CN103267787A - Method for simultaneous detection of hydroquinone and pyrocatechol, and preparation method for applied nitrogen-doped graphene-modified glassy carbon electrode - Google Patents

Method for simultaneous detection of hydroquinone and pyrocatechol, and preparation method for applied nitrogen-doped graphene-modified glassy carbon electrode Download PDF

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CN103267787A
CN103267787A CN2013101565029A CN201310156502A CN103267787A CN 103267787 A CN103267787 A CN 103267787A CN 2013101565029 A CN2013101565029 A CN 2013101565029A CN 201310156502 A CN201310156502 A CN 201310156502A CN 103267787 A CN103267787 A CN 103267787A
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卢小泉
袁彩霞
张村
王永兰
周喜斌
杜娇
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Northwest Normal University
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Abstract

The invention discloses a novel method for simultaneous detection of hydroquinone and pyrocatechol by using a nitrogen-doped graphene-modified electrode. The method comprises the following steps: 1) placing the nitrogen-doped graphene-modified electrode in a sodium phosphate buffer solution which has a concentration of 0.1 mol/L and a pH value of 7 and contains hydroquinone and pyrocatechol with a total concentration of 1* 10<-4> mol/L and carrying out cyclic voltammetric scanning of different scanning speeds with a platinum wire electrode used as a counter electrode and a saturated calomel electrode used as a reference electrode; 2) placing the nitrogen-doped graphene-modified electrode in a sodium phosphate buffer solution which has a concentration of 0.1 mol/L and a pH value of 7 and contains pyrocatechol with a concentration of 1* 10<-5> mol/L and hydroquinone with different concentrations and carrying out differential pulse voltammetric scanning with the platinum wire electrode used as the counter electrode and the saturated calomel electrode used as the reference electrode; and 3) placing the nitrogen-doped graphene-modified electrode in a sodium phosphate buffer solution which has a concentration of 0.1 mol/L and a pH value of 7 and contains hydroquinone with a concentration of 1* 10<-5> mol/L and pyrocatechol with different concentrations and carrying out differential pulse voltammetric scanning with the platinum wire electrode used as the counter electrode and the saturated calomel electrode used as the reference electrode.

Description

Detect the method for p-dihydroxy-benzene and catechol and the preparation method of applied nitrogen-doped graphene modified glassy carbon electrode simultaneously
Technical field
The present invention relates to a kind of new method that simultaneously detects p-dihydroxy-benzene and catechol.
Background technology
Benzenediol is a kind of as phenolic compound, is widely used in many industrial circles such as medicine, plastics, agricultural chemicals, dyestuff, but because it is poisonous and difficult degradation, therefore become the important sources that in environment, water pollutes, harm humans health; On the other hand, two kinds of isomerss (p-dihydroxy-benzene, catechol) of benzenediol similar structure and performance under low concentration, this just makes people be difficult to the two is distinguished and detects.The method that the differentiation that oneself reports at present detects benzenediol mainly contains spectrophotometric method, high performance liquid chromatography, Electrochemiluminescince.Thereby these methods owing to there being complicated operation, the application of shortcoming limited its rapid and accurate determination such as consuming time, the instrument operating cost is high and reagent stability is poor, therefore, a kind of set up quick, stable distinguishing assay benzenediol isomers method just has important meaning.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing defect, provides a kind of quick, stable nitrogen-doped graphene modified electrode that utilizes to measure the method for p-dihydroxy-benzene and catechol simultaneously.
Purpose of the present invention is carried out specific implementation by the following technical programs:
A kind of method with nitrogen-doped graphene (NG) modified glassy carbon electrode, comprise the steps,
1) nitrogen-doped graphene is scattered in the perfluorinated sulfonic acid that the includes 0.05wt%-water of polytetrafluoroethyl-ne alkene copolymer (Nafion) and the mixed solution of isopropyl alcohol, forms the graphene suspension of 1mg/ml, wherein, the volume ratio of water and isopropyl alcohol is 1:3-5;
2) glass-carbon electrode is polished to minute surface with the alundum (Al2O3) suspension of 0.3 μ m, 0.05 μ m successively, then after the ethanol that is 95% through volume fraction successively, redistilled water ultrasonic cleaning, the glass-carbon electrode after being processed;
3) by step 2) after glass-carbon electrode after the processing nitrogen that is 99.999% through purity dries up, drip 2ulNG suspending liquid on glass-carbon electrode, through infrared lamp, dry, obtain the nitrogen-doped graphene modified electrode.
Preferably, in described step 1), the volume ratio of water and isopropyl alcohol is 1:4.
The film forming that perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer (Nafion) has had, play a fixedly effect of modified electrode, but excessive concentration can hinder electronics, shifts, and concentration is too low, and modified electrode is unstable.While only having the volume ratio 1:4 when water and isopropyl alcohol, NG disperses best.
When above-mentioned glass-carbon electrode is used, after having detected one, because having adsorbed the detection thing on electrode, if will detect again the next item down, must grind off the trim of electrode, repeating step 1 at every turn) to 3) again modify again.
Above-mentioned nitrogen-doped graphene preferably makes in accordance with the following steps,
1) be dispersed in water graphene oxide is ultrasonic, add concentrated hydrochloric acid to make it become HCI concentration 1mol L -1solution A, wherein, graphene oxide: water is 150-200mg:30-40ml;
2) then in solution A, add pyrroles 100mg;
3) to 1mol L -1hydrochloric acid solution in add (NH 4) 2s 2o 8rear formation solution B, wherein, (NH 4) 2s 2o 8: 1mol L -1hydrochloric acid solution be 0.15-0.2g:3-4ml;
4) solution B is joined in the solution A that is mixed with the pyrroles, under room temperature, reaction is 24 hours, form the GO-PPy compound, filter, washing, 55 ℃ be after lower vacuum drying 10-15 hour, 800-1000 ℃ of thermal decomposition 30min in argon gas atmosphere again, obtain the Graphene of nitrogen doping, wherein, solution A: the volume ratio of solution B is 10:1.
Preferably, in described step 1), graphene oxide: water is 5mg:1ml.
Preferably, described step 2) in, (NH 4) 2s 2o 8: 1mol L -1hydrochloric acid solution be 0.17g:4ml;
Preferably, in described step 3), solution A: the volume ratio of solution B is 10:1.
Preferably, in described step 3), heat decomposition temperature is 900 ℃.Temperature is the highest herein must not surpass 1000 ℃, and research shows, best results in the time of 900 ℃.
A kind of method that simultaneously detects p-dihydroxy-benzene and catechol, comprise the steps,
1) by claim, above-mentioned nitrogen-doped graphene modified electrode is placed in the sodium phosphate buffer that the pH that contains p-dihydroxy-benzene and catechol is 7, take platinum electrode as to electrode, take saturated calomel electrode as contrast electrode, carry out difference and sweep fast cyclic voltammetry scan, wherein, described p-dihydroxy-benzene and the catechol total concentration in damping fluid is 1 * 10 -4mol L -1, the concentration of described sodium phosphate in damping fluid is 0.1mol L -1;
2) by claim, above-mentioned nitrogen-doped graphene modified electrode is placed in to containing 1 * 10 -5mol L -1the 0.1mol L of the p-dihydroxy-benzene of catechol, variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode;
3) by claim, above-mentioned nitrogen-doped graphene modified electrode is placed in and contains 1 * 10 -5mol L -1the 0.1mol L of the catechol of p-dihydroxy-benzene, variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode.
Beneficial effect of the present invention:
The present invention is by setting up the nitrogen-doped graphene modified electrode, thereby proposed a kind of new method that simultaneously detects p-dihydroxy-benzene and catechol.The Graphene that the nitrogen prepared in the present invention mixes is three-dimensional porous structure (referring to Fig. 2), utilizes its large specific surface area and outstanding catalytic performance, p-dihydroxy-benzene can well be separated with catechol.Wherein, the oxidation peak current of p-dihydroxy-benzene and catechol increases (referring to Fig. 3) gradually along with sweeping fast increase, and peak current and sweep fast square root and be directly proportional (referring to Fig. 4) illustrates that its oxidizing process on this modified electrode is subject to diffusion control; And, when one timing of catechol concentration, p-dihydroxy-benzene is 6.15 * 10 -7mol L -1～1.22 * 10 -5mol L -1concentration range in peak current proportional (referring to Fig. 5 and 6), detect and be limited to 2.0 * 10 -7molL -1(S/N=3),, when one timing of p-dihydroxy-benzene concentration, catechol is 5.00 * 10 -7mol L -1～1.29 * 10 -5mol L -1concentration range in peak current proportional (referring to Fig. 7 and 8), detect and be limited to 1.6 * 10 -7molL -1(S/N=3).Therefore, during the separation that this novel modified electrode is applied to the benzenediol isomers detects, separate detectability strong, the separation detection means of actual implementation benzenediol isomers is had to certain guiding function.
In sum, the method of the graphene modified glass-carbon electrode of the nitrogen doping that the present invention adopts, utilize the outstanding catalytic performance of nitrogen-doped graphene, better to the detection sensitivity curvilinear correlation high, that scanning obtains of p-dihydroxy-benzene and catechol, simple to operate, expense is low.
The accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms the part of instructions, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
The scanning electron microscope (SEM) photograph that Fig. 1 is the made graphene oxide of the present invention;
The scanning electron microscope (SEM) photograph that Fig. 2 is the made three-dimensional porous nitrogen-doped graphene of the present invention;
Fig. 3 is that nitrogen-doped graphene modified electrode of the present invention is respectively containing 1 * 10 -4mol L -1p-dihydroxy-benzene (HQ) and the 0.1mol L of catechol (CC) -1in the sodium phosphate buffer that pH is 7, sweep speed and be respectively 10,20 from a → m, 30,40,50,70,100,130,160,200,230,260 and 300 mVs -1cyclic voltammetry curve;
Fig. 4 is that nitrogen-doped graphene modified electrode of the present invention is respectively containing 1 * 10 -4mol L -1p-dihydroxy-benzene (HQ) and the 0.1mol L of catechol (CC) -1in the sodium phosphate buffer that pH is 7, sweep speed and be respectively 10,20 from a → m, 30,40,50,70,100,130,160,200,230,260 and 300 mVs -1sweep accordingly the linear relationship of fast square root and peak current;
The modified electrode that Fig. 5 is nitrogen-doped graphene of the present invention is 1 * 10 in catechol concentration -5mol L -1, p-dihydroxy-benzene concentration is respectively 0 mol L from a → i -1, 6.15 * 10 -7mol L -1, 1.23 * 10 -6mol L -1, 3.07 * 10 -6mol L -1, 4.90 * 10 -6mol L -1, 6.75 * 10 -6mol L -1, 8.58 * 10 -6mol L -1, 1.04 * 10 -5mol L -1, 1.22 * 10 -5mol L -1the differential pulse curve;
The linear relationship that Fig. 6 is p-dihydroxy-benzene concentration and peak current, related coefficient is R=0.99708;
The modified electrode that Fig. 7 is nitrogen-doped graphene of the present invention is 1 * 10 in p-dihydroxy-benzene (HQ) concentration -5mol L -1, catechol concentration is respectively 0 mol L from a → i -1, 5.0 * 10 -7mol L -1, 7.50 * 10 -7mol L -1, 9.99 * 10 -7mol L -1, 2.99 * 10 -6mol L -1, 4.98 * 10 -6mol L -1, 6.96 * 10 -6mol L -1, 8.94 * 10 -6mol L -1, 1.09 * 10 -5mol L -1, 1.29 * 10 -5mol L -1the differential pulse curve;
The linear relationship that Fig. 8 is catechol concentration and peak current, related coefficient is R=0.99511.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
The water used in experimentation is redistilled water, test reagent used be analyze pure.Experiment is all at room temperature carried out.
The instrument and the reagent that use:
The automatic dual pure water distiller of quartz ampoule heated type (1810B, Asian-Pacific Glass-Tech. Co., Shanghai City) is for steaming redistilled water; Electronic balance (Beijing Sai Duolisi Instrument Ltd.) is for the weighing medicine; Ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.); Alundum (Al2O3) polishing powder (0.30 mm, 0.05 mm, Shanghai occasion China instrument reagent company) is for the treatment of glass-carbon electrode; Mercurous chloride electrode (CHI III, U.S. CH instrument company) is contrast electrode; Platinum electrode is to electrode; P-dihydroxy-benzene, catechol (Aladdin reagent Shanghai company limited); Sodium nitrate; Potassium permanganate; Dag; Concentrated hydrochloric acid; The pyrroles; Ammonium persulfate; Perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer (Nafion); The potassium ferricyanide, potassium ferrocyanide (Beijing chemical reagents corporation); High pure nitrogen (purity is 99.999%).
embodiment 1:
the preparation method of the Graphene (NG) of nitrogen doping
First prepare graphene oxide (GO) standby: adopt the Hummer legal system standby.
Assemble the reaction bulb of 250 mL in ice-water bath, add the appropriate concentrated sulphuric acid, add the solid mixture of 2 g dags and 1 g sodium nitrate under stirring, then gradation adds 6 g potassium permanganate, control temperature of reaction and be no more than 20 ℃, stirring reaction a period of time, then be warmed up to 35 ℃ of left and right, continues to stir 30 min, slowly add again a certain amount of deionized water, continuous mix 20 min after, and add appropriate hydrogen peroxide to reduce residual oxygenant, make solution become glassy yellow.Filter while hot, and with 5%HCl solution and deionized water wash until in filtrate sulfate radical-free be detected.Again filtrate is disperseed to 2h under ultrasound condition, obtain the dispersion liquid that sepia is stable.Again that this dispersion liquid is centrifugal, filter, the product obtained is fully dry in the vacuum drying chamber of 60 ℃, saves backup.
The Graphene (NG) for preparing the nitrogen doping: by the ultrasonic 40ml of the being dispersed in water of 200mgGO, add a certain amount of dense HCl and make it form 1mol L -1solution.Again 100mg pyrroles is added to above-mentioned solution, then 4ml is contained to 0.17g (NH 4) 2s 2o 81mol L -1hCl solution joins (graphene oxide solution: contain (NH in above-mentioned solution 4) 2s 2o 81mol L -1the HCl liquor capacity is than 10:1), under room temperature, reaction after 24 hours is filtered the GO-ppy compound formed, and washing, spend the night in 55 ℃ of lower vacuum drying.Finally, by GO-ppy 900 ℃ of thermal decomposition 30min in argon atmosphere, obtain the Graphene of nitrogen doping.
embodiment 2:
the preparation method of the Graphene (NG) of nitrogen doping
Be dispersed in 30ml water 150mgGO is ultrasonic, add a certain amount of dense HCl and make it form 1mol L -1solution.Again 100mg pyrroles is added to above-mentioned solution, then 3ml is contained to 0.15g (NH 4) 2s 2o 81mol L -1hCl solution joins (graphene oxide solution: contain (NH in above-mentioned solution 4) 2s 2o 81mol L -1the HCl liquor capacity is than 10:1), under room temperature, reaction after 24 hours is filtered the GO-ppy compound formed, and washing, spend the night in 55 ℃ of lower vacuum drying.Finally, by GO-ppy 800 ℃ of thermal decomposition 30min in argon atmosphere, obtain the Graphene of nitrogen doping.
embodiment 3:
the preparation method of the Graphene (NG) of nitrogen doping
Be dispersed in 36ml water 180mgGO is ultrasonic, add a certain amount of dense HCl and make it form 1mol L -1solution.Again 100mg pyrroles is added to above-mentioned solution, then 3.6ml is contained to 0.2g (NH 4) 2s 2o 81mol L -1hCl solution joins (graphene oxide solution: contain (NH in above-mentioned solution 4) 2s 2o 81mol L -1the HCl liquor capacity is than 10:1), under room temperature, reaction after 24 hours is filtered the GO-ppy compound formed, and washing, spend the night in 55 ℃ of lower vacuum drying.Finally, by GO-ppy 1000 ℃ of thermal decomposition 30min in argon atmosphere, obtain the Graphene of nitrogen doping.
embodiment 4:
method with the nitrogen-doped graphene modified glassy carbon electrode
1) a certain amount of NG is scattered in the water and the mixed liquid (V:V=4:1) of isopropyl alcohol that includes 0.05 wt% perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer, forms 1mg/ml NG suspending liquid;
2) glass-carbon electrode is polished to minute surface with the alundum (Al2O3) suspension of 0.3 μ m, 0.05 μ m successively, then after the ethanol that is 95 % through volume fraction successively, redistilled water ultrasonic cleaning, the glass-carbon electrode after being processed;
3) after the nitrogen that is 99.999% by the glass-carbon electrode after described processing through purity dries up, drip 2ulNG suspending liquid on glass-carbon electrode, dry through infrared lamp, obtain nitrogen-doped graphene modified electrode (NG/GCE) .
embodiment 5:
a kind of method that simultaneously detects p-dihydroxy-benzene and catechol
1) will make NG/GCE is placed in and respectively contains 1 * 10 -4mol L -1p-dihydroxy-benzene (HQ) and the 0.1mol L of catechol (CC) -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, take saturated calomel electrode as contrast electrode, carry out difference and sweep fast cyclic voltammetry scan;
2) will make NG/GCE is placed in and contains 1 * 10 -5mol L -1cC, the 0.1mol L of the HQ of variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode;
3) will make NG/GCE is placed in and contains 1 * 10 -5mol L -1hQ, the 0.1mol L of the CC of variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment, the present invention is had been described in detail, for a person skilled in the art, its technical scheme that still can put down in writing aforementioned each embodiment is modified, or part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (9)

1. the method with the nitrogen-doped graphene modified glassy carbon electrode is characterized in that: comprises the steps,
1) nitrogen-doped graphene is scattered in the perfluorinated sulfonic acid that the includes 0.05wt%-water of polytetrafluoroethyl-ne alkene copolymer and the mixed solution of isopropyl alcohol, forms the nitrogen-doped graphene suspending liquid of 1mg/ml, wherein, the volume ratio of water and isopropyl alcohol is 1:3-5;
2) glass-carbon electrode is polished to minute surface with the alundum (Al2O3) suspension of 0.3 μ m, 0.05 μ m successively, then after the ethanol that is 95 % through volume fraction successively, redistilled water ultrasonic cleaning, the glass-carbon electrode after being processed;
3) by step 2) after glass-carbon electrode after the processing nitrogen that is 99.999% through purity dries up, drip 2ul nitrogen-doped graphene suspending liquid on glass-carbon electrode, through infrared lamp, dry, obtain the nitrogen-doped graphene modified electrode.
2. the method with the nitrogen-doped graphene modified glassy carbon electrode according to claim 1, it is characterized in that: in described step 1), the volume ratio of water and isopropyl alcohol is 1:4.
3. the method with the nitrogen-doped graphene modified glassy carbon electrode according to claim 1, it is characterized in that: described nitrogen-doped graphene makes in accordance with the following steps,
Be dispersed in water graphene oxide is ultrasonic, add concentrated hydrochloric acid to make it become concentration 1mol L -1solution A, wherein, graphene oxide: water is 150-200mg:30-40ml;
Then in solution A, add pyrroles 100mg;
To 1mol L -1hydrochloric acid solution in add (NH 4) 2s 2o 8rear formation solution B, wherein, (NH 4) 2s 2o 8: 1mol L -1hydrochloric acid solution be 0.15-0.2g:3-4ml;
Solution B is joined in the solution A that is mixed with the pyrroles, under room temperature, reaction is 24 hours, form the GO-PPy compound, filter, washing, 55 ℃ be after lower vacuum drying 10-15 hour, 800-1000 ℃ of thermal decomposition 30min in argon gas atmosphere again, obtain the Graphene of nitrogen doping, wherein, solution A: the volume ratio of solution B is 10:1.
4. the method with the nitrogen-doped graphene modified glassy carbon electrode according to claim 3, it is characterized in that: in described step 1), graphene oxide: water is 5mg:1ml.
5. the method for preparing nitrogen-doped graphene according to claim 3 is characterized in that: described step 2), and (NH 4) 2s 2o 8: 1mol L -1hydrochloric acid solution be 0.17g:4ml.
6. the method for preparing nitrogen-doped graphene according to claim 3, it is characterized in that: in described step 3), solution A: the volume ratio of solution B is 10:1.
7. the method for preparing nitrogen-doped graphene according to claim 3, it is characterized in that: in described step 3), heat decomposition temperature is 900 ℃.
8. a method that simultaneously detects p-dihydroxy-benzene and catechol is characterized in that: comprises the steps,
1) the described nitrogen-doped graphene modified electrode of claim 1-7 any one is placed in to the sodium phosphate buffer that the pH that contains p-dihydroxy-benzene and catechol is 7, take platinum electrode as to electrode, take saturated calomel electrode as contrast electrode, carry out difference and sweep fast cyclic voltammetry scan, wherein, described p-dihydroxy-benzene and the catechol total concentration in damping fluid is 1 * 10 -4mol L -1, the concentration of described sodium phosphate in damping fluid is 0.1mol L -1;
2) the described nitrogen-doped graphene modified electrode of claim 1-7 any one is placed in and contains 1 * 10 -5mol L -1the 0.1mol L of the p-dihydroxy-benzene of catechol, variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode;
3) the described nitrogen-doped graphene modified electrode of claim 1-7 any one is placed in and contains 1 * 10 -5mol L -1the 0.1mol L of the catechol of p-dihydroxy-benzene, variable concentrations -1in the sodium phosphate buffer that pH is 7, take platinum electrode as to electrode, the saturated calomel electrode of take is carried out the scanning of differential pulse volt-ampere as contrast electrode.
9. a nitrogen-doped graphene modified electrode detects the sensor of p-dihydroxy-benzene and catechol simultaneously, it is characterized in that: p-dihydroxy-benzene and catechol are adopting the detection limit on the described nitrogen-doped graphene modified electrode of claim 1-7 any one to be respectively 2.0 * 10 -7molL -1with 1.6 * 10 -7molL -1.
CN2013101565029A 2013-04-28 2013-04-28 Method for simultaneous detection of hydroquinone and pyrocatechol, and preparation method for applied nitrogen-doped graphene-modified glassy carbon electrode Pending CN103267787A (en)

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