CN103048374A - Electrochemical method for detecting anthracene of polycyclic aromatic hydrocarbon - Google Patents
Electrochemical method for detecting anthracene of polycyclic aromatic hydrocarbon Download PDFInfo
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- CN103048374A CN103048374A CN2012105187960A CN201210518796A CN103048374A CN 103048374 A CN103048374 A CN 103048374A CN 2012105187960 A CN2012105187960 A CN 2012105187960A CN 201210518796 A CN201210518796 A CN 201210518796A CN 103048374 A CN103048374 A CN 103048374A
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Abstract
The invention relates to the technical field of assay determination of anthracene of polycyclic aromatic hydrocarbon, and in particular relates to an electrochemical method for performing quantitative determination on anthracene content in a water system by taking alizarin red as a probe for modifying a mesoporous material. The material synthesis of a functional modified electrode taking the probe for modifying the mesoporous material is simple and convenient; the modified electrode is simple and convenient to manufacture; the material cost is low; the electrode is easy to update, good in reproducibility and non-toxic, and does not cause environment pollution; and the determining method reduces the interference of coexist substances effectively, and is good in selectivity and high in sensitivity.
Description
Technical field
The present invention relates to polynuclear aromatics anthracene analysis determining technology field, particularly relate to a kind of sodium alizarinsulfonate of utilizing and quantitatively detect the electrochemical method of anthracene content in the aqueous systems as the probe modification mesoporous material and with it.
Background technology
Along with coal, oil are widely used in commercial production, communications and transportation and life, consequent palycyclic aromatic has strong teratogenesis, carcinogenicity and mutagenicity, has therefore become the common organic contaminant of paying close attention in countries in the world.Anthracene extensively is present in the waste water that the industry production such as textile, pharmacy, papermaking, dyestuff emit, the mankind, animal, plant there are serious toxic action, thereby the research of anthracene detection method in the water are more and more received analytical chemistry worker's concern.
Along with method and the instrument of the various detection arene of the development of science and technology material are come out one after another, wherein method commonly used has: the methods such as gravimetric method, infrared method, ultraviolet spectrophotometry, fluorescence, immune modification electrode, photocatalysis and Electrochemical Modification electrode.
1, gravimetric method: measure the quantitative analysis method of content of material by the weight of weighing product.Gravimetric method take precipitation reaction as the basis, also can be utilized volatilization usually, and the means such as extraction are analyzed.
2, infrared method: utilize material the selectivity of the electromagnetic radiation in infrared light district to be absorbed to carry out a kind of method of structure analysis and qualitative and quantitative analysis.
3, ultraviolet spectrophotometry: the method that this material carries out qualitative and quantitative analysis is called ultraviolet spectrophotometry according to the absorbance log of measured matter in the certain wave strong point of ultraviolet light or certain wavelength coverage.Ultraviolet method is simple to operate, precision and highly sensitive, is applicable to measure the oil-containing water sample of 0.05～50mg/ L.
4, fluorescence method: the fluorescence of utilizing polynuclear aromatics.Can realize the chemiluminescence analysis of PAHs, provide and be enough to chemical energy that it is excited but be necessary for the PAHs molecule.
5, photocatalysis: catalysis titanium dioxide photo-degradation palycyclic aromatic is widely studied in the past few years in water.Adopt artificial or sunlight can accelerate the oxidation of PAHs effectively as radiation source catalyzer titania.
6, Electrochemical Modification electrode: the polynuclear aromatics that does not manifest electrochemical activity in water solution system can carry out the electrooxidation reduction in non-aqueous solvent.
But these methods generally need to be carried out pre-treatment to sample, and complex operation is time-consuming, needs support equipment more, is difficult to realize on-the-spot emergency monitoring and on-line analysis.And because many reasons, selectivity, the detection limit of a lot of methods are undesirable, can't detect the anthracene of trace even trace.Wherein the scheme the most close with the present invention is to adopt immune modification electrode pair polynuclear aromatics to detect: anthracene antibody is fixed in electrode surface, then anthracene is carried out mark, make it produce electrochemical signals, then the anthracene behind the mark and antibody are carried out combination, this modified electrode is positioned in the solution to be measured, in the solution unmarked anthracene and electrode surface the anthracene of mark can form competitive mode and be combined, thereby cause the decline of electrochemical signals.But the preparation of immune modification electrode is too complicated, and cost is higher.In addition, because several polynuclear aromaticss usually occur simultaneously, therefore just need the method for measuring anthracene content in the aqueous solution that is directly used in of a kind of more convenient and quicker of development.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of electrochemical method that detects the palycyclic aromatic anthracene for above-mentioned shortcoming, adopt with the material that electrochemical signals is arranged of tested polynuclear aromatics structural similarity and make the Electrochemical Modification electrode as electrochemical probe, the target polynuclear aromatics is detected, by the π-πconjugation between polynuclear aromatics and the probe, thereby the electrochemical signals of the probe of electrode surface is changed, by the detection of intensity of variation being measured the content of target polynuclear aromatics in the solution.Utilize the functional modification electrode of probe modification mesoporous material, its material is synthetic simple and convenient, electrode fabrication is easier, and material price is cheap, and electrode is easy to upgrade, favorable reproducibility, nontoxic, free from environmental pollution, and this assay method has effectively lowered the interference of coexisting substances, selectivity is good, and is highly sensitive.
Technical scheme of the present invention is: a kind of electrochemical method that detects the palycyclic aromatic anthracene, and utilize sodium alizarinsulfonate (ARS) to make the Electrochemical Modification electrode as the probe modification mesoporous material, quantitatively detect anthracene content with it.
Utilize ARS to modify SBA15, the steps include: that the ARS that takes by weighing 0.5g is dissolved among the DMF of an amount of drying, add excessive NaH vigorous stirring a period of time, the unreacted NaH of elimination.In filtrate, add 2.0mLKH-560, under blanket of nitrogen, react, add 2gSBA15, then heat up and continue reaction; Cooling is filtered, and product with DMF, ethanol, acetone and intermediate water washing, can obtain the SBA15 mesoporous material that the probe sodium alizarinsulfonate is modified successively.
Utilize the SBA15 after ARS modifies to make modified electrode, the steps include: to take by weighing the SBA15 material after 0.0020gARS modifies, 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 A RS-SBA15/CPE.
Take modified electrode ARS-SBA15/CPE as working electrode, the Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode, utilizes differential pulse voltammetry that the palycyclic aromatic anthracene is carried out electrochemical measurement.
A kind of electrochemical method that detects the palycyclic aromatic anthracene, concrete steps are:
(1) in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, take modified electrode ARS-SBA15/CPE 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured the second derivative peak point current, is blank peak point current Ip
0
(2) get a certain amount of anthracene solution with microsyringe and join in the electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram is measured second derivative peak point current Ip
1The difference DELTA Ip of peak current behind the calculating adding anthracene
1(Ip
1-Ip
0).According to said method, add the anthracene standard solution of variable concentrations, can obtain the difference DELTA Ip of corresponding peak current.The logarithm of peak point current difference DELTA Ip and anthracene concentration presents good linear relationship, and the range of linearity is 1.0 * 10
-12-1.0 * 10
-8Mol/L, linear equation are Δ Ip=-2.24 * 10
-4-1.54 * 10
-5LogC, C are concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, and linearly dependent coefficient r=0.9995 detects and is limited to 9.0 * 10
-13Mol/L;
(3) in conjunction with above-mentioned linear relationship, anthracene sample to unknown concentration is measured, and calculates anthracene concentration: in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, take modified electrode ARS-SBA15/CPE 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process; Then add a certain amount of solution to be measured, in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process, obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration of calculating anthracene in the liquid to be measured.
Beneficial effect of the present invention is: a kind of electrochemical method that detects the palycyclic aromatic anthracene, employing is made Electrochemical Modification electrode pair target polynuclear aromatics with the material that electrochemical signals is arranged of tested polynuclear aromatics structural similarity as electrochemical probe and is detected, by the π-πconjugation between polynuclear aromatics and the probe, thereby the electrochemical signals of the probe of electrode surface is changed, by the detection of intensity of variation being measured the content of target polynuclear aromatics in the solution.
Utilize the functional modification electrode of 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; Utilize the characterization of adsorption of ordered porous monox, improved sensitivity, utilized porous oxidation silicon face great amount of hydroxy group that probe is fixed on electrode surface, be made into the Electrochemical Modification electrode.Convert the effect between polynuclear aromatics and the probe variation of the electric signal that can detect to, realized the Electrochemical Detection of polynuclear aromatics in the aqueous systems.The scanning of employing differential pulse voltammetry, and data are carried out second derivative process, the interference of effectively having lowered coexisting substances has further improved detection selectivity and sensitivity.
The method does not need the steps such as cultivation under the specific condition and sample pre-treatments, and 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 detection limit of anthracene, has higher practical value, can get rid of the interference of other polynuclear aromaticss under the concentration of suitable anthracene, the interference of effectively having lowered coexisting substances, and selectivity is good, and is highly sensitive.
Description of drawings:
Figure 1 shows that the cyclic voltammogram of naked glass-carbon electrode CPE and the rear glass-carbon electrode (ARS-SBA15/CPE) of modification;
Figure 2 shows that the anthracene of variable concentrations is on the DPV reduction peak figure of modified electrode electrochemical signals impact;
Figure 3 shows that the anthracene of variable concentrations is on the DPV second derivative figure of modified electrode electrochemical signals impact;
Figure 4 shows that peak current difference of the present invention and logc linear relationship chart;
Figure 5 shows that the log-linear graph of a relation of peak current and anthracene, phenanthrene, naphthols, pyrene, BAP concentration, the HAc-NaAc solution of pH=4.5 is made end liquid.
Wherein, represent respectively reagent blank, anthracene concentration 0,1.0 * 10 by a to the reduction peak figure of f among Fig. 2
-12, 1.0 * 10
-11, 1.0 * 10
-10, 1.0 * 10
-9, 1.0 * 10
-8Mol/L;
Represent respectively reagent blank, anthracene concentration 0,1.0 * 10 by a to the reduction peak figure of f among Fig. 3
-12, 1.0 * 10
-11, 1.0 * 10
-10, 1.0 * 10
-9, 1.0 * 10
-8Mol/L;
1-ARS-SBA15/CPE, 2-CPE, 3-is luxuriant and rich with fragrance, 4-pyrene, 5-BAP, 6-naphthols, 7-anthracene.
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
A kind of electrochemical method that detects the palycyclic aromatic anthracene adopts probe sodium alizarinsulfonate (ARS) to modify mesoporous material SBA15 Electrochemical Modification electrode, and this modified electrode is with mesoporous material ARS-SBA15 and glass-carbon electrode preparation, for detection of anthracene content in the aqueous solution.
1 mesoporous material SBA15 is synthetic: SBA15's is synthetic, and 4g Pluronic P123 is dissolved in the 30g deionized water, adds 120g 2mol/L HCl, after 40 ℃ of lower stirrings obtain clear solution, adds 8.5g TEOS, keeps 40 ℃ of lower continuous stirring 20h.Then continue behind 100 ℃ of lower aging 2-3d, to filter washing, drying.Be warming up to 500 ℃ with 1 ℃/min speed at last, obtain the SBA15 sample behind the calcining 4-6h.
2 sodium alizarinsulfonate probes (ARS) are modified mesoporous material (SBA15), the steps include: that the ARS that takes by weighing 0.5g is dissolved among the DMF of an amount of drying, add excessive NaH vigorous stirring a period of time, the unreacted NaH of elimination.In filtrate, add 2.0mLKH-560, under blanket of nitrogen, react, add the 2gSBA15(laboratory and synthesize voluntarily), then heat up and continue reaction.Cooling is filtered, and product is successively with DMF, ethanol, acetone and intermediate water washing.Can obtain the SBA15 mesoporous material that the probe sodium alizarinsulfonate is modified.
3 modified electrodes are made, and the steps include: to take by weighing the SBA15 material after the 0.0020g sodium alizarinsulfonate is modified, and it are 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.Make Electrochemical Modification electrode (ARS-SBA15/CPE).
4 utilize above-mentioned ARS-SBA15/CPE modified electrode to measure anthracene in the solution, and concrete steps are:
(1) in the electrolytic cell that contains 10mL NaAc-HAc solution (pH4.5), take above-mentioned modified electrode (ARS-SBA15/CPE) 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured the second derivative peak point current, is blank peak point current Ip
0
(2) get a certain amount of anthracene solution with microsyringe and join in the electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram is measured second derivative peak point current Ip
1The difference DELTA Ip of peak current behind the calculating adding anthracene
1(Ip
1-Ip
0).According to said method, add the anthracene standard solution of variable concentrations, can obtain the difference DELTA Ip of corresponding peak current.The logarithm of peak point current difference DELTA Ip and anthracene concentration presents good linear relationship, and the range of linearity is 1.0 * 10
-12-1.0 * 10
-8Mol/L, linear equation are Δ Ip=-2.24 * 10
-4-1.54 * 10
-5LogC, C are concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, and linearly dependent coefficient r=0.9995 detects and is limited to 9.0 * 10
-13Mol/L;
(3) in conjunction with above-mentioned linear relationship, anthracene sample to unknown concentration is measured, calculate anthracene concentration: in the electrolytic cell that contains 10mL NaAc-HAc solution (pH4.5), take above-mentioned modified electrode (ARS-SBA15/CPE) 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process.Then add a certain amount of solution to be measured, in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process.Obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration of calculating anthracene in the liquid to be measured.
Because polynuclear aromatics seldom separately exists in the environment, therefore must consider in the detection of anthracene that other polynuclear aromaticss are to the response condition of probe, the present invention has investigated polynuclear aromatics naphthalene common in the environment, phenanthrene, benzopyrene to the response of modified electrode, sees also Figure of description Fig. 5.Get the HAc-NaAc buffer solution of 10mLpH=4.5, add respectively therein naphthalene, phenanthrene, the benzopyrene solution of variable concentrations.As working electrode, carry out DPV scanning with ARS-SBA15-CPE, the result is carried out second derivative process, and it is less on anthracene detection impact to calculate other polynuclear aromaticss.
The present invention adopts and the material that electrochemical signals is arranged of tested polynuclear aromatics structural similarity detects as electrochemical probe making Electrochemical Modification electrode pair target polynuclear aromatics.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.Utilize the characterization of adsorption of ordered porous monox, improved sensitivity, utilized porous oxidation silicon face great amount of hydroxy group that probe is fixed on electrode surface, be made into the Electrochemical Modification electrode.Convert the effect between polynuclear aromatics and the probe variation of the electric signal that can detect to, realized the Electrochemical Detection of polynuclear aromatics in the aqueous systems.The scanning of employing differential pulse voltammetry, and data are carried out second derivative process, the interference of effectively having lowered coexisting substances has further improved detection selectivity and 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 sample detection that contains anthracene.
Claims (5)
1. an electrochemical method that detects the palycyclic aromatic anthracene is characterized in that, utilizes sodium alizarinsulfonate to make the Electrochemical Modification electrode as the probe modification mesoporous material, quantitatively detects anthracene content with it.
2. a kind of electrochemical method that detects the palycyclic aromatic anthracene according to claim 1, it is characterized in that, utilize sodium alizarinsulfonate to modify SBA15, the steps include: that the sodium alizarinsulfonate that takes by weighing 0.5g is dissolved among the DMF of an amount of drying, add excessive NaH vigorous stirring a period of time, the unreacted NaH of elimination, in filtrate, add 2.0mLKH-560, under blanket of nitrogen, react, add 2gSBA15, then heat up and continue reaction; Cooling is filtered, and product with DMF, ethanol, acetone and intermediate water washing, can obtain the SBA15 mesoporous material that the probe sodium alizarinsulfonate is modified successively.
3. a kind of electrochemical method that detects the palycyclic aromatic anthracene according to claim 2, it is characterized in that, utilize sodium alizarinsulfonate to modify SBA15 and make modified electrode, the steps include: to take by weighing the SBA15 material after the 0.0020g sodium alizarinsulfonate is modified, 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 modified electrode ARS-SBA15/CPE.
4. a kind of electrochemical method that detects the palycyclic aromatic anthracene according to claim 1, it is characterized in that, take modified electrode ARS-SBA15/CPE as working electrode, the Ag/AgCl electrode is contrast electrode, platinum electrode is to electrode, utilizes differential pulse voltammetry that the palycyclic aromatic anthracene is carried out electrochemical measurement.
5. the described a kind of electrochemical method that detects the palycyclic aromatic anthracene of arbitrary claim according to claim 1-4 is characterized in that concrete steps are:
(1) in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, take modified electrode ARS-SBA15/CPE 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then carry out differential pulse scanning in 0～-0.6 V potential range, record differential pulse voltammetry voltammogram is measured the second derivative peak point current, is blank peak point current Ip
0
(2) get a certain amount of anthracene solution with microsyringe and join in the electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram is measured second derivative peak point current Ip
1, the difference DELTA Ip of peak current behind the calculating adding anthracene
1(Ip
1-Ip
0), according to said method, add the anthracene standard solution of variable concentrations, can obtain the difference DELTA Ip of corresponding peak current, the logarithm of peak point current difference DELTA Ip and anthracene concentration presents good linear relationship, and the range of linearity is 1.0 * 10
-12-1.0 * 10
-8Mol/L, linear equation are Δ Ip=-2.24 * 10
-4-1.54 * 10
-5LogC, C are concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, and linearly dependent coefficient r=0.9995 detects and is limited to 9.0 * 10
-13Mol/L;
(3) in conjunction with above-mentioned linear relationship, anthracene sample to unknown concentration is measured, and calculates anthracene concentration: in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, take modified electrode ARS-SBA15/CPE 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～-0.6 V potential range, carry out cyclic voltammetry scan 5 circles, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process; Then add a certain amount of solution to be measured, in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, and carry out second derivative and process, obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration of calculating anthracene in the liquid to be measured.
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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 |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN109991294A (en) * | 2019-04-23 | 2019-07-09 | 南京腾森分析仪器有限公司 | A kind of membrane electrode, preparation method and sensor, electrochemical workstation and its application using it |
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| US20050157445A1 (en) * | 2003-09-18 | 2005-07-21 | Keith Bradley | Nanostructures with electrodeposited nanoparticles |
| CN101713759A (en) * | 2008-09-25 | 2010-05-26 | 米利波尔公司 | Electrochemical method for detecting boron in water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN109991294A (en) * | 2019-04-23 | 2019-07-09 | 南京腾森分析仪器有限公司 | A kind of membrane electrode, preparation method and sensor, electrochemical workstation and its application using it |
| CN109991294B (en) * | 2019-04-23 | 2022-02-18 | 南京腾森分析仪器有限公司 | Membrane electrode, preparation method thereof, sensor using membrane electrode, electrochemical workstation and application of electrochemical workstation |
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