CN101792137B - Method for preparing novel high-performance composite nanometer material modified electrode - Google Patents
Method for preparing novel high-performance composite nanometer material modified electrode Download PDFInfo
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- CN101792137B CN101792137B CN2010100308442A CN201010030844A CN101792137B CN 101792137 B CN101792137 B CN 101792137B CN 2010100308442 A CN2010100308442 A CN 2010100308442A CN 201010030844 A CN201010030844 A CN 201010030844A CN 101792137 B CN101792137 B CN 101792137B
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Abstract
The invention belongs to the technology for preparing a graphene and prussian blue composite nanometer sheet material modified electrode and particularly relates to a method for preparing the graphene and prussian blue composite nanometer sheet material modified electrode by utilizing a simple wet chemical method. The method has the advantages of simple operation, low cost, large specific surface area of the prepared material, good dispersibility and the like. The invention uses graphite, ferric chloride, potassium ferricyanate and potassium chloride as the raw materials and adopts the wet chemical method to prepare a graphene/prussian blue composite nanometer sheet. The invention utilizes the reduction performance of the graphene sheet so as to directionally load prussian blue on the surface of the graphene sheet. An H2O2 electrochemical sensor with better response recovery, high sensitivity and low detection limit can be prepared by the method. The method has the advantages of simple operation, low cost, high performance, easy popularization and the like and can meet the wide application in the fields of chemistry, clinical medicine, biomedicine and the like.
Description
Technical field
The invention belongs to the technology of preparing of Graphene and Prussian blue composite Nano sheet material modified electrode, be specifically related to a kind of method of utilizing simple wet chemistry method to prepare Graphene and Prussian blue composite Nano sheet material modified electrode.
Background technology
Graphene (graphene) is just found in recent years a kind of novel carbonaceous material, and it is a kind of novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline network.Graphene has excellent electric property, is expected to be used widely in fields such as the high-performance nanometer electronic device and the energy, therefore from beginning to occur just having caused the extensive concern of scientists.Therefore graphene-based matrix material has also obtained deep research owing to combine Graphene and the common advantage of other material.For example that Graphene and polymkeric substance is compound, can improve the mechanical property of polymkeric substance.Graphene and metal nanoparticle is compound, can be used for fuel-cell catalyst or the like.Prussian blue is a class important functional material, nanoscale Prussian blue to H
2O
2Have extraordinary selective reduction, therefore in various chemistry and biosensor, be widely used in H
2O
2Detection.But the control that how to realize the prussian blue nano yardstick is synthetic, thereby and how becomes more and more important now with mutually compound its performance as biosensor that improves of other functional material with nanoscale is Prussian blue.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing wet chemistry method to prepare Graphene and Prussian blue composite Nano sheet material modified electrode.
The research of Graphene and inorganic nano composite material recently attracts much attention gradually, this is because conductive graphene and inorganic nano composite material not only can be in conjunction with both excellent properties in one, and may be because synergy between the two produces some new properties that neither possess.
We adopt simple wet chemistry method to prepare a kind of novel graphene-based matrix material---Graphene and Prussian blue composite nano plate in the aqueous solution.The novelty of this material is Graphene for its component and Prussian bluely is combined with each other preferably that whole pattern with nanometer sheet exists.This method is simple, and production cost is low, and the Graphene of output and Prussian blue composite nano plate have good advantages such as dispersiveness in multiple solvent.The present invention utilize Prussian blue in Graphene and the Prussian blue composite nano plate can be to H
2O
2Advantages such as it is good in conjunction with graphene conductive to have the electrocatalysis response, and specific surface area is big are prepared modified electrode easy to use.Electrode preparation method is simple, and is highly sensitive.
Wet chemistry method prepares Graphene and Prussian blue composite Nano sheet material modified electrode, and it comprises the steps:
A. prepare graphite oxide, then graphite oxide is dispersed in the solution that is mixed with 1～5mg/mL in the water, ultrasonic 8～10h, add sodium polystyrene sulfonate then, make its concentration reach 10～20mg/mL, add 10～20mL hydrazine hydrate again, under 85～95 ℃ of conditions, stir 24～60h then, centrifugation is washed with water to pH=6～8, and the aqueous dispersions that then it is mixed with 15～30mL is stand-by;
B. prepare Prussian bluely, dispersion liquid 0.04～0.4mL that steps A is obtained joins in the above-mentioned solution then, stirring at room reaction 12～24h; Centrifugation, water and ethanol wash respectively, and drying obtains Graphene and Prussian blue composite nano plate;
C. the product ultra-sonic dispersion that step B is obtained is configured to the alcohol dispersion liquid that contains Graphene and Prussian blue composite nano plate that concentration is 0.5～2.0mg/mL in ethanol, get the above-mentioned alcohol dispersion liquid of 5～10 μ L with microsyringe and be added drop-wise to the glass-carbon electrode surface of having polished, the perfluorinated sulfonic acid solution that adds 2～4 μ L, 0.5wt% then treats that ethanol at room temperature obtains containing Graphene and Prussian blue composite Nano sheet modified electrode after the volatilization fully.
Further, prepare graphite oxide in the steps A, be with 0.1～1.0g graphite and 0.1～1.0g SODIUMNITRATE join 4～40mL, concentration is in the vitriol oil of 95wt%～98wt%, stir down at 0 ℃～4 ℃, add 0.6～6g potassium permanganate again, under 35～40 ℃ of conditions, stir 1～2h; In above-mentioned solution, add 8～80mL water then, stir 30～60min under 90～95 ℃ of conditions; In above-mentioned solution, add 20～200mL water, the H of 0.6～6mL, 30wt% then again
2O
2, suction filtration, washing to pH value of solution=6.5～7.5, thereby obtains graphite oxide.The described preparation of step B is Prussian blue, is the hydrochloric acid soln 20～100mL of preparation pH=1.0～2.0, adds 0.02～0.15g FeCl then
36H
2O, 0.02～0.2g K
3Fe (CN)
6, 0.07～0.7g KCl, thereby obtain Prussian blue.
Used graphite and iron trichloride can be buied from Chemical Reagent Co., Ltd., Sinopharm Group in the inventive method, and the Tripotassium iron hexacyanide can be recovered fine chemistry industry institute and buied from Tianjin, and Repone K can be buied from northization glass purchase and sale center, Tianjin.
Mechanism of the present invention can be done following understanding:
1. the formation mechanism of Graphene and Prussian blue composite Nano sheet material: under normal circumstances, FeCl
3Can not with K
3Fe (CN)
6Reaction generates Prussian blue.Under the condition that Graphene exists, electronics can be transferred to FeCl from Graphene
3On, thereby generated Fe
2+, Fe
2+With K
3Fe (CN)
6Reaction can generate Prussian blue.Because Fe
2+Can only be formed at the surface of graphene film, therefore the Prussian blue surface that also just has been formed on graphene film.Pattern (as shown in Figure 1) with transmission electron microscope (TEM) observation product has also confirmed this formation mechanism.
2. the principle of work of Graphene and Prussian blue composite Nano sheet material modified electrode: Prussian blue modified electrode is used to detect H
2O
2Electrochemical process be: the Prussian blue electronics that on electrode, obtains, it is white to generate the Prussian, the Prussian is in vain again by the H in the solution
2O
2Be oxidized to Prussian blue.Wherein electron gain is a fast response from the electrode, the speed of decision entire electrode reaction.The introducing of Graphene helps electron transport, reduces overpotential Prussian blue and the white conversion in Prussian, improves the accuracy and the measurement range that detect.
The modified electrode that present method obtains, it is simple to have the preparation method, highly sensitive and advantage such as repeat, to H
2O
2Have stable electrocatalysis response, can be used as hydrogen peroxide electrochemical sensor modified electrode, can all have broad application prospects, obtain promotion and application easily in many fields such as chemistry, clinical medicine and biomedicines.
Description of drawings
Fig. 1: be the transmission electron microscope photo of Graphene and Prussian blue composite nano plate product;
Fig. 2: be the infrared spectra of Graphene and Prussian blue composite nano plate product;
Fig. 3: be the X-ray diffraction spectrogram of Graphene and Prussian blue composite nano plate (a) and Graphene (b);
Fig. 4: embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode are at 0.1MH
3PO
4, contain different concns H in the 1.0M KCl aqueous solution
2O
2The CV curve;
Fig. 5: embodiment 4 obtained Graphenes and Prussian blue composite Nano sheet modified electrode be at-0.05V, under the agitation condition to 5mL0.1M H
3PO
4With the continuous 1 μ L 100mM H that adds in the 1.0M KCl mixed aqueous solution
2O
2The i-t curve;
Fig. 6: electric current is to H among Fig. 5
2O
2The calibration curve of concentration;
Fig. 7: embodiment 4 obtained Graphenes and Prussian blue composite Nano sheet modified electrode are at 0.1MH
3PO
4, the CV curve in the 1.0M KCl aqueous solution under the different scanning speed;
Fig. 8: electric current is to the curve of sweep velocity evolution among Fig. 7;
Fig. 9: embodiment 4 obtained Graphenes and Prussian blue composite Nano sheet modified electrode resist the anti-interference curve of bad hematic acid, citric acid and halfcystine;
As shown in Figure 1, embodiment 3 prepared Graphenes and Prussian blue composite nano plate transmission electron microscope photo, the composite nano plate pattern that makes of the present invention is good as can be seen, and the prussian blue nano particle is covering on graphene film uniformly.
As shown in Figure 2, embodiment 3 prepared Graphenes and Prussian blue composite nano plate infrared spectra utilize present method can realize the compound of Prussian blue and graphene film as can be seen.
As shown in Figure 3, embodiment 2 and embodiment 3 prepared Graphenes and Graphene and Prussian blue composite nano plate X-ray diffraction spectrum, utilize the Prussian blue and graphene film matrix material of present method preparation Prussian blue characteristic X-ray diffraction peak to occur as can be seen, prove generated Prussian blue.
As shown in Figure 4, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode are containing the H of different concns
2O
20.1M H
3PO
4, the CV curve in the 1.0M KCl aqueous solution: 0,0.1,0.5,1,2mM.Response current is with H as can be seen
2O
2The increase of concentration and increasing.
As shown in Figure 5, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode be at-0.05V, under the agitation condition to 5mL 0.1M H
3PO
4, add 1 μ L 100mM H in the 1.0M KCl aqueous solution continuously
2O
2The i-t curve.Response current is with H as can be seen
2O
2The increase of concentration and linear increasing.
As shown in Figure 6, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode electric current are to H
2O
2The calibration curve of concentration.H as can be seen
2O
2Concentration when being 0.02～0.2mM, follow the linear relationship that slope is 13.89848 μ A/mM, R
2=0.99846.Under the S/N=3 situation, detecting that it is minimum is limited to 1.94 μ M.
As shown in Figure 7, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode are at 0.1M H
3PO
4, the CV curve in the 1.0M KCl aqueous solution under the different scanning speed: 40,60,80,100,120,140,160,180,200,220mV/s; Response current increases with the increase of sweep velocity as can be seen.
As shown in Figure 8, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode are at 0.1M H
3PO
4, the electric current in the 1.0M KCl aqueous solution under the different scanning speed is to the curve of sweep velocity evolution.Response current and sweep velocity extraction of square root is linear as can be seen, selects different scanning speed to H
2O
2Carry out METHOD FOR CONTINUOUS DETERMINATION, its reduction process is carried out in the diffusion control mode.
As shown in Figure 9, embodiment 4 prepared Graphenes and Prussian blue composite Nano sheet modified electrode resist the anti-interference curve of bad hematic acid, citric acid and halfcystine.Illustrate that Graphene and Prussian blue composite Nano sheet modified electrode are to H
2O
2Catalytic reduction have selectivity.
Embodiment
1, utilize wet chemistry method to prepare Graphene and Prussian blue composite nano plate
Embodiment 1:
With 0.5g graphite and 0.5g SODIUMNITRATE join 23mL, concentration is in the vitriol oil of 98wt%, stirs down at 0 ℃, slowly adds 3g potassium permanganate then, stirs 1h under 35 ℃ of conditions.In above-mentioned solution, add 40mL water then, stir 30min under 90 ℃ of conditions.In above-mentioned solution, add 100mL water, 3mLH then again
2O
2(30wt%).Suction filtration is washed then, to pH value of solution=7, obtains graphite oxide.
Embodiment 2:
Graphite oxide is dispersed in the solution that is mixed with 1mg/mL in the water, and ultrasonic 8h adds sodium polystyrene sulfonate then and makes its concentration reach 10mg/mL, adds the 10mL hydrazine hydrate, stirs 48h then under 85 ℃ of conditions.Centrifugation is washed with water to pH=7～8.The aqueous dispersions that then it is mixed with 15mL is stand-by.
Embodiment 3:
The hydrochloric acid soln 50mL of configuration pH=1.5 adds 0.065g iron trichloride (FeCl
36H
2O), 0.084g potassium ferricyanate (K
3Fe (CN)
6), 0.372g Repone K (KCl).The dispersion liquid taking-up 0.2mL that embodiment 2 is obtained joins in the above-mentioned solution, stirring at room reaction 12h.Centrifugation, water and ethanol wash respectively, and drying obtains Graphene and Prussian blue composite nano plate.
2, utilize chemical method to prepare Graphene and Prussian blue composite Nano sheet modified electrode
Embodiment 4:
It is the alcohol dispersion liquid that 1.0mg/mL contains Graphene and Prussian blue composite nano plate that the product ultra-sonic dispersion that embodiment 3 is obtained is configured to concentration in the 10mL ethanol.Get the above-mentioned dispersant liquid drop of 5 μ L with microsyringe and be added to the glass-carbon electrode surface of having polished, perfluorinated sulfonic acid (the Nafion that adds 2 μ L then, 0.5wt%) solution treats that ethanol at room temperature obtains containing Graphene and Prussian blue composite Nano sheet modified electrode after the volatilization fully.
Preparation 0.1M H
3PO
4With the blended aqueous solution of 1.0M KCl, add the H of different concns
2O
2Solution, H
2O
2Concentration be 0mM, 0.1mM, 0.5mM, 1mM, 2mM carries out CV test.Response current is with H
2O
2The increase of concentration and increasing illustrates that the Graphene of gained and Prussian blue composite Nano sheet modified electrode are to H
2O
2Have good electrocatalysis response, repeatability is good.
Containing 0.2mM H
2O
2Preparation 0.1M H
3PO
4, in the 1.0M KCl aqueous solution, select different scanning speed to H
2O
2The aqueous solution carries out METHOD FOR CONTINUOUS DETERMINATION, and its reduction process is carried out in the diffusion control mode.H
2O
2Concentration when being 0.02～0.2mM, follow the linear relationship that slope is 13.89848 μ A/mM, R
2=0.99846.Under the S/N=3 situation, detecting that it is minimum is limited to 1.94 μ M.
Embodiment 5:
Graphene and Prussian blue composite Nano sheet modified electrode that embodiment 4 is obtained are used for carrying out containing H
2O
2, xitix, citric acid and halfcystine solution carry out the CV test.Detailed process is: preparation 0.1M H
3PO
4With the blended aqueous solution of 1.0M KCl, the modified electrode that embodiment 4 is obtained carries out the CV test in this solution, as shown in Figure 9, add the H of 5 μ L, 100mM when 50s
2O
2Solution (A), the ascorbic acid solution (B) that when 120s, adds 5 μ L, 100mM, the citric acid solution (C) that adds 5 μ L, 100mM when 160s adds the halfcystine solution (D) of 5 μ L, 100mM when 200s, add the H of 5 μ L, 100mM when 260s again
2O
2Solution (A).By these three kinds and H in the body fluid
2O
2The material of coexistence shows and has only adding H in the effect of electrode surface as can be seen
2O
2Just there is tangible electric current to raise during solution, illustrates that modified electrode is only to H
2O
2Have the electrical catalyze reduction effect, illustrated that also Graphene and Prussian blue composite Nano sheet modified electrode are to H simultaneously
2O
2Catalytic reduction have selectivity.
Claims (3)
1. method for preparing Graphene and Prussian blue composite Nano sheet material modified electrode, it comprises the steps:
A. prepare graphite oxide, then graphite oxide is dispersed in the solution that is mixed with 1～5mg/mL in the water, ultrasonic 8～10h, add sodium polystyrene sulfonate then, make its concentration reach 10～20mg/mL, add 10～20mL hydrazine hydrate again, under 85～95 ℃ of conditions, stir 24～60h then, centrifugation is washed with water to pH=6～8, and the aqueous dispersions that then it is mixed with 15～30mL is stand-by;
B. prepare Prussian blue solution, dispersion liquid 0.04～0.4mL that steps A is obtained joins in the above-mentioned solution then, stirring at room reaction 12～24h; Centrifugation, water and ethanol wash respectively, and drying obtains Graphene and Prussian blue composite nano plate;
C. the product ultra-sonic dispersion that step B is obtained is configured to the alcohol dispersion liquid that contains Graphene and Prussian blue composite nano plate that concentration is 0.5～2.0mg/mL in ethanol, get the above-mentioned alcohol dispersion liquid of 5～10 μ L with microsyringe and be added drop-wise to the glass-carbon electrode surface of having polished, the perfluorinated sulfonic acid solution that adds 2～4 μ L, 0.5wt% then treats that ethanol at room temperature obtains containing Graphene and Prussian blue composite Nano sheet modified electrode after the volatilization fully.
2. a kind of method for preparing Graphene and Prussian blue composite Nano sheet material modified electrode as claimed in claim 1, it is characterized in that: prepare graphite oxide in the steps A, be with 0.1～1.0g graphite and 0.1～1.0g SODIUMNITRATE join 4～40mL, concentration is in the vitriol oil of 95wt%～98wt%, stir down at 0 ℃～4 ℃, add 0.6～6g potassium permanganate again, under 35～40 ℃ of conditions, stir 1～2h; In above-mentioned solution, add 8～80mL water then, stir 30～60min under 90～95 ℃ of conditions; In above-mentioned solution, add 20～200mL water, the H of 0.6～6mL, 30wt% then again
2O
2, suction filtration, washing to pH value of solution=6.5～7.5, thereby obtains graphite oxide.
3. a kind of method for preparing Graphene and Prussian blue composite Nano sheet material modified electrode as claimed in claim 1, it is characterized in that: the Prussian blue solution of the described preparation of step B, be the hydrochloric acid soln 20～100mL of preparation pH=1.0～2.0, add 0.02～0.15g FeCl then
36H
2O, 0.02～0.2gK
3Fe (CN)
6, 0.07～0.7g KCl, thus Prussian blue solution obtained.
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| CN102288669B (en) * | 2011-05-04 | 2013-06-26 | 青岛大学 | Electrochemical method based on graphene-modified electrode for simultaneous determination of rutin and quercetin |
| CN102443285B (en) * | 2011-09-05 | 2013-07-24 | 福州坤彩精化有限公司 | Prussian blue pearlescent pigment and preparation method thereof |
| CN102507693A (en) * | 2011-11-03 | 2012-06-20 | 桂林医学院 | Functional-material-based glucose biosensor and manufacturing method thereof |
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| CN102824883B (en) * | 2012-08-27 | 2014-11-05 | 北京理工大学 | Composite aerogel of graphene/Prussian-blue complexes, and preparation method and application thereof |
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| CN105842438B (en) * | 2016-03-28 | 2017-12-29 | 南京邮电大学 | A kind of preparation method of Prussian blue cubic block/molybdenum disulfide nano-composite material |
| CN109065847B (en) * | 2018-05-25 | 2020-10-23 | 浙江大学 | Prussian white composite material and preparation method and application thereof |
| CN110652981B (en) * | 2018-06-29 | 2022-05-31 | 天津大学 | Application of RCW nanosheet modified carbon felt material as cathode in degradation of CIP |
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| CN111487299A (en) * | 2020-05-15 | 2020-08-04 | 宿州学院 | Preparation method of AuNWs @ PB nanocomposite and modified electrode |
| CN112240899B (en) * | 2020-08-25 | 2023-03-31 | 兰州大学 | Prussian blue/molybdenum selenide-based dopamine sensor material and preparation method thereof |
| CN112014447A (en) * | 2020-08-31 | 2020-12-01 | 南京工业大学 | Simple preparation method of sucrose biosensor |
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