CN104947134B - Preparation method of porous graphene - Google Patents
Preparation method of porous graphene Download PDFInfo
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- CN104947134B CN104947134B CN201510406071.6A CN201510406071A CN104947134B CN 104947134 B CN104947134 B CN 104947134B CN 201510406071 A CN201510406071 A CN 201510406071A CN 104947134 B CN104947134 B CN 104947134B
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Abstract
The invention relates to a preparation method of porous graphene. The method includes the steps of dispersing graphene and graphene oxide in a phosphate buffer to obtain a mixture of graphene and graphene oxide, and conducting cyclic voltammetry scan on the mixture of graphene and graphene oxide through a three-electrode system so that a working electrode for decorating the porous graphene can be obtained, that is, the porous graphene can be obtained on the working electrode. The method is easy to operate, few in steps, rapid and low in cost.
Description
Technical field
The present invention relates to the method for preparing Graphene, particularly a kind of method for preparing porous graphene.
Background technology
Graphene is a kind of two-dimentional material with carbon element, is the general designation of single-layer graphene, bilayer graphene and few layer graphene, due to
Its excellent electronics, mechanically and thermally stability, in the side such as battery, ultracapacitor, electronic device, sensor and composite
The application in face has obtained the extensive concern of people.
Graphene oxide (graphene oxide) is the oxide of Graphene, and on graphene oxide, oxygen-containing functional group increases
Make its property more active than Graphene more.
Porous graphene is a kind of Graphene of three-dimensional structure, as which has the specific surface area bigger compared with Graphene, is had
Beneficial to load capacity and catalysis；Its loose structure is favorably improved material mass transfer, rapidly becomes battery, ultracapacitor, electricity at present
The study hotspot of the aspects such as sub- device, sensor and composite.
The method for preparing porous graphene at present mainly has：Solution self-assembly method, interface self-assembly method, template mediation synthesis
The methods such as method, but these method operations are more complicated, and condition is difficult to be precisely controlled.
The content of the invention
Based on this, the present invention provides a kind of simple to operate, step few, quick, inexpensive side for preparing porous graphene
Method.
The preparation method of porous graphene of the present invention, including step：
Graphene and graphene oxide are dispersed in phosphate buffer solution, the mixing of Graphene and graphene oxide is obtained
Liquid；
With first electrode as working electrode, the mixed liquor of the Graphene and graphene oxide is entered using three-electrode system
Row cyclic voltammetry scan, obtains the working electrode of porous graphene modification, obtains final product porous graphene.
The preparation method of above-mentioned porous graphene, is made in Graphene and graphene oxide liquid mixture using electrochemical method
Graphene oxide is reduced to Graphene, while obtaining porous graphene, operating procedure letter with original Graphene reconstruct in mixed liquor
Single, efficiency high, environmental protection, the porous graphene specific surface area for obtaining are big, and activity is high.
Wherein, the pH value of the phosphate buffer solution is 4-6.
Wherein, the first electrode is gold electrode, platinum electrode, glass-carbon electrode, graphite electrode, carbon fiber electrode, carbon cloth electricity
Any one in pole and carbon paste electrode.
Wherein, the Graphene be Graphene, by chemical reducing agent or biological reductant scene in situ oxygen reduction in real time
Any one in the Graphene that graphite alkene is obtained.
Wherein, it is described with first electrode as working electrode, using three-electrode system to the Graphene and graphene oxide
Mixed liquor be circulated voltammetric scan, the working electrode for obtaining porous graphene modification is concretely comprised the following steps：
The mixed liquor of the Graphene and graphene oxide is added drop-wise in the first electrode, is dried, then with described the
One electrode be working electrode, to electrode be platinum plate electrode, reference electrode be saturated calomel electrode, be placed in blank phosphate buffer solution
（PH value is 4-6）In be circulated voltammetric scan, obtain the working electrode of porous graphene modification.
Wherein, voltammetric scan is circulated to the mixed liquor of the Graphene and graphene oxide using three-electrode system,
The concrete steps for obtaining the working electrode of porous graphene modification are alternatively：
With first electrode as working electrode, to electrode as platinum plate electrode, reference electrode as saturated calomel electrode, be placed in described
Voltammetric scan is circulated in the mixed liquor of Graphene and graphene oxide, the work electricity of the porous graphene modification is obtained
Pole.
Wherein, it is described with first electrode as working electrode, using three-electrode system to the Graphene and graphene oxide
Mixed liquor be circulated voltammetric scan scanning current potential be 0 V to -2.0 V, sweep speed is 10-500mV/s.
The preparation method of above-mentioned porous graphene, is made in Graphene and graphene oxide liquid mixture using electrochemical method
Graphene oxide is reduced to Graphene, while obtaining porous graphene, operating procedure letter with original Graphene reconstruct in mixed liquor
Single, efficiency high, environmental protection, the porous graphene specific surface area for obtaining are big, and activity is high.
Description of the drawings
The step of Fig. 1 is the preparation method of the porous graphene of embodiment schematic diagram；
Scanning electron microscope (SEM) photographs of the Fig. 2 for porous graphene obtained in embodiment 1.
Specific embodiment
For the ease of understanding the present invention, the present invention is more fully retouched below with reference to related embodiment and accompanying drawing
State.Shown below is the preferred embodiment of the present invention.But, the present invention can be realized in many different forms, not
It is limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make the reason to the disclosure
Solution is more thorough comprehensive.
Reference Fig. 1, a kind of preparation method of porous graphene of the invention, including：
Step S100：By graphene oxide and graphene dispersion in phosphate buffer solution, Graphene and oxidation stone is obtained
The mixed liquor of black alkene.
Wherein in one embodiment, step S100 is specially：Graphene and graphene oxide are dispersed in into phosphoric acid buffer
In solution, concentration of the Graphene in phosphate buffer solution is 1mg/mL, and graphene oxide and Graphene are in phosphate buffer solution
In concentration ratio be 1:50-5:1, obtain the mixed liquor of Graphene and graphene oxide.
Wherein in one embodiment, the pH value of phosphate buffer solution is 4-6.
Wherein in one embodiment, graphene oxide is prepared using Hummers methods, and Hummers methods prepare graphite oxide
Alkene is classical way, the graphene oxide reliable in quality of preparation.Graphene is the oxygen prepared by hydrazine hydrate reduction Hummers methods
Graphite alkene is obtained, this method be classical way, the Graphene reliable in quality of preparation.
Step S200：With first electrode as working electrode, Graphene and graphene oxide are mixed using three-electrode system
Close liquid and be circulated voltammetric scan, obtain the working electrode of porous graphene modification.
Step S200 in cyclic voltammetry scan scans the reduction potential that current potential reaches graphene oxide, subsequently repeatedly follows
Ring voltammetric scan obtains the working electrode of porous graphene modification.
Wherein in one embodiment, first electrode is gold electrode, platinum electrode, glass-carbon electrode, graphite electrode, carbon fiber electrically
Any one in pole, carbon cloth electrode and carbon paste electrode.
Preferably, first electrode is glass-carbon electrode.Wherein in one embodiment, glass-carbon electrode is used on polishing cloth oxygen
Change aluminium powder to be polished, cleaned in ultrasonic cleaner with absolute ethyl alcohol and water successively standby.
Wherein in one embodiment, step S200 is concretely comprised the following steps：By Graphene and the mixed liquor of graphene oxide
Be added drop-wise in first electrode, be dried, then with first electrode as working electrode, to electrode as platinum plate electrode, reference electrode is as saturation
Calomel electrode, is placed in 0.1M blank phosphate buffer solutions（PH value is 4-6）In be circulated voltammetric scan, obtain porous graphene
The working electrode of modification.
Wherein, wherein in one embodiment, the electrolyte solution in step S200 is phosphate buffer solution.Preferred phosphorus
The concentration of acid buffering solution is 0.1mol/L.
In another embodiment, step S200 is concretely comprised the following steps：With first electrode as working electrode, to electrode as platinum
Plate electrode, reference electrode are saturated calomel electrode, are placed in and are circulated volt-ampere in the mixed liquor of Graphene and graphene oxide and sweep
Retouch, obtain the working electrode of porous graphene modification.
Wherein in one embodiment, with first electrode as working electrode, using three-electrode system to Graphene and oxidation
It is 0 V to -2.0 V that the mixed liquor of Graphene is circulated the scanning current potential of voltammetric scan, and sweep speed is 10-500mV/s.It is excellent
Choosing, sweep speed is 50mV/s.
The preparation method of above-mentioned porous graphene, is made in Graphene and graphene oxide liquid mixture using electrochemical method
Graphene oxide is reduced to Graphene, while obtaining porous graphene, operating procedure letter with original Graphene reconstruct in mixed liquor
Single, efficiency high, environmental protection, the porous graphene specific surface area for obtaining are big, and activity is high.
It is below specific embodiment.
Embodiment 1
Graphene and graphene oxide are dispersed in the phosphate buffer solution that pH value is 4, Graphene is in 0.1mol/L phosphorus
Concentration in acid buffering solution is 1mg/mL, and concentration of the graphene oxide in phosphate buffer solution is 1mg/mL, obtains graphite
Alkene and graphene oxide liquid mixture.
With glass-carbon electrode as working electrode, Graphene and graphene oxide liquid mixture dispersion are added drop-wise on glass-carbon electrode,
Be dried, then with modify glass-carbon electrode as working electrode, to electrode as platinum plate electrode, reference electrode as saturated calomel electrode, put
Voltammetric scan is circulated in the blank phosphate buffer solution that 0.1mol/L pH value is 4, and scanning current potential is 0 V to -2.0 V,
Sweep speed is 50mV/s, obtains the working electrode of porous graphene modification, i.e., obtains porous graphene on the working electrode (s.
Embodiment 2
It is 0.1 mg/mL that the difference of embodiment 2 and embodiment 1 is the concentration of Graphene, phosphate buffer solution
PH value is 5, with graphite electrode as working electrode, to electrode as platinum plate electrode, reference electrode as saturated calomel electrode, be placed in
0.1mol/L pH value be 5 blank phosphate buffer solution in be circulated voltammetric scan, scanning current potential is 0 V to -2.0 V, is swept
It is 50mV/s to retouch speed, obtains the working electrode of porous graphene modification, i.e., obtains porous graphene on the working electrode (s.
Embodiment 3
It is 0.05 mg/mL that the difference of embodiment 3 and embodiment 1 is the concentration of Graphene, phosphate buffer solution
PH value is 6, with carbon cloth electrode as working electrode, to electrode as platinum plate electrode, reference electrode as saturated calomel electrode, be placed in
0.1mol/L pH value be 6 blank phosphate buffer solution in be circulated voltammetric scan, scanning current potential is 0 V to -2.0 V, is swept
It is 50mV/s to retouch speed, obtains the working electrode of porous graphene modification, i.e., obtains porous graphene on the working electrode (s.
Embodiment 4
It is by the real-time oxygen reduction in ascorbic acid scene in situ that the difference of embodiment 4 and embodiment 1 is Graphene
The Graphene that graphite alkene is obtained.Specially：Graphene oxide is dispersed in into the 0.1mol/L phosphate buffer solutions that pH value is 4
In, concentration of the graphene oxide in phosphate buffer solution is 2mg/mL, and then under conditions of stirring, addition ultimate density is
The ascorbic acid reaction half an hour of 1mg/mL, obtain Graphene and graphene oxide liquid mixture.With glass-carbon electrode as working electrode,
To electrode be platinum plate electrode, reference electrode be saturated calomel electrode, be placed in gained Graphene and graphene oxide liquid mixture in enter
Row cyclic voltammetry scan, scanning current potential is 0 V to -2.0 V, and sweep speed is 50mV/s, obtains the work of porous graphene modification
Make electrode, i.e., obtain porous graphene on the working electrode (s.
Embodiment 5
It is by the real-time oxygen reduction in sodium borohydride scene in situ that the difference of embodiment 5 and embodiment 1 is Graphene
The Graphene that graphite alkene is obtained, specially：Graphene oxide is dispersed in into the 0.1mol/L phosphate buffer solutions that pH value is 5
In, concentration of the graphene oxide in phosphate buffer solution is 2mg/mL, and then under conditions of stirring, addition ultimate density is
The sodium borohydride reaction half an hour of 1mg/mL, obtain Graphene and graphene oxide liquid mixture.With graphite electrode as working electrode,
To electrode be platinum plate electrode, reference electrode be saturated calomel electrode, be placed in gained Graphene and graphene oxide liquid mixture in enter
Row cyclic voltammetry scan, scanning current potential is 0 V to -2.0 V, and sweep speed is 50mV/s, obtains the work of porous graphene modification
Make electrode, i.e., obtain porous graphene on the working electrode (s.
The porous graphene that embodiment 1 is obtained is made into sem test, scanning electron microscope (SEM) photograph is obtained as shown in Figure 2.By Fig. 2
Understand, the specific surface area of gained porous graphene is big.
Each technical characteristic of embodiment described above arbitrarily can be combined, for making description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (6)
1. a kind of preparation method of porous graphene, it is characterised in that be including step：
Graphene and graphene oxide are dispersed in phosphate buffer solution, the mixed liquor of Graphene and graphene oxide is obtained；
With first electrode as working electrode, the mixed liquor of the Graphene and graphene oxide is followed using three-electrode system
Ring voltammetric scan, obtains the working electrode of porous graphene modification, obtains final product porous graphene.
2. the preparation method of porous graphene according to claim 1, it is characterised in that the pH of the phosphate buffer solution
It is worth for 4-6.
3. the preparation method of porous graphene according to claim 1, it is characterised in that the first electrode is gold electricity
Any one in pole, platinum electrode, glass-carbon electrode, graphite electrode, carbon fiber electrode, carbon cloth electrode and carbon paste electrode.
4. the preparation method of porous graphene according to claim 1, it is characterised in that the Graphene is by chemistry
Any one in reducing agent or the biological reductant scene in situ Graphene that redox graphene is obtained in real time.
5. the preparation method of porous graphene according to claim 1, it is characterised in that described with first electrode as work
Electrode, is circulated voltammetric scan using three-electrode system to the mixed liquor of the Graphene and graphene oxide, obtains porous
The working electrode of graphene modified is concretely comprised the following steps：
The mixed liquor of the Graphene and graphene oxide is added drop-wise in the first electrode, is dried, then it is electric with described first
Extremely working electrode, to electrode be platinum plate electrode, reference electrode be saturated calomel electrode, be placed in pH value be 4-6 blank phosphoric acid
Voltammetric scan is circulated in cushioning liquid, obtains the working electrode of the porous graphene modification.
6. the preparation method of porous graphene according to claim 1, it is characterised in that described with first electrode as work
Electrode, is circulated voltammetric scan using three-electrode system to the mixed liquor of the Graphene and graphene oxide, obtains porous
The working electrode of graphene modified is concretely comprised the following steps：
With first electrode as working electrode, to electrode as platinum plate electrode, reference electrode as saturated calomel electrode, be placed in the graphite
Voltammetric scan is circulated in the mixed liquor of alkene and graphene oxide, the working electrode of the porous graphene modification is obtained.
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| CN106978606B (en) * | 2016-11-30 | 2019-01-01 | 哈尔滨工业大学（威海） | A kind of high thermal conductivity graphene/titanium composite material and preparation method thereof |
| CN107083557B (en) * | 2017-02-21 | 2018-12-11 | 鑑道生命科技有限公司 | A kind of equipment using graphene high-efficiency oxygen and hydrogen-rich ionized water |
| CN107271505A (en) * | 2017-06-01 | 2017-10-20 | 赵云飞 | Composite electrode and preparation method thereof, Quercetin sensor |
| CN110453260B (en) * | 2019-08-23 | 2020-06-30 | 厦门大学 | Wearable sensor for sweat detection and preparation method thereof |
| CN114324545B (en) * | 2022-01-07 | 2024-05-28 | 三只松鼠股份有限公司 | Reduced graphene oxide sensor, preparation method thereof and method for rapidly detecting capsaicin content |
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