glassy carbon electrodes. The results show that the electrochemical reduction mechanism of HMX on the glassy carbon electrode is an irreversible process. An obvious reduction peak can be seen at the potential of -1.0 V, and the peak current value is linearly related to the HMX concentration between 42 and 182 μmol /L, and the lowest detection limit is 1.0 μmol /L. The modified electrode was successfully used in soil Electrochemical detection of residual HMX.
the
发明内容 Contents of the invention
本发明的目的在于提供一种用于对环境有害炸药HMX快速检测的电化学方法，所述方法操作简单、快速灵敏、对环境友好、价格低廉。 The object of the present invention is to provide an electrochemical method for rapid detection of environmentally harmful explosive HMX, which is simple to operate, fast and sensitive, environmentally friendly and low in price.
实现本发明目的的技术解决方案为： The technical solution that realizes the object of the present invention is:
一种检测炸药HMX的电化学方法，所述电化学方法包括以下步骤： A kind of electrochemical method that detects explosive HMX, described electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（B-GE/GCE）的制备：将硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得硼掺杂石墨烯分散液。然后取硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (B-GE/GCE): Boron-doped graphene was diluted with N,N-dimethylformamide and then ultrasonically dispersed to obtain boron-doped graphite olefin dispersion. Then the boron-doped graphene dispersion liquid is taken and coated on the surface of a clean glassy carbon electrode, and the boron-doped graphene-modified glassy carbon electrode covered with a sensitive film is obtained after the solvent is volatilized.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值5.0~8.0的缓冲溶液中，通氮气，加入HMX，使用循环伏安法，扫描速度为50~200 mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a buffer solution with a pH value of 5.0-8.0, pass nitrogen gas, add HMX, and use cyclic voltammetry at a scanning speed of 50-200 mV/s, to detect the electrochemical response of boron-doped graphene-modified glassy carbon electrode to pesticide HMX.
其中，步骤（1）中制得的硼掺杂石墨烯分散液浓度为0.1-1 mg/mL。 Wherein, the concentration of the boron-doped graphene dispersion prepared in step (1) is 0.1-1 mg/mL.
步骤（1）中硼掺杂石墨烯分散液用量为2-10 μL。 The amount of boron-doped graphene dispersion in step (1) is 2-10 μL.
步骤（2）所述缓冲溶液为柠檬酸/磷酸氢二钠体系。 The buffer solution in step (2) is a citric acid/disodium hydrogen phosphate system.
步骤（2）所述HMX的量为2-100 μmol/L。 The amount of HMX in step (2) is 2-100 μmol/L.
本发明与现有技术，其显著优点是：（1）硼掺杂石墨烯修饰电极制备成本低廉、操作简单、选择性强和环境友好。（2）硼掺杂石墨烯修饰玻碳电极对炸药HMX的检测具有良好的电催化性能、快速的电流响应、高的灵敏度、宽的线性范围、低的检测限、良好的重现性和稳定性等特点。对农药HMX的检测限为0.83μmol/L，是一种优良的检测电极。 The significant advantages of the present invention and the prior art are: (1) The preparation cost of the boron-doped graphene-modified electrode is low, the operation is simple, the selectivity is strong and the environment is friendly. (2) The boron-doped graphene-modified glassy carbon electrode has good electrocatalytic performance, fast current response, high sensitivity, wide linear range, low detection limit, good reproducibility and stability for the detection of explosive HMX characteristics such as sex. The detection limit of the pesticide HMX is 0.83μmol/L, which is an excellent detection electrode.
下面结合附图对本发明作进一步详细描述。 The present invention will be described in further detail below in conjunction with the accompanying drawings.
附图说明 Description of drawings
图1 本发明实施例1中不同电极GCE和B-GE/GCE的交流阻抗谱图。 Fig. 1 AC impedance spectra of different electrodes GCE and B-GE/GCE in Example 1 of the present invention.
图2 本发明实施例1中不同电极GCE和B-GE/GCE对HMX的循环伏安响应。 Fig. 2 Cyclic voltammetry responses of different electrodes GCE and B-GE/GCE to HMX in Example 1 of the present invention.
图3 本发明实施例1中A为B-GE/GCE修饰电极在不同扫速下（从a到h分别为50、60、70、80、90、100、150、200 mV/s）的循环伏安曲线，B为扫速与还原峰电流的线性关系。 Figure 3 In Example 1 of the present invention, A is the cycle of the B-GE/GCE modified electrode at different scan rates (from a to h are 50, 60, 70, 80, 90, 100, 150, 200 mV/s) Voltammetry curve, B is the linear relationship between scan rate and reduction peak current.
图4本发明实施例1中A为B-GE/GCE修饰电极在不同pH值下的循环伏安曲线，B为pH与还原峰电流的关系。 Fig. 4 A in Example 1 of the present invention is the cyclic voltammetry curve of the B-GE/GCE modified electrode at different pH values, and B is the relationship between pH and reduction peak current.
图5 本发明实施例1中A为B-GE/GCE修饰电极检测不同浓度HMX的部分循环伏安曲线，B为HMX浓度与还原峰电流的线性关系。 Figure 5. In Example 1 of the present invention, A is part of the cyclic voltammetry curves of different concentrations of HMX detected by the B-GE/GCE modified electrode, and B is the linear relationship between the HMX concentration and the reduction peak current.
具体实施方式 Detailed ways
下面的实施例可以使本专业技术人员更全面地理解本发明。 The following examples can enable those skilled in the art to understand the present invention more fully.
实施例1 Example 1
一种检测炸药HMX的电化学方法，其特征在于所述电化学方法包括以下步骤： An electrochemical method for detecting explosive HMX is characterized in that said electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（B-GE/GCE）的制备：将一定量的的硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得0.5 mg/mL的硼掺杂石墨烯分散液。然后取6μL硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (B-GE/GCE): Dilute a certain amount of boron-doped graphene with N,N-dimethylformamide and then ultrasonically disperse it to obtain 0.5 mg/mL boron-doped graphene dispersion. Then, 6 μL of boron-doped graphene dispersion liquid was dropped and coated on the surface of a clean glassy carbon electrode. After the solvent evaporated, a boron-doped graphene-modified glassy carbon electrode covered with a sensitive film was obtained.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值6.5的柠檬酸/磷酸氢二钠缓冲溶液中，通氮气20分钟，加入100 μmol/L的HMX，使用循环伏安法，扫描速度为100 mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a citric acid/disodium hydrogen phosphate buffer solution with a pH value of 6.5, blow nitrogen gas for 20 minutes, and add 100 μmol/L of HMX, Using cyclic voltammetry with a scan rate of 100 mV/s, the electrochemical response of the boron-doped graphene-modified glassy carbon electrode to the pesticide HMX was detected.
图1由高频的半圆直径可知,裸GCE（a）在[Fe (CN) 6]3-/4-表征液中的电阻较大。当电极表面修饰N-GE后电阻值明显减小, 表明电子在B-GE修饰玻碳电极具有更好的导电性和更快的的电子迁移能力。 Figure 1 shows that the resistance of bare GCE (a) in the [Fe (CN) 6 ] 3-/4- liquid is relatively large from the diameter of the high-frequency semicircle. When the surface of the electrode is modified with N-GE, the resistance value is significantly reduced, indicating that the electrons in the B-GE modified glassy carbon electrode have better conductivity and faster electron transfer ability.
图2无论GCE还是B-GE/GCE在含有100 μmol/LHMX的缓冲溶液中都只有一个不可逆还原峰。与GCE相比，修饰电极的还原电位更正，而且峰电流显著的增强。这个现象说明B-GE/GCE对HMX还原具有更优异的电催化活性和更高的灵敏度，使得B-GE/GCE可以作为一种电化学传感器，快速方便的检测HMX。 Figure 2 No matter GCE or B-GE/GCE, there is only one irreversible reduction peak in the buffer solution containing 100 μmol/LHMX. Compared with GCE, the reduction potential of the modified electrode is more positive, and the peak current is significantly enhanced. This phenomenon indicates that B-GE/GCE has more excellent electrocatalytic activity and higher sensitivity for HMX reduction, which makes B-GE/GCE can be used as an electrochemical sensor to detect HMX quickly and conveniently.
图3A随着扫速的增加，还原峰电流逐渐增加，最终选择测定的扫速为100 mV/s。从图B可以看出，扫速与还原峰电流呈线性关系，表明HMX在修饰电极表面的还原反应是一个吸附控制过程。 Figure 3A As the scan rate increases, the reduction peak current gradually increases, and the final scan rate selected for measurement is 100 mV/s. It can be seen from Figure B that the scan rate has a linear relationship with the reduction peak current, indicating that the reduction reaction of HMX on the surface of the modified electrode is an adsorption-controlled process.
图4A B-GE/GCE在不同pH值下的循环伏安曲线，图B为pH与还原峰电流的关系。随着pH值的增加，还原峰电流先增加后下降，最终选择测定的pH值为6.5。 Fig. 4A Cyclic voltammetry curves of B-GE/GCE at different pH values, and Fig. B shows the relationship between pH and reduction peak current. With the increase of pH value, the reduction peak current first increased and then decreased, and the final selected pH value was 6.5.
图5A B-GE/GCE在不同浓度HMX下的部分循环伏安曲线，图B为HMX浓度与还原峰电流的线性关系。HMX浓度在2~100μmol/L区间逐渐增加时，对应的还原峰电流分段线性增加，最低检出限为0.83μmol/L。 Figure 5A Partial cyclic voltammetry curves of B-GE/GCE at different concentrations of HMX, and Figure B shows the linear relationship between HMX concentration and reduction peak current. When the concentration of HMX gradually increased in the range of 2-100 μmol/L, the corresponding reduction peak current increased linearly step by step, and the lowest detection limit was 0.83 μmol/L.
实施例2 Example 2
一种检测农药HMX的电化学方法，其特征在于所述电化学方法包括以下步骤： An electrochemical method for detecting pesticide HMX, characterized in that said electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（N-GE/GCE）的制备：将一定量的的硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得0.1 mg/mL的硼掺杂石墨烯分散液。然后取10 μL硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (N-GE/GCE): Dilute a certain amount of boron-doped graphene with N,N-dimethylformamide and then ultrasonically disperse it to obtain 0.1 mg/mL boron-doped graphene dispersion. Then take 10 μL of boron-doped graphene dispersion and apply it on the surface of a clean glassy carbon electrode. After the solvent evaporates, a boron-doped graphene-modified glassy carbon electrode covered with a sensitive film is obtained.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值5.0的柠檬酸/磷酸氢二钠缓冲溶液中，通氮气20分钟，加入50 μmol/L的HMX，使用循环伏安法，扫描速度为50mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a citric acid/disodium hydrogen phosphate buffer solution with a pH value of 5.0, blow nitrogen gas for 20 minutes, and add 50 μmol/L of HMX, Using cyclic voltammetry with a scan rate of 50mV/s, the electrochemical response of the boron-doped graphene-modified glassy carbon electrode to the pesticide HMX was detected.
实施例3 Example 3
一种检测农药HMX的电化学方法，其特征在于所述电化学方法包括以下步骤： An electrochemical method for detecting pesticide HMX, characterized in that said electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（N-GE/GCE）的制备：将一定量的的硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得1 mg/mL的硼掺杂石墨烯分散液。然后取2 μL硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (N-GE/GCE): Dilute a certain amount of boron-doped graphene with N,N-dimethylformamide and then ultrasonically disperse it to obtain 1 mg/mL boron-doped graphene dispersion. Then take 2 μL of boron-doped graphene dispersion and apply it on the surface of a clean glassy carbon electrode. After the solvent evaporates, a boron-doped graphene-modified glassy carbon electrode covered with a sensitive film is obtained.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值8.0的柠檬酸/磷酸氢二钠缓冲溶液中，通氮气20分钟，加入2 μmol/L的HMX，使用循环伏安法，扫描速度为100 mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a citric acid/disodium hydrogen phosphate buffer solution with a pH value of 8.0, blow nitrogen for 20 minutes, and add 2 μmol/L of HMX, Using cyclic voltammetry with a scan rate of 100 mV/s, the electrochemical response of the boron-doped graphene-modified glassy carbon electrode to the pesticide HMX was detected.
实施例4 Example 4
一种检测农药HMX的电化学方法，其特征在于所述电化学方法包括以下步骤： An electrochemical method for detecting pesticide HMX, characterized in that said electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（B-GE/GCE）的制备：将一定量的的硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得0.5 mg/mL的硼掺杂石墨烯分散液。然后取10 μL硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (B-GE/GCE): Dilute a certain amount of boron-doped graphene with N,N-dimethylformamide and then ultrasonically disperse it to obtain 0.5 mg/mL boron-doped graphene dispersion. Then take 10 μL of boron-doped graphene dispersion and apply it on the surface of a clean glassy carbon electrode. After the solvent evaporates, a boron-doped graphene-modified glassy carbon electrode covered with a sensitive film is obtained.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值8.0的柠檬酸/磷酸氢二钠缓冲溶液中，通氮气20分钟，加入100 μmol/L的HMX，使用循环伏安法，扫描速度为200 mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a citric acid/disodium hydrogen phosphate buffer solution with a pH value of 8.0, blow nitrogen for 20 minutes, and add 100 μmol/L of HMX, Using cyclic voltammetry with a scan rate of 200 mV/s, the electrochemical response of the boron-doped graphene-modified glassy carbon electrode to the pesticide HMX was detected.
实施例5 Example 5
一种检测农药HMX的电化学方法，其特征在于所述电化学方法包括以下步骤： An electrochemical method for detecting pesticide HMX, characterized in that said electrochemical method comprises the following steps:
（1）硼掺杂石墨烯修饰玻碳电极（N-GE/GCE）的制备：将一定量的的硼掺杂石墨烯，用N,N-二甲基甲酰胺稀释然后超声分散，制得1 mg/mL的硼掺杂石墨烯分散液。然后取6μL硼掺杂石墨烯分散液滴涂在洁净玻碳电极表面，溶剂挥发后得到覆有敏感膜的硼掺杂石墨烯修饰的玻碳电极。 (1) Preparation of boron-doped graphene-modified glassy carbon electrode (N-GE/GCE): Dilute a certain amount of boron-doped graphene with N,N-dimethylformamide and then ultrasonically disperse it to obtain 1 mg/mL boron-doped graphene dispersion. Then, 6 μL of boron-doped graphene dispersion liquid was dropped and coated on the surface of a clean glassy carbon electrode. After the solvent evaporated, a boron-doped graphene-modified glassy carbon electrode covered with a sensitive film was obtained.
（2）将步骤（1）得到的硼掺杂石墨烯修饰的玻碳电极放置于pH值6.5的柠檬酸/磷酸氢二钠缓冲溶液中，通氮气20分钟，加入100μmol/L的HMX，使用循环伏安法，扫描速度为200 mV/s, 检测硼掺杂石墨烯修饰的玻碳电极对农药HMX的电化学响应。 (2) Place the boron-doped graphene-modified glassy carbon electrode obtained in step (1) in a citric acid/disodium hydrogen phosphate buffer solution with a pH value of 6.5, blow nitrogen gas for 20 minutes, add 100 μmol/L HMX, and use Cyclic voltammetry, with a scan rate of 200 mV/s, was used to detect the electrochemical response of the boron-doped graphene-modified glassy carbon electrode to the pesticide HMX.
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