CN102980935A - Electrochemical method for detecting anthracene-phenanthrene resultant of polycyclic aromatic hydrocarbon - Google Patents
Electrochemical method for detecting anthracene-phenanthrene resultant of polycyclic aromatic hydrocarbon Download PDFInfo
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- CN102980935A CN102980935A CN2012105185819A CN201210518581A CN102980935A CN 102980935 A CN102980935 A CN 102980935A CN 2012105185819 A CN2012105185819 A CN 2012105185819A CN 201210518581 A CN201210518581 A CN 201210518581A CN 102980935 A CN102980935 A CN 102980935A
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Abstract
The invention relates to the technical field of electrochemical analysis and measurement, and in particular relates to a method for detecting the anthracene-phenanthrene resultant; according to the method, thionine is as a probe and is mixed with graphene to prepare an electrochemical modified electrode, and then the electrochemical modified electrode is used for quantitative detection of anthracene-phenanthrene resultant. The functional modified electrode in which a mesoporous material is modified by using the probe has the advantages that the material synthesis is simple and convenient, the modified electrode is relatively simple to prepare, the material is low in price, the electrode is easy to update, good in reproducibility and free of toxicity and does not cause environment pollution, and moreover by utilizing the detection method, the interference of coexisting substances is effectively reduced; and selectivity and sensation are high.
Description
Technical field
The present invention relates to electrochemical analysis determination techniques field, particularly relate to and a kind ofly utilize the sulphur a beautiful gem to mix with Graphene as probe and make the Electrochemical Modification electrode and with the method for the luxuriant and rich with fragrance resultant of anthracene in its quantitative detection assay.
Background technology
Anthracene extensively is present in the waste water that the industry production such as textile, pharmacy, papermaking, dyestuff emit with luxuriant and rich with fragrance, and the mankind, animal, plant are had serious toxic action, and palycyclic aromatic is as organic contaminant main in the environment, and its source is very extensive.Because its stable ring texture, be difficult to be degraded at occurring in nature again, therefore in vivo constantly enrichment is huge to the mankind's harm.And in daily life, we will contact with these palycyclic aromatics unconsciously.Machine work is for example arranged, the organic waste of burning, vehicle exhaust, cigarette combustion etc.
Along with the development of science and technology, also at Change and Development little by little, developed is spectral technique to the detection method of palycyclic aromatic (PAHs) at first, also has mass spectrophotometry, nuclear magnetic resonance and infrared spectrum technology etc.Comparatively commonly used is reversed-phased high performace liquid chromatographic and spectrophotometric method.These methods generally need enrichment of analytes, and are comparatively time-consuming, are difficult to Site Detection, and cost is high.Other detection method of polynuclear aromatics also has more report, comprises biology sensor, electroluminescence detection, the oxidation of polymkeric substance catalytic electrochemical etc.Wherein the scheme the most close with the present invention is to adopt ruthenium complex that polynuclear aromatics is detected.In this scheme, utilize the signal amplification agent mechanism of sodium oxalate, obtain amplification with the electrochemical signals of the PAHs of ruthenium complex mark.When the PAHs of detected material PAHs and mark competition in conjunction with the time, cause signal to descend, thereby PAH carried out quantitative test.Said method all exist electrode prepare loaded down with trivial details, test condition is complicated, sensitivity and the not high defective of selectivity.Therefore need being directly used in of a kind of more convenient and quicker of development to measure the method for the luxuriant and rich with fragrance resultant of anthracene in the aqueous solution, to be used for sample screening, on-the-spot emergency monitoring and on-line analysis etc.
Summary of the invention
Purpose of the present invention is exactly that a kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene is provided for the shortcoming in the said determination, this functional modification electrode that utilizes the probe modification mesoporous material, its material is synthetic simple and convenient, and modified electrode is made easier, material price is cheap, electrode is easy to upgrade, and favorable reproducibility is nontoxic, free from environmental pollution, and this assay method has effectively lowered the interference of coexisting substances, and selectivity is good, and is highly sensitive.
A kind of electrochemical method technical scheme that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene of the present invention is: adopt the sulphur a beautiful gem as probe and Graphene mixing manufacture Electrochemical Modification electrode, quantitatively detect the luxuriant and rich with fragrance resultant of anthracene with it.
Mix with Graphene as probe with the sulphur a beautiful gem, step is: the graphene oxide that takes by weighing 0.04g is dissolved in the suitable quantity of water, adds thermal agitation, is warming up to 75 ℃, then adds 40mg sulphur a beautiful gem, is warmed up to 90 ℃, then adds 2g NaBH
4, stir, reacted 24 hours, then solution being dialysed obtains probe material TH-GNs.
The modified electrode making step is: take by weighing the 0.0020g probe material, it is added among the Nafion solution 1.0mL ultrasonic mixing; Microsyringe is drawn 10 μ L and is dropped in the glass-carbon electrode surface, dries under the infrared lamp, makes Electrochemical Modification electrode (TH-GNs/GCE).
A kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene, detecting step is:
(1) in the electrolytic cell of the PBS damping fluid that contains 10mL pH6.5, take the TH-GNs/GCE modified electrode as working electrode, the Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out at the CHI842C Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In 0.1～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0.1～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured blank peak point current Ip
0
(2) get the luxuriant and rich with fragrance mixed standard solution of a certain amount of anthracene with microsyringe and join in the above-mentioned electrolytic solution cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram obtains peak point current Ip
1, the difference DELTA Ip of peak current behind the calculating adding anthracene phenanthrene
1(Ip
1-Ip
0).According to said method, add the luxuriant and rich with fragrance mixed standard solution of anthracene of variable concentrations, can obtain the difference DELTA Ip of corresponding peak current, ask again and calculate peak current difference DELTA Ip and blank peak point current Ip
0Ratio (Δ Ip/Ip
0), the logarithm of the luxuriant and rich with fragrance melting concn of this ratio and anthracene presents good linear relationship, and the range of linearity is 1.0 * 10
-11-1.0 * 10
-7Mol/L, linear equation are Δ Ip/Ip
0=-0.0698lgc-0.8111, c are concentration, and unit is mol/L, peak current Ip
0, Δ Ip, unit is μ A, linearly dependent coefficient r=0.9995 detects and is limited to 1.0 * 10
-12Mol/L;
(3) in conjunction with above-mentioned linear relationship, the luxuriant and rich with fragrance biased sample of the anthracene of unknown concentration is measured, calculated the melting concn of anthracene phenanthrene: in the electrolytic cell of the PBS solution that contains 10mL pH6.5, take above-mentioned modified electrode as working electrode, the Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out at the CHI842C Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In 0.1～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then in 0.1～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram; Then add a certain amount of solution to be measured, in 0.1～-0.6 V potential range, carry out differential pulse scanning, record the differential pulse voltammetry voltammogram, obtain difference DELTA Ip and the Δ Ip/Ip of peak current
0, with Δ Ip/Ip
0Bring above-mentioned equation into, can ask the melting concn of calculating anthracene phenanthrene in the liquid to be measured.
Beneficial effect of the present invention is: a kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene, the material that electrochemical signals is arranged of employing and tested polynuclear aromatics structural similarity is as electrochemical probe, be combined with Graphene and be prepared into probe material, be modified at electrode surface.Thereby by the π-πconjugation between polynuclear aromatics and the probe electrochemical signals of the probe of electrode surface is changed, detect the content of target polynuclear aromatics in the solution by the detection to intensity of variation.Do not need the steps such as cultivation under the specific condition and sample pre-treatments; Detection speed is fast, and sense cycle is shorter, does not need to carry out loaded down with trivial details operation.
This method is relatively low to the resultant detection limit of anthracene phenanthrene, has higher practical value.Under the concentration of suitable anthracene phenanthrene, can get rid of the interference of other polynuclear aromaticss, the interference of effectively having lowered coexisting substances, selectivity is good, and is highly sensitive.This functional modification electrode that utilizes the probe modification mesoporous material, its material is synthetic simple and convenient, and modified electrode is made easier, and material price is cheap, and electrode is easy to upgrade, and favorable reproducibility is nontoxic, free from environmental pollution.
Description of drawings:
Figure 1 shows that the cyclic voltammogram of TH-GNs/GCE modified electrode in the PBS damping fluid of pH6.5;
Figure 2 shows that the anthracene of variable concentrations, the differential pulse voltammetry figure when phenanthrene exists, represent respectively blank solution, anthracene, luxuriant and rich with fragrance concentration 1.0 10 by a to the reduction peak figure of f
-11, 1.0 10
-10, 1.0 10
-9, 1.0 10
-8, 1.0 10
-7Mol/L;
Figure 3 shows that anthracene, luxuriant and rich with fragrance resultant setting-out line sexual intercourse figure.
Embodiment:
In order to understand better the present invention, the below describes technical scheme of the present invention in detail with instantiation, but the present invention is not limited thereto.
Embodiment 1
The synthesis step of probe material is: the graphene oxide that takes by weighing 0.04g is dissolved in the suitable quantity of water, adds thermal agitation, is warming up to 75 ℃, then adds 40mg sulphur a beautiful gem, is warmed up to 90 ℃, then adds 2g NaBH
4, stir, reacted 24 hours, then solution being dialysed obtains probe material TH-GNs.
Modified electrode is made, and the steps include: to take by weighing the 0.0020g probe material, it is added among the Nafion solution 1.0mL ultrasonic mixing.Microsyringe is drawn 10uL and is dropped in the glass-carbon electrode surface, dries under the infrared lamp, makes Electrochemical Modification electrode (TH-GNs/GCE).
Utilize above-mentioned modified electrode to measure anthracene phenanthrene in the solution, concrete steps are:
(1) in the electrolytic cell that contains 10mL PBS damping fluid (pH6.5), take above-mentioned modified electrode TH-GNs/GCE as working electrode, the Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out at the CHI842C Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In 0.1～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0.1～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured blank peak point current Ip
0
(2) get the luxuriant and rich with fragrance mixed standard solution of a certain amount of anthracene with microsyringe and join in the above-mentioned electrolytic solution cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram obtains peak point current Ip
1, the difference DELTA Ip of peak current behind the calculating adding anthracene phenanthrene
1(Ip
1-Ip
0) and peak current difference DELTA Ip and blank peak point current Ip
0Ratio (Δ Ip/Ip
0).According to said method, add the luxuriant and rich with fragrance mixed standard solution of anthracene of variable concentrations, can obtain corresponding peak current ratios delta Ip/Ip
0The logarithm of the luxuriant and rich with fragrance melting concn of this ratio and anthracene presents good linear relationship, and the range of linearity is 1.0 * 10
-11-1.0 * 10
-7Mol/L, linear equation are Δ Ip/Ip
0=-0.0698lgc-0.8111, c are concentration, and unit is mol/L, peak current Ip
0, Δ Ip, unit is μ A, linearly dependent coefficient r=0.9995 detects and is limited to 1.0 * 10
-12Mol/L;
(3) in conjunction with above-mentioned linear relationship, the luxuriant and rich with fragrance biased sample of the anthracene of unknown concentration is measured, calculated the melting concn of anthracene phenanthrene: in the electrolytic cell that contains 10mL PBS solution (pH6.5), take above-mentioned modified electrode as working electrode, the Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out at the CHI842C Electrochemical Comprehensive Tester, and its attached computer software is made for the acquisition and processing of experimental data; In 0.1～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0.1～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured blank peak point current Ip
0Then add a certain amount of solution to be measured, in 0.1～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram.Obtain difference DELTA Ip and the Δ Ip/Ip of peak current
0, with Δ Ip/Ip
0Bring above-mentioned equation into, can ask the melting concn of calculating anthracene phenanthrene in the liquid to be measured.
Therefore (4) because polynuclear aromatics seldom separately exists in the environment, must consider other polynuclear aromaticss to the response condition of probe in anthracene and luxuriant and rich with fragrance detection, the present invention has investigated polynuclear aromatics naphthalene, the response of benzopyrene to measuring common in the environment.Get the PBS buffer solution of 10mL pH=6.5, add respectively therein naphthalene, the benzopyrene solution of variable concentrations.Carry out DPV scanning, and it is less on anthracene detection impact to calculate other polynuclear aromaticss.
The present invention adopts mixed method that probe sulphur a beautiful gem is modified at electrode surface, with the interact variation of the electrochemical signals that is converted into the sulphur a beautiful gem of the π of polynuclear aromatics and probe sulphur a beautiful gem-π, realizes the Electrochemical Detection in the polynuclear aromatics aqueous systems with this.Utilize simultaneously the electric conductivity of Graphene, further improve sensitivity.This functional mesoporous material is synthetic simple and convenient, and material price is cheap, and modified electrode is simple for production, and electrode is easy to upgrade, and favorable reproducibility is nontoxic, free from environmental pollution; It can be directly applied to the detection of the luxuriant and rich with fragrance resultant of anthracene in the sample that contains polynuclear aromatics.
Claims (4)
1. an electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene is characterized in that, adopts the sulphur a beautiful gem as probe and Graphene mixing manufacture Electrochemical Modification electrode, quantitatively detects the luxuriant and rich with fragrance resultant of anthracene with it.
2. a kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene according to claim 1, it is characterized in that, mix with Graphene as probe with the sulphur a beautiful gem, step is: the graphene oxide that takes by weighing 0.04g is dissolved in the suitable quantity of water, add thermal agitation, be warming up to 75 ℃, then add 40mg sulphur a beautiful gem, be warmed up to 90 ℃, then add 2g NaBH
4, stir, reacted 24 hours, then solution being dialysed obtains probe material TH-GNs.
3. a kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene according to claim 1 is characterized in that the modified electrode making step is: take by weighing the 0.0020g probe material, it is added among the Nafion solution 1.0mL ultrasonic mixing; Microsyringe is drawn 10 μ L and is dropped in the glass-carbon electrode surface, dries under the infrared lamp, makes Electrochemical Modification electrode (TH-GNs/GCE).
4. a kind of electrochemical method that detects the luxuriant and rich with fragrance resultant of palycyclic aromatic anthracene according to claim 1 is characterized in that detecting step is:
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Cited By (7)
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| CN103837591A (en) * | 2014-03-11 | 2014-06-04 | 济南大学 | Electrochemical method for detecting polyaromatic hydrocarbon [k] benzofluoranthrene |
| CN103926290A (en) * | 2014-05-05 | 2014-07-16 | 济南大学 | Electrochemical method for rapidly screening polycyclic aromatic hydrocarbon |
| CN105158318A (en) * | 2015-08-03 | 2015-12-16 | 济南大学 | Preparation method of electrochemical sensor for detection of polycyclic aromatic hydrocarbons |
| CN106596942A (en) * | 2016-12-21 | 2017-04-26 | 山东理工大学 | Construction method and application of sandwich-type hepatitis B virus marker immunosensor |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN107490609A (en) * | 2017-07-18 | 2017-12-19 | 济南大学 | Acetamiprid aptamers electrochemical sensor based on mesoporous silicon dioxde film |
| CN108732219A (en) * | 2018-05-30 | 2018-11-02 | 遵义师范学院 | A kind of electrochemical sensor preparation method and applications of detection polycyclic aromatic hydrocarbon |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103837591A (en) * | 2014-03-11 | 2014-06-04 | 济南大学 | Electrochemical method for detecting polyaromatic hydrocarbon [k] benzofluoranthrene |
| CN103926290A (en) * | 2014-05-05 | 2014-07-16 | 济南大学 | Electrochemical method for rapidly screening polycyclic aromatic hydrocarbon |
| CN103926290B (en) * | 2014-05-05 | 2016-04-20 | 济南大学 | A kind of electrochemical method of rapid screening palycyclic aromatic |
| CN105158318A (en) * | 2015-08-03 | 2015-12-16 | 济南大学 | Preparation method of electrochemical sensor for detection of polycyclic aromatic hydrocarbons |
| CN105158318B (en) * | 2015-08-03 | 2017-12-12 | 济南大学 | A kind of preparation method for the electrochemical sensor for detecting polycyclic aromatic hydrocarbon |
| CN106596942A (en) * | 2016-12-21 | 2017-04-26 | 山东理工大学 | Construction method and application of sandwich-type hepatitis B virus marker immunosensor |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN107490609A (en) * | 2017-07-18 | 2017-12-19 | 济南大学 | Acetamiprid aptamers electrochemical sensor based on mesoporous silicon dioxde film |
| CN107490609B (en) * | 2017-07-18 | 2019-11-01 | 济南大学 | Acetamiprid aptamers electrochemical sensor based on mesoporous silicon dioxde film |
| CN108732219A (en) * | 2018-05-30 | 2018-11-02 | 遵义师范学院 | A kind of electrochemical sensor preparation method and applications of detection polycyclic aromatic hydrocarbon |
| CN108732219B (en) * | 2018-05-30 | 2020-10-16 | 遵义师范学院 | Preparation method and application of electrochemical sensor for detecting polycyclic aromatic hydrocarbon |
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