CN102645458A - Electrochemical sensor for fast detecting sulfides by grapheme modified electrode as well as building and application of electrochemical sensor - Google Patents
Electrochemical sensor for fast detecting sulfides by grapheme modified electrode as well as building and application of electrochemical sensor Download PDFInfo
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Abstract
本发明涉及到对于环境检测，具体的说是一种石墨烯修饰电极快速检测硫化物的电化学传感器及其构建和应用。电化学传感器以玻碳电极为载体，载体负载50-60μg cm-2的石墨烯作为识别元件。本发明提供了一种快速而灵敏的检测技术。而且相对于其他电化学检测技术来说显著提高了其检测信号强度，具有很宽的线性检测范围。同时本发明电化学传感器构建技术方便，参数比较容易控制，相对于其他光学检测方法来说，本发明方法更加快速，简便，所需的设备更加简单，材料更廉价。The invention relates to environmental detection, in particular to an electrochemical sensor for rapid detection of sulfide with a graphene-modified electrode and its construction and application. The electrochemical sensor uses a glassy carbon electrode as a carrier, and the carrier supports 50-60 μg cm -2 of graphene as a recognition element. The present invention provides a rapid and sensitive detection technique. Moreover, compared with other electrochemical detection technologies, the detection signal intensity is significantly improved, and it has a wide linear detection range. At the same time, the construction technology of the electrochemical sensor of the present invention is convenient, and the parameters are relatively easy to control. Compared with other optical detection methods, the method of the present invention is faster and simpler, and the required equipment is simpler and the materials are cheaper.
Description
Technical field
The present invention relates to for environment measuring a kind of specifically electrochemical sensor and structure and application of Graphene modified electrode fast detecting sulfide.
Background technology
Sulfide especially sulfuretted hydrogen has very strong reactivity and toxic.The people knows from experience and feels uncomfortable when concentration of hydrogen sulfide reaches 10ppm, when concentration reaches 250ppm, just has very big harmfulness even makes the people dead.The detection method that a lot of sulfide are arranged at present, but major part is still adopting optical means and chromatographic detection method, however the time that these two class methods need is long, and the sulfide particularly volatilization of sulfuretted hydrogen can bring inevitable detection error.Long-time in addition the contact with sulfide known from experience the very big damage of generation to the people.The research that electrochemical method detects sulfide also has a lot, and the subject matter of existence is insufficient sensitivity, and it is very big that the sulfide of low concentration detects error.The potential application of grapheme material aspect sensor and biology sensor recently is by broad research.These researchs mainly are based on the excellent electrochemical properties of grapheme material, have good catalytic activity and very high electron transfer rate.Grapheme material is considered to a kind of very potential electrode modified material and is used for the Electrochemical Detection field.
Summary of the invention
The object of the invention is to provide a kind of electrochemical sensor and structure and application of Graphene modified electrode fast detecting sulfide.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of electrochemical sensor of Graphene modified electrode fast detecting sulfide: electrochemical sensor is carrier with the glass-carbon electrode, carrier loaded 50-60 μ g cm
-2Graphene as recognition component.
Said Graphene prepares as follows:
1) with 0.5-2g native graphite, 0.5-2g NaNO
3Mix with the 40-60mL concentrated sulphuric acid, stir 3-5h, add 5-7g KMnO more slowly at 0 ℃ of condition of ice bath lower magnetic force
4After remove ice bath, about under field conditions (factors) 30-40 ℃ is stirred 1-3h, add 80-100mL water slowly and under 90-100 ℃ of water-bath stirring 10-20min, add 200-300mL warm water and 10-30mL H again
2O
2, then with liquid with HCl and water centrifuge washing, promptly get graphite oxide at 40-60 ℃ of dry 24-48h;
2) taking by weighing graphite oxide 0.05-0.2g is dispersed in the 50-200mL water; The ultrasonic graphite oxide of peeling off is faint yellow colloid, adds 1-4mL hydrazine hydrate (80%) again; Boiling reflux 16-30h generates black precipitate under 100 ℃ of water-baths, and the vacuum filtration drying must be gone back ortho states Graphene powder;
3) the ortho states Graphene of going back with step 2 preparation joins in the Milli-Q water, and making and going back ortho states Graphene content is 0.5-2g/L, and sonic oscillation 20-40 minute, what obtain that black disperses homogeneous went back ortho states Graphene suspension.
Said concentrated sulphuric acid concentration is 98%.
The preparation of the electrochemical sensor of Graphene modified electrode fast detecting sulfide:
A. glass-carbon electrode is used Al
2O
3Burnishing powder, then ultrasonic cleaning is handled in Milli-Q water;
B. with 0.5-2g native graphite, 0.5-2g NaNO
3Mix with the 40-60mL concentrated sulphuric acid, stir 3-5h, add 5-7g KMnO more slowly at 0 ℃ of condition of ice bath lower magnetic force
4After remove ice bath, about under field conditions (factors) 30-40 ℃ is stirred 1-3h, add 80-100mL water slowly and under 90-100 ℃ of water-bath stirring 10-20min, add 200-300mL warm water and 10-30mL H again
2O
2, then with liquid with HCl and water centrifuge washing, promptly get graphite oxide at 40-60 ℃ of dry 24-48h;
C. taking by weighing graphite oxide 0.05-0.2g is dispersed in the 50-200mL water; The ultrasonic graphite oxide of peeling off is faint yellow colloid, adds 1-4mL hydrazine hydrate (80%) again; Boiling reflux 16-30h generates black precipitate under 100 ℃ of water-baths, and the vacuum filtration drying must be gone back ortho states Graphene powder;
D. the ortho states Graphene of going back with step c preparation joins in the Milli-Q water, and making and going back ortho states Graphene content is 0.5-2g/L, and sonic oscillation 20-40 minute, what obtain that black disperses homogeneous went back ortho states Graphene suspension;
E. ortho states Graphene modified glassy carbon electrode is gone back in preparation: the suspension 1-4 μ L that will adopt step c to be prepared drips to be coated onto and adopts the handled glass-carbon electrode of step a surface; At room temperature dry; Make solvent evaporates, promptly obtaining with the glass-carbon electrode is carrier, carrier loaded 50-60 μ g cm
-2Graphene as the electrochemical sensor of the Graphene modified electrode fast detecting sulfide of recognition component.
The application of the electrochemical sensor of Graphene modified electrode fast detecting sulfide is characterized in that: said electrochemical sensor is as using in environmental monitoring and the water analysis.Said electrochemical sensor is as using in the metabolic product that detects corrosion-causing bacteria.
The advantage that the present invention had:
Among the present invention grapheme material is modified in electrode surface, realized detection sulfide concentration through its excellent catalysis characteristics and signal amplification characteristic.It can be quick, sensitive detection sulfide, and this sulfide detection method has very wide sensing range, and the good reproducibility of detection, electrode are prone to preserve, and the detection of institute's sulfide is had tangible specificity.
Description of drawings
Fig. 1. the Graphene solution atomic force microscope phenogram that the embodiment of the invention provides.Fig. 2 is the comparison of the electrochemical properties of Graphene modified electrode and bare electrode.Fig. 3. the linear detection range figure of Graphene sensor.Fig. 4. the Interference Detection figure of other inorganic ions.
Embodiment
Through embodiment the present invention is further specified below.
Embodiment 1
The 1g native graphite, 1gNaNO
3Be blended in the 46mL concentrated sulphuric acid (98%) and react 4h in the ice-water bath.Then with 6gKMnO
4Join in the mixture solution simultaneously temperature is risen to 35 ℃ and keep temperature of reaction, reaction is carried out adding 92mlH behind the 2h
2O also rises to 98 ℃ with temperature, and reaction carries out adding after two hours 200mL warm water, the H of 20mL30%
2O
2, and at room temperature continue will remain stirring in the reaction 1h. entire reaction course.The product for preparing is filtered, after using the distilled water washing in 60 ℃ baking oven dry 24h, obtain yellow solid.With this reaction product grind broken after, take by weighing 0.1g and join ultrasonic 1h among the Milli-Q of 100mL, obtain the mixed solution of homogeneous, add 2mLN
2H
4After be divided in the agitated reactor at 121 ℃ of reaction 12h down, obtain grapheme material.
The above-mentioned Graphene that obtains is loose in the WS; The dispersion soln of getting 10 μ L drips to be coated with earlier polishes with sand paper and burnishing powder successively; Cleaning up with ultrapure water and ethanol successively, then electrode is being swept in potassium ferricyanide solution on the good glass-carbon electrode surface of reversible pre-service at N
2Dry in the stream, promptly obtain the Graphene modified glassy carbon.The electrode that obtains at last is connected with electrochemical workstation, simultaneously with the Pt silk as to electrode, the Ag/AgCl electrode is as contrast electrode.This sensor response is rapid, and has very high sensitivity.
A. at first glass-carbon electrode is used 1 μ m successively, 0.3 μ m, 0.05 μ m Al
2O
3Burnishing powder polishes on polishing cloth, and after each polishing, all ultrasonic cleaning is handled in Milli-Q water;
B. the ortho states Graphene is gone back in preparation: with 1g native graphite, 1g NaNO
3The 250mL beaker is put in mixing with the 50mL concentrated sulphuric acid, stirs 4h at 0 ℃ of condition of ice bath lower magnetic force, adds 6g KMnO more slowly
4After remove ice bath, about under field conditions (factors) 35 ℃ are stirred 2h, add 90mL water slowly and under 98 ℃ of water-baths stirring 15min, add 200mL warm water and 20mL H again
2O
2, liquid is transferred to centrifuge tube earlier with HCl and water centrifuge washing, promptly get graphite oxide at 50 ℃ of dry 48h.Take by weighing graphite oxide 0.1g and be dispersed in and be placed with in the 100mL water beaker, the ultrasonic graphite oxide of peeling off is faint yellow colloid; Move into the 250mL there-necked flask again; Add 2mL hydrazine hydrate (80%), boiling reflux 24h generates black precipitate under 100 ℃ of water-baths, and the vacuum filtration drying must be gone back ortho states Graphene powder.
C. the ortho states Graphene of going back with step b preparation joins in the Milli-Q water, and making and going back ortho states Graphene content is 2g/L, sonic oscillation 20 minutes, and what obtain that black disperses homogeneous goes back ortho states Graphene suspension;
D. ortho states Graphene modified glassy carbon electrode is gone back in preparation: will adopt suspension that step c prepared to pipette 2 μ L with micro syringe and drip to be coated onto and adopt the handled glass-carbon electrode of step a surperficial; At room temperature dry, make solvent evaporates prepare gained Graphene modified glassy carbon electrode.
Embodiment 3
According to the sensor that makes up among the embodiment (1); Simultaneously with Graphene modified glassy carbon or exposed glass-carbon electrode as working electrode; The conduct of Pt silk is to electrode; The Ag/AgCl electrode is as contrast electrode, and research sulfide at first leads to N in the electrochemical behavior (see figure 2) of grapheme material modified electrode with the glass-carbon electrode that exposes in the PBS damping fluid in the PBS damping fluid
2Discharge the air in the solution in 15 minutes, and afterwards electrode was connected with electrochemical workstation, adopt electrochemical cyclic voltammetry (0.6-0.8V, stand-by period 2s, sweep velocity 100mV s
-1) electrochemical behavior of research sulfide on Graphene modified electrode and exposed glass-carbon electrode.By can finding out among the figure, grapheme material is modified the oxidation that rear electrode can catalysis sulfide, and significantly promotes oxidation current signal (about 80 μ A).
Embodiment 4
Adopt the prepared sensor of the foregoing description; Simultaneously with the Graphene modified glassy carbon as working electrode; The conduct of Pt silk is to electrode, and the Ag/AgCl electrode changes the pH value that detects used sweep velocity and detect solution the oxidation mechanism of sulfide is studied as contrast electrode.At first in the PBS damping fluid, lead to N
2Discharged the air in the solution in 15 minutes; Afterwards electrode is connected with electrochemical workstation; Adopt research electrochemical cyclic voltammetry (0.6-0.8V; Stand-by period 2s) in different scanning speed the influence of oxidation current and the pH value of PBS damping fluid are studied its oxidation mechanism the influence of spike potential.Electrochemical sensor mechanism to sulfide oxidation in alkaline solution that this Graphene is modified is divided into two types: the oxidation mechanism of sulfide is HS when low concentration (being lower than 450 μ M)
-→ S+H
++ 2e
-Oxidation mechanism at high concentration sulfide when (being higher than 550 μ M) is HS
-→ H
++ 1/2S
2 2-+ e
-
Adopt the foregoing description to prepare a series of sulfide concentration of sensor of gained.At first in the PBS damping fluid, lead to N
2Discharged the air in the solution in 15 minutes; Afterwards in containing without the PBS damping fluid of concentration sulfide with the Graphene modified glassy carbon as working electrode; The conduct of Pt silk is to electrode, and the Ag/AgCl electrode is connected with electrochemical workstation as contrast electrode, adopts electrochemical cyclic voltammetry (0.6-0.8V; Stand-by period 2s, sweep velocity 100mV s
-1), analyze sulfide concentration from 0.05 to 1.15 * 10
4The oxidation current of sulfide and the relation between the sulfide concentration between the μ M find that it is 5 to 7.4 * 10 that electrochemical sensor that this Graphene is modified detects the range of linearity that obtains
3μ M has very wide linear detection range.(see figure 3)
Embodiment 6
Adopt the foregoing description to prepare the sensor of gained, the while, as working electrode, the conduct of Pt silk was to electrode with the Graphene modified glassy carbon, and the Ag/AgCl electrode at first leads to N as contrast electrode in the PBS damping fluid
2Discharge the air in the solution in 15 minutes, and afterwards electrode was connected with electrochemical workstation, adopt galvanochemistry time current curve method to judge the selectivity of its detection; At voltage is under the 0.16V, through adding other interference inorganic ions (inferior sulfate radical, sulfate radicals; Thiosulfate anion, carbonate, nitrate radical) find that current signal changes not quite; And after the sulfide solution that adds same concentrations, electric current increases sharply.The electrochemical sensor that this explanation grapheme material is modified has good detection selectivity.(see figure 4)
Claims (7)
1. the electrochemical sensor of a Graphene modified electrode fast detecting sulfide, it is characterized in that: electrochemical sensor is carrier with the glass-carbon electrode, carrier loaded 50-60 μ g cm
-2Graphene as recognition component.
2. by the electrochemical sensor of the described Graphene modified electrode of claim 1 fast detecting sulfide, it is characterized in that: said Graphene prepares as follows:
1) with 0.5-2g native graphite, 0.5-2g NaNO
3Mix with the 40-60mL concentrated sulphuric acid, stir 3-5h, add 5-7g KMnO more slowly at 0 ℃ of condition of ice bath lower magnetic force
4After remove ice bath, about under field conditions (factors) 30-40 ℃ is stirred 1-3h, add 80-100mL water slowly and under 90-100 ℃ of water-bath stirring 10-20min, add 200-300mL warm water and 10-30mL H again
2O
2, then with liquid with HCl and water centrifuge washing, promptly get graphite oxide at 40-60 ℃ of dry 24-48h;
2) taking by weighing graphite oxide 0.05-0.2g is dispersed in the 50-200mL water; The ultrasonic graphite oxide of peeling off is faint yellow colloid, adds 1-4mL hydrazine hydrate (80%) again; Boiling reflux 16-30h generates black precipitate under 100 ℃ of water-baths, and the vacuum filtration drying must be gone back ortho states Graphene powder;
3) the ortho states Graphene of going back with step 2 preparation joins in the Milli-Q water, and making and going back ortho states Graphene content is 0.5-2g/L, and sonic oscillation 20-40 minute, what obtain that black disperses homogeneous went back ortho states Graphene suspension.
3. by the electrochemical sensor of the described Graphene modified electrode of claim 2 fast detecting sulfide, it is characterized in that: said concentrated sulphuric acid concentration is 98%.
4. the preparation of the electrochemical sensor of the described Graphene modified electrode of claim 1 a fast detecting sulfide is characterized in that:
A. glass-carbon electrode is used Al
2O
3Burnishing powder, then ultrasonic cleaning is handled in Milli-Q water;
B. with 0.5-2g native graphite, 0.5-2g NaNO
3Mix with the 40-60mL concentrated sulphuric acid, stir 3-5h, add 5-7g KMnO more slowly at 0 ℃ of condition of ice bath lower magnetic force
4After remove ice bath, about under field conditions (factors) 30-40 ℃ is stirred 1-3h, add 80-100mL water slowly and under 90-100 ℃ of water-bath stirring 10-20min, add 200-300mL warm water and 10-30mL H again
2O
2, then with liquid with HCl and water centrifuge washing, promptly get graphite oxide at 40-60 ℃ of dry 24-48h;
C. taking by weighing graphite oxide 0.05-0.2g is dispersed in the 50-200mL water; The ultrasonic graphite oxide of peeling off is faint yellow colloid, adds 1-4mL hydrazine hydrate (80%) again; Boiling reflux 16-30h generates black precipitate under 100 ℃ of water-baths, and the vacuum filtration drying must be gone back ortho states Graphene powder;
D. the ortho states Graphene of going back with step c preparation joins in the Milli-Q water, and making and going back ortho states Graphene content is 0.5-2g/L, and sonic oscillation 20-40 minute, what obtain that black disperses homogeneous went back ortho states Graphene suspension;
E. ortho states Graphene modified glassy carbon electrode is gone back in preparation: the suspension 1-4 μ L that will adopt step c to be prepared drips to be coated onto and adopts the handled glass-carbon electrode of step a surface; At room temperature dry; Make solvent evaporates, promptly obtaining with the glass-carbon electrode is carrier, carrier loaded 50-60 μ g cm
-2Graphene as the electrochemical sensor of the Graphene modified electrode fast detecting sulfide of recognition component.
5. press the preparation of the electrochemical sensor of the described Graphene modified electrode of claim 4 fast detecting sulfide, it is characterized in that: said concentrated sulphuric acid concentration is 98%.
6. the application of the electrochemical sensor of the described Graphene modified electrode of claim 1 a fast detecting sulfide, it is characterized in that: said electrochemical sensor is as using in environmental monitoring and the water analysis.
7. the application of the electrochemical sensor of the described Graphene modified electrode of claim 1 a fast detecting sulfide is characterized in that: said electrochemical sensor is as using in the metabolic product that detects corrosion-causing bacteria.
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| CN103424447A (en) * | 2013-08-22 | 2013-12-04 | 中国科学院上海微系统与信息技术研究所 | Nano-particle enhancement detection device based on non-modified monolayer graphene being used as working electrode and application thereof |
| CN115078773A (en) * | 2022-05-30 | 2022-09-20 | 华东师范大学 | Ultrafast atomic force microscope system |
| CN117929677A (en) * | 2024-03-20 | 2024-04-26 | 普利莱（天津）燃气设备有限公司 | Multifunctional natural gas odorizing agent concentration analyzer and analysis method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102910621A (en) * | 2012-10-23 | 2013-02-06 | 上海乘鹰新材料有限公司 | Preparation methods and applications of multilayer graphene and multilayer graphene modified electrode |
| CN102910621B (en) * | 2012-10-23 | 2015-05-13 | 上海乘鹰新材料有限公司 | Preparation methods and applications of multilayer graphene and multilayer graphene modified electrode |
| CN103424447A (en) * | 2013-08-22 | 2013-12-04 | 中国科学院上海微系统与信息技术研究所 | Nano-particle enhancement detection device based on non-modified monolayer graphene being used as working electrode and application thereof |
| CN103424447B (en) * | 2013-08-22 | 2015-05-13 | 中国科学院上海微系统与信息技术研究所 | Nano-particle enhancement detection device based on non-modified monolayer graphene being used as working electrode and application thereof |
| CN115078773A (en) * | 2022-05-30 | 2022-09-20 | 华东师范大学 | Ultrafast atomic force microscope system |
| CN117929677A (en) * | 2024-03-20 | 2024-04-26 | 普利莱（天津）燃气设备有限公司 | Multifunctional natural gas odorizing agent concentration analyzer and analysis method |
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