CN103048374B - 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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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 aqueous systems as 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 is extensively present in the waste water that the industry production such as textile, pharmacy, papermaking, dyestuff emit, the mankind, animal, plant are had to serious toxic action, thereby the research of anthracene detection method in water is more and more received to analytical chemistry worker's concern.
Along with method and the instrument of the various detection arene of scientific and technical development material are come out one after another, wherein conventional method 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 weighing the weight of product.Gravimetric method taking precipitation reaction as basis, also can be utilized volatilization conventionally, and the means such as extraction are analyzed.
2, infrared method: utilize the selectivity of the electromagnetic radiation of material to infrared light district to absorb to carry out a kind of method of structure analysis and qualitative and quantitative analysis.
3, ultraviolet spectrophotometry: the method that the absorbance log according to measured matter in the certain wave strong point of ultraviolet light or certain wavelength coverage is carried out qualitative and quantitative analysis to this material is called ultraviolet spectrophotometry.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 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 effectively accelerate the oxidation of PAHs 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 electrooxidation reduction in non-aqueous solvent.
But these methods generally need to be carried out pre-treatment to sample, complex operation is time-consuming, needs support equipment more, is difficult to realize on-the-spot emergency monitoring and on-line analysis.And due to many reasons, selectivity, the detection limit of a lot of methods are undesirable, cannot detect the even anthracene of trace of 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 on to electrode surface, then anthracene is carried out to mark, make it produce electrochemical signals, then the anthracene after mark and antibody are carried out to combination, this modified electrode is positioned in solution to be measured, in 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 to develop a kind of method of measuring anthracene content in aqueous solution that is directly used in of more convenient and quicker.
Summary of the invention
Object of the present invention is exactly to provide a kind of electrochemical method that detects palycyclic aromatic anthracene for above-mentioned shortcoming, adopt with the material that has electrochemical signals of tested polynuclear aromatics structural similarity and make Electrochemical Modification electrode as electrochemical probe, target polynuclear aromatics is detected, by the π-πconjugation between polynuclear aromatics and probe, thereby the electrochemical signals of the probe of electrode surface is changed, by the detection of intensity of variation being measured to the content of target polynuclear aromatics in 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, highly sensitive.
Technical scheme of the present invention is: a kind of electrochemical method that detects palycyclic aromatic anthracene, and utilize sodium alizarinsulfonate (ARS) to make Electrochemical Modification electrode as probe modification mesoporous material, quantitatively detect anthracene content with it.
Utilize ARS to modify SBA15, the steps include: that the ARS that takes 0.5g is dissolved in appropriate dry DMF, adds 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, filter, product with DMF, ethanol, acetone and intermediate water washing, can obtain the SBA15 mesoporous material that probe sodium alizarinsulfonate is modified successively.
Utilize the SBA15 after ARS modifies to make modified electrode, the steps include: to take the SBA15 material after 0.0020gARS modifies, added in Nafion solution 1.0mL ultrasonic mixing; Microsyringe is drawn 10uL and is dropped in glass-carbon electrode surface, under infrared lamp, dries, and makes Electrochemical Modification electrode A RS-SBA15/CPE.
Taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode, utilizes differential pulse voltammetry to carry out electrochemical measurement to palycyclic aromatic anthracene.
Detect an electrochemical method for palycyclic aromatic anthracene, concrete steps are:
(1) in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current, be blank peak point current Ip
0.
(2) get a certain amount of anthracene solution with microsyringe and join in electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current Ip
1.Calculating adds the difference DELTA Ip of peak current after 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 is Δ Ip=-2.24 × 10
-4-1.54 × 10
-5logC, C is concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, 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, taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, 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 processing; 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 processing, obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration that calculates anthracene in liquid to be measured.
Beneficial effect of the present invention is: a kind of electrochemical method that detects palycyclic aromatic anthracene, adopt with the material that has electrochemical signals of tested polynuclear aromatics structural similarity and detect as electrochemical probe making Electrochemical Modification electrode pair target polynuclear aromatics, by the π-πconjugation between polynuclear aromatics and probe, thereby the electrochemical signals of the probe of electrode surface is changed, by the detection of intensity of variation being measured to the content of target polynuclear aromatics in 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 to electrode surface, be made into Electrochemical Modification electrode.Effect between polynuclear aromatics and probe is converted to the variation of the electric signal that can detect, realized the Electrochemical Detection of polynuclear aromatics in aqueous systems.The scanning of employing differential pulse voltammetry, and data are carried out to second derivative processing, effectively lower the interference of coexisting substances, further improve detection selectivity and sensitivity.
The method does not need the step such as cultivation and sample pre-treatments under specific condition, 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, highly sensitive.
brief description of the 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;
The DPV reduction peak figure of the anthracene that Figure 2 shows that variable concentrations on the impact of modified electrode electrochemical signals;
The DPV second derivative figure of the anthracene that Figure 3 shows that variable concentrations on the impact of modified electrode electrochemical signals;
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, in Fig. 2, represent respectively reagent blank by a to the reduction peak figure of f, anthracene concentration 0,1.0 × 10
-12, 1.0 × 10
-11, 1.0 × 10
-10, 1.0 × 10
-9, 1.0 × 10
-8mol/L;
In Fig. 3, represent respectively reagent blank by a to the reduction peak figure of f, anthracene concentration 0,1.0 × 10
-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-phenanthrene, 4-pyrene, 5-BAP, 6-naphthols, 7-anthracene.
embodiment:
In order to understand better the present invention, describe technical scheme of the present invention in detail with instantiation below, but the present invention is not limited thereto.
Embodiment 1
Detect an electrochemical method for palycyclic aromatic anthracene, adopt probe sodium alizarinsulfonate (ARS) to modify mesoporous material SBA15 Electrochemical Modification electrode, this modified electrode is with mesoporous material ARS-SBA15 and glass-carbon electrode preparation, for detection of anthracene content in aqueous solution.
1 mesoporous material SBA15 is synthetic: SBA15's is synthetic, and 4g Pluronic P123 is dissolved in 30g deionized water, adds 120g 2mol/L HCl, stirs at 40 DEG C and obtains after clear solution, adds 8.5g TEOS, keep 40 DEG C at continuous stirring 20h.Then continue after aging 2-3d, to filter at 100 DEG C, washing, dry.Finally be warming up to 500 DEG C with 1 DEG C/min speed, after calcining 4-6h, obtain SBA15 sample.
2 sodium alizarinsulfonate probes (ARS) are modified mesoporous material (SBA15), the steps include: that the ARS that takes 0.5g is dissolved in appropriate dry DMF, adds 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(laboratory to synthesize voluntarily), then heat up and continue reaction.Cooling, filter, product is successively with DMF, ethanol, acetone and intermediate water washing.Can obtain the SBA15 mesoporous material that probe sodium alizarinsulfonate is modified.
3 modified electrodes are made, and the steps include: to take the SBA15 material after 0.0020g sodium alizarinsulfonate is modified, and are added in Nafion solution 1.0mL ultrasonic mixing.Microsyringe is drawn 10uL and is dropped in glass-carbon electrode surface, under infrared lamp, dries.Make Electrochemical Modification electrode (ARS-SBA15/CPE).
4 utilize above-mentioned ARS-SBA15/CPE modified electrode to measure anthracene in solution, and concrete steps are:
(1) in the electrolytic cell that contains 10mL NaAc-HAc solution (pH4.5), taking above-mentioned modified electrode (ARS-SBA15/CPE) as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current, be blank peak point current Ip
0.
(2) get a certain amount of anthracene solution with microsyringe and join in electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current Ip
1.Calculating adds the difference DELTA Ip of peak current after 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 is Δ Ip=-2.24 × 10
-4-1.54 × 10
-5logC, C is concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, 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), taking above-mentioned modified electrode (ARS-SBA15/CPE) as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, 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 processing.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 processing.Obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration that calculates anthracene in liquid to be measured.
Because polynuclear aromatics seldom separately exists in environment, therefore in the detection of anthracene, must consider the response condition of other polynuclear aromaticss to probe, the present invention has investigated polynuclear aromatics naphthalene, phenanthrene, the response of benzopyrene to modified electrode common in environment, refers to 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.Using ARS-SBA15-CPE as working electrode, carry out DPV scanning, result is carried out to second derivative processing, and it is less on anthracene detection impact to calculate other polynuclear aromaticss.
The present invention adopts with the material that has electrochemical signals of tested polynuclear aromatics structural similarity and detects as electrochemical probe making Electrochemical Modification electrode pair target polynuclear aromatics.Thereby by the π-πconjugation between polynuclear aromatics and probe, the electrochemical signals of the probe of electrode surface is changed.By the detection of intensity of variation being detected to the content of target polynuclear aromatics in solution.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 to electrode surface, be made into Electrochemical Modification electrode.Effect between polynuclear aromatics and probe is converted to the variation of the electric signal that can detect, realized the Electrochemical Detection of polynuclear aromatics in aqueous systems.The scanning of employing differential pulse voltammetry, and data are carried out to second derivative processing, effectively lower the interference of coexisting substances, further improve 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; Can be directly applied to the sample detection containing anthracene.
Claims (2)
1. an electrochemical method that detects palycyclic aromatic anthracene, is characterized in that, utilizes sodium alizarinsulfonate to make Electrochemical Modification electrode as probe modification mesoporous material, quantitatively detects anthracene content with it;
Utilize sodium alizarinsulfonate to modify SBA15, the steps include: that the sodium alizarinsulfonate that takes 0.5g is dissolved in appropriate dry DMF, 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, filter, product with DMF, ethanol, acetone and intermediate water washing, can obtain the SBA15 mesoporous material that probe sodium alizarinsulfonate is modified successively;
Utilize sodium alizarinsulfonate to modify SBA15 and make modified electrode, the steps include: to take the SBA15 material after 0.0020g sodium alizarinsulfonate is modified, added in Nafion solution 1.0mL ultrasonic mixing; Microsyringe is drawn 10 μ L and is dropped in glass-carbon electrode surface, under infrared lamp, dries, and makes modified electrode ARS-SBA15/CPE;
Taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode, utilizes differential pulse voltammetry to carry out electrochemical measurement to palycyclic aromatic anthracene.
2. a kind of electrochemical method that detects palycyclic aromatic anthracene according to claim 1, is characterized in that, concrete steps are:
(1) in the electrolytic cell of the NaAc-HAc solution that contains 10mL pH4.5, taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, sweep velocity 100mV/s; Then in 0～-0.6 V potential range, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current, be blank peak point current Ip
0;
(2) get a certain amount of anthracene solution with microsyringe and join in electrolytic cell, carry out differential pulse scanning, record differential pulse voltammetry voltammogram, measure second derivative peak point current Ip
1, calculate the difference DELTA Ip that adds peak current after 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 is Δ Ip=-2.24 × 10
-4-1.54 × 10
-5logC, C is concentration, and unit is mol/L, and Δ Ip is that peak current is poor, and unit is μ A, 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, taking modified electrode ARS-SBA15/CPE as working electrode, Ag/AgCl electrode is contrast electrode, and platinum electrode is to electrode; Experiment is carried out on 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 and enclose, 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 processing; 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 processing, obtain the difference DELTA Ip of peak current, bring Δ Ip into above-mentioned equation, can ask the concentration that calculates anthracene in 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 |
| CN103926290B (en) * | 2014-05-05 | 2016-04-20 | 济南大学 | A kind of electrochemical method of rapid screening palycyclic aromatic |
| 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 |
| CN107121484B (en) * | 2017-05-19 | 2019-01-22 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| 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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| WO2012018632A2 (en) * | 2010-07-26 | 2012-02-09 | Senova Systems, Inc. | Analyte sensor |
| CN102788832A (en) * | 2012-07-24 | 2012-11-21 | 太原重工股份有限公司 | Detection method for sodium anthraquinone disulfonate |
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| WO2012018632A2 (en) * | 2010-07-26 | 2012-02-09 | Senova Systems, Inc. | Analyte sensor |
| CN102788832A (en) * | 2012-07-24 | 2012-11-21 | 太原重工股份有限公司 | Detection method for sodium anthraquinone disulfonate |
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