CN103991861A - Nitrogen-doped graphene and preparation method thereof - Google Patents
Nitrogen-doped graphene and preparation method thereof Download PDFInfo
- Publication number
- CN103991861A CN103991861A CN201310054663.7A CN201310054663A CN103991861A CN 103991861 A CN103991861 A CN 103991861A CN 201310054663 A CN201310054663 A CN 201310054663A CN 103991861 A CN103991861 A CN 103991861A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- hours
- graphite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
Abstract
The invention relates to a preparation method for nitrogen-doped graphene. The method comprises the steps of: preparing graphite oxide from graphite; adding the graphite oxide into deionized water, conducting ultrasonic treatment, then adding aniline and carrying out ultrasonic mixing, thus obtaining a suspending solution; at a temperature of 0DEG C-10DEG C, adding hydrochloric acid into the suspending solution till the pH value of the suspending solution reaches 3-5, then adding benzoyl peroxide, carrying out polymerization reaction under stirring for 12h-20h, and then performing filtering, washing and drying to obtain a graphene oxide-polyaniline mixture; and in an oxygen-free atmosphere, subjecting the graphene oxide-polyaniline mixture to heating and heat preservation reaction, and conducting cooling, thus obtaining the nitrogen-doped graphene. The nitrogen-doped grapheme prepared by the method provided by the invention has a high nitrogen content. In addition, the invention also relates to a nitrogen-doped graphene.
Description
Technical field
The present invention relates to the synthetic field of material, particularly a kind of nitrogen-doped graphene and preparation method thereof.
Background technology
Graphene, due to the two-dimentional unimolecular layer structure of its uniqueness and excellent physical properties (high theoretical specific surface area, high conductivity, high-mechanical property etc.), has been subject to the extensive concern from every field since 2004 prepare.Its appearance produces tremendous influence to Material Field, brought very large opportunities and challenges also to material researcher simultaneously, believe that it can bring once and change to Material Field in several years of future, also to people's life, bring the product of many excellent performances.Graphene is due to unimolecular layer, and its theoretical capacity can reach 2630m
2/ g is with a wide range of applications in lithium ion battery and electrode material for super capacitor, also has relevant report at present.Wherein nitrogen-doped graphene is because the mixing of nitrogen (nitrogen replaces the carbon atom on Graphene) improved its energy-storage property greatly, but according to current report, in Graphene, nitrogen incorporation is limited, and this has greatly limited the raising of energy-storage property.
Summary of the invention
Given this, be necessary to provide nitrogen-doped graphene that a kind of nitrogen content is higher and preparation method thereof.
A preparation method for nitrogen-doped graphene, comprises the steps:
Use graphite-made for graphite oxide;
According to mass volume ratio, be 0.5mg ~ 1mg:1ml, described graphite oxide is joined in deionized water, supersound process 1 hour ~ 3 hours, then adds the ultrasonic mixing of aniline, obtains suspension; In temperature, be under the condition of 0 ℃ ~ 10 ℃, in described suspension, add hydrochloric acid until the pH value of described suspension is 3 ~ 5, then add benzoyl peroxide, after stirring is carried out polyreaction 12 hours ~ 20 hours, after filtration, clean and dry, obtain graphene oxide-polyaniline mixture; Wherein, the mass ratio of described aniline and described graphite oxide is 0.5:1 ~ 1:0.4; The mass ratio of described benzoyl peroxide and described aniline is 0.005:0.5 ~ 0.001:0.4; And
In oxygen-free atmosphere, described graphene oxide-polyaniline mixture is heated to 750 ℃ ~ 1000 ℃ insulation reaction 0.5 hour ~ 2 hours, through cooling, obtain nitrogen-doped graphene.
In an embodiment, use described graphite-made to comprise for the step of described graphite oxide therein:
According to mass volume ratio, be 0.5 gram ~ 1.5 grams: 110ml ~ 120ml, described graphite is joined in the mixed solution being comprised of the vitriol oil and concentrated nitric acid, and be placed in frozen water and mix bathe and to be uniformly mixed, form mixing solutions; And
According to the mass ratio of described graphite and potassium permanganate, be 0.5 ~ 1.5:3 ~ 12, described potassium permanganate is joined in described mixing solutions, stir and within 0.5 hour ~ 3 hours, carry out intercalation, then be heated to 25 ℃ ~ 45 ℃ insulation reaction 10 minutes ~ 40 minutes, then add deionized water, reheat to 60 ℃ ~ 95 ℃ insulation reaction 10 minutes ~ 40 minutes, obtain reaction solution, in described reaction solution, add hydrogen peroxide, through suction filtration, and use successively dilute hydrochloric acid and deionized water wash, then drying, graphite oxide obtained; Wherein, described potassium permanganate is 1g:15ml ~ 50ml with the mass volume ratio of the described deionized water adding; And the described hydrogen peroxide adding and the mass ratio of described potassium permanganate are 0.352 ~ 1.407:1.
In an embodiment, the time that adds the ultrasonic mixing of described aniline is while being 0.5 hour ~ 2 hours therein.
In an embodiment, the reaction solution that described polyreaction obtains cleaning step is after filtering: the filter residue that the reaction solution of described polyreaction is obtained is after filtering used acetone and deionized water wash successively therein.
Therein in an embodiment, the drying conditions of the reaction solution that described polyreaction obtains after filtration and after cleaning is: 40 ℃ ~ 80 ℃ vacuum-drying 8 hours ~ 16 hours.
In an embodiment, the temperature rise rate during by described graphene oxide-polyaniline mixture heating is 2 ℃/min ~ 10 ℃/min therein.
A nitrogen-doped graphene of preparing according to the preparation method of above-mentioned nitrogen-doped graphene, in described nitrogen-doped graphene, the quality percentage composition of nitrogen is 3.4% ~ 7.8%.
The preparation method of above-mentioned nitrogen-doped graphene, by first graphite oxide being peeled off into graphene oxide, and be prepared into graphene oxide-polyaniline mixture with aniline, make oxygen and the nitrogen element in aniline in graphene oxide form chemical combination key, again by the at high temperature cracking of graphene oxide-polyaniline mixture, nitrogen element forms bonding with carbon, thereby makes the nitrogen-doped graphene preparing have higher nitrogen content, and the quality percentage composition of nitrogen reaches as high as 7.8%.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the nitrogen-doped graphene of an embodiment.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments nitrogen-doped graphene and preparation method thereof is described in further detail below.
As shown in Figure 1, the preparation method of the nitrogen-doped graphene of an embodiment, comprises the steps:
Step S110: use graphite-made for graphite oxide.
Use graphite-made can adopt ordinary method to prepare for graphite oxide, preferred, use graphite-made to comprise for the step of graphite oxide:
According to mass volume ratio, be 0.5 gram ~ 1.5 grams: 110ml ~ 120ml, graphite is joined in the mixed solution being comprised of the vitriol oil and concentrated nitric acid, and be placed in frozen water and mix bathe and to be uniformly mixed, form mixing solutions; And
According to the mass ratio of graphite and potassium permanganate, be 0.5 ~ 1.5:3 ~ 12, potassium permanganate is joined in mixing solutions, stir and carry out intercalation in 0.5 hour ~ 3 hours, be then heated to 25 ℃ ~ 45 ℃ insulation reaction 10 minutes ~ 40 minutes, then add deionized water, reheat to 60 ℃ ~ 95 ℃ insulation reaction 10 minutes ~ 40 minutes, obtain reaction solution, in reaction solution, add hydrogen peroxide, through suction filtration, and use successively dilute hydrochloric acid and deionized water wash, then drying, graphite oxide obtained; Wherein, potassium permanganate is 1g:15ml ~ 50ml with the mass volume ratio of the deionized water adding; And the hydrogen peroxide adding and the mass ratio of potassium permanganate are 0.352 ~ 1.407:1.
Wherein, graphite can be the conventional graphite in this area, is preferably purity and is 99.5% graphite.
Wherein, to refer to massfraction be 98% sulfuric acid to the vitriol oil; It is 65% nitric acid that concentrated nitric acid refers to massfraction.Preferably, the mixed solution being formed by the vitriol oil and concentrated nitric acid, wherein, the volume ratio of the vitriol oil and concentrated nitric acid is 85 ~ 90:25 ~ 30.
Wherein, it is 20 minutes that graphite joins the time of stirring in the mixed solution being comprised of the vitriol oil and concentrated nitric acid, by stirring, graphite can be dispersed in the mixed solution being comprised of the vitriol oil and concentrated nitric acid more fully.
In specific embodiment, need to lentamente potassium permanganate be joined in mixing solutions.
After being joined to mixing solutions, potassium permanganate reacts by stirring, in the process of reaction, emit heat, potassium permanganate is oxidized the edge of graphite aspect, sulfate ion and sulfuric acid molecule in mixing solutions is adsorbed on the edge of graphite aspect by the effect of static simultaneously, along with the continuation of stirring, heat is constantly emitted in potassium permanganate reaction, the cellular lattice plane of graphite gradually becomes the plane macromole of positively charged, sulfate ion and sulfuric acid molecule are inserted into the interlayer of graphite, form sulfuric acid-compound between graphite layers.
It is 0.5 hour ~ 3 hours that the intercalation time is carried out in stirring, makes to have more abundant that time enough is undertaken by intercalation.
Then be heated to 25 ℃ ~ 45 ℃ insulation reaction 10 minutes ~ 40 minutes, can make sulfuric acid-compound between graphite layers that the more oxidation of the degree of depth occurs.
Then by adding deionized water, and be heated to 60 ℃ ~ 95 ℃ insulation reaction 10 minutes ~ 40 minutes, make sulfuric acid-compound between graphite layers generation hydrolysis reaction, large quantity of moisture enters into sulfuric acid-compound between graphite layers, the distance of graphite layers increases, and volumetric expansion, by being heated to 60 ℃ ~ 95 ℃ insulation reaction 10 minutes ~ 40 minutes, sulfuric acid-compound between graphite layers is peeled off, thereby forms graphite oxide.
Potassium permanganate is 1g:15ml ~ 50ml with the mass volume ratio of the deionized water adding, thereby better dissolves potassium permanganate.
Reaction solution before filtering, add hydrogen peroxide can remove reaction solution in remaining potassium permanganate, and the mass ratio of the hydrogen peroxide adding and potassium permanganate is 0.352 ~ 1.407:1, to guarantee that in reaction solution, remaining potassium permanganate is completely removed.
In specific embodiment, dilute hydrochloric acid and deionized water wash are three times altogether, the remaining vitriol oil, concentrated nitric acid and hydrogen peroxide etc. in reaction solution.
Preferably, the drying conditions of reaction solution after filtration and after cleaning is: 40 ℃ ~ 80 ℃ vacuum-drying 8 hours ~ 16 hours.
Step S120: be 0.5mg ~ 1mg:1ml according to mass volume ratio, graphite oxide is joined in deionized water, supersound process 1 hour ~ 3 hours, then adds the ultrasonic mixing of aniline, obtains suspension; In temperature, be under the condition of 0 ℃ ~ 10 ℃, in suspension, add hydrochloric acid until the pH value of suspension is 3 ~ 5, then add benzoyl peroxide, after stirring is carried out polyreaction 12 hours ~ 20 hours, after filtration, clean and dry, obtain graphene oxide-polyaniline mixture; Wherein, the mass ratio of aniline and graphite oxide is 0.5:1 ~ 1:0.4; The mass ratio of benzoyl peroxide and aniline is 0.005:0.5 ~ 0.001:0.4.
By graphite oxide is joined to deionized water for ultrasonic, processing, is in order to make graphite oxide be dispersed into graphene oxide by supersound process.
Suspension being placed under the condition of 0 ℃ ~ 10 ℃, is to reunite for fear of suspended particle.
By adding hydrochloric acid that the pH value of suspension is adjusted to 3 ~ 5, neutralize excessive aniline, make suspension be acid, be convenient to polyreaction and carry out smoothly.
By adding benzoyl peroxide to stir, carry out polyreaction, object is to use benzoyl peroxide as initiator, causes aniline polymerization reaction take place, thereby obtains polyaniline.
Preferably, adding the time of the ultrasonic mixing of aniline is 0.5 hour ~ 2 hours.
Preferably, the reaction solution that polyreaction obtains cleaning step is after filtering: the filter residue that the reaction solution of polyreaction is obtained is after filtering used acetone and deionized water wash successively.
Preferably, the drying conditions of the reaction solution that polyreaction obtains after filtration and after cleaning is: 40 ℃ ~ 80 ℃ vacuum-drying 8 hours ~ 16 hours.
Step S130: in oxygen-free atmosphere, graphene oxide-polyaniline mixture is heated to 750 ℃ ~ 1000 ℃ insulation reaction 0.5 hour ~ 2 hours, through cooling, obtains nitrogen-doped graphene.
By step S120, first graphite oxide is peeled off into graphene oxide, and be prepared into graphene oxide-polyaniline mixture with aniline, make oxygen and the nitrogen element in polyaniline in graphene oxide form chemical combination key, by step S130, make it after Pintsch process, nitrogen element forms bonding with carbon, makes nitrogen-doped graphene prepared by aforesaid method have higher nitrogen content.
Wherein, oxygen-free atmosphere can be for being full of the inert atmospheres such as nitrogen, helium, argon gas.In specific embodiment, by the speed with 200ml/ minute ~ 400ml/ minute, pass into rare gas element, form oxygen-free atmosphere.
In specific embodiment, before graphene oxide-polyaniline mixture is placed in to oxygen-free atmosphere, first pass into the rare gas element of 30 minutes, to remove air.
Preferably, temperature rise rate when graphene oxide-polyaniline mixture is heated is 2 ℃/min ~ 10 ℃/min, by being rapidly heated, accelerates the cracking of graphite oxide.
The preparation method of above-mentioned nitrogen-doped graphene, by first graphite oxide being peeled off into graphene oxide, and be prepared into graphene oxide-polyaniline mixture with aniline, make oxygen and the nitrogen element in aniline in graphene oxide form chemical combination key, again by the at high temperature cracking of graphene oxide-polyaniline mixture, nitrogen element forms bonding with carbon, thereby makes the nitrogen-doped graphene preparing have higher nitrogen content, and the quality percentage composition of nitrogen reaches as high as 7.8%.
And above-mentioned preparation method is simple, is conducive to suitability for industrialized production.
The nitrogen-doped graphene that one embodiment is prepared according to the preparation method of above-mentioned nitrogen-doped graphene, the quality percentage composition of its nitrogen is 3.4% ~ 7.8%.
Above-mentioned nitrogen-doped graphene prepares according to the preparation method of above-mentioned nitrogen-doped graphene, makes above-mentioned doped graphene have higher nitrogen content, and nitrogen content reaches as high as 7.8%.
Be below specific embodiment part:
Embodiment 1
Being prepared as follows of the nitrogen-doped graphene of the present embodiment:
(1) in the mixed solution that the concentrated nitric acid that the vitriol oil that 1g graphite (massfraction 99.5%) to be joined by 90 milliliters of massfractions be 98% and 25 milliliters of massfractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixing solutions.
(2) 6g potassium permanganate is slowly joined in mixing solutions, stir and within 1 hour, carry out intercalation, then be heated to 25 ℃ of insulation reaction 40 minutes, then the deionized water that adds 92ml, reheat to 85 ℃ of insulation reaction 30 minutes, obtain reaction solution, in reaction solution, add 10ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, filter residue through suction filtration is used the dilute hydrochloric acid of 100ml and the deionized water wash of 150ml totally three times successively, then in 60 ℃ of vacuum drying ovens, be dried 12 hours, obtain graphite oxide.
(3) according to mass volume ratio, be that 1mg:1ml joins graphite oxide in deionized water, supersound process 2 hours; Then according to the mass ratio of aniline and graphite oxide, be 1:0.5, add aniline solid granulates, ultrasonic mixing 0.5 hour, obtains suspension; In temperature, be under the condition of 0 ℃, in suspension, add hydrochloric acid until the pH value of suspension is 4, then according to the mass ratio of benzoyl peroxide and aniline, be 0.005:0.5, add benzoyl peroxide, stir and carry out polyreaction 12 hours, obtain reaction solution, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water wash, and then 60 ℃ of vacuum drying ovens are dried 12 hours, obtain graphene oxide-polyaniline mixture.
(4) graphene oxide-polyaniline mixture is placed in to argon gas (passing into speed is 400ml/ minute) atmosphere, pass into argon gas 30 minutes to remove air, then with the temperature rise rate of 5 ℃/min, be heated to 800 ℃ of insulation reaction 2 hours, in argon gas (passing into speed is 400ml/ minute) atmosphere, be cooled to room temperature, obtain nitrogen-doped graphene.The quality percentage composition of each element of nitrogen-doped graphene prepared by the present embodiment is in Table 1.
Embodiment 2
Being prepared as follows of the nitrogen-doped graphene of the present embodiment:
(1) in the mixed solution that the concentrated nitric acid that the vitriol oil that 0.5g graphite (massfraction 99.5%) to be joined by 85 milliliters of massfractions be 98% and 25 milliliters of massfractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixing solutions.
(2) 3g potassium permanganate is slowly joined in mixing solutions, stir and within 1 hour, carry out intercalation, then be heated to 35 ℃ of insulation reaction 30 minutes, then the deionized water that adds 92ml, reheat to 60 ℃ of insulation reaction 40 minutes, obtain reaction solution, in reaction solution, add 10ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, filter residue through suction filtration is used the dilute hydrochloric acid of 100ml and the deionized water wash of 150ml totally three times successively, then in 40 ℃ of vacuum drying ovens, be dried 16 hours, obtain graphite oxide.
(3) according to mass volume ratio, be that 1mg:1ml joins graphite oxide in deionized water, supersound process 2 hours; Then according to the mass ratio of aniline and graphite oxide, be 0.4:1, add aniline solid granulates, ultrasonic mixing 1 hour, obtains suspension; In temperature, be under the condition of 10 ℃, in suspension, add hydrochloric acid until the pH value of suspension is 5, then according to the mass ratio of benzoyl peroxide and aniline, be 0.001:0.4, add benzoyl peroxide, stir and carry out polyreaction 15 hours, the reaction solution obtaining, the filter residue obtaining after filtering, filter residue is used and uses successively acetone and deionized water wash, and then 40 ℃ of vacuum drying ovens are dried 16 hours, obtain graphene oxide-polyaniline mixture.
(4) graphene oxide-polyaniline mixture is placed in to argon gas (passing into speed is 400ml/ minute) atmosphere, pass into argon gas 30 minutes to remove air, then with the temperature rise rate of 5 ℃/min, be heated to 900 ℃ of insulation reaction 30 hours, in argon gas (passing into speed is 400ml/ minute) atmosphere, be cooled to room temperature, obtain nitrogen-doped graphene.The quality percentage composition of each element of nitrogen-doped graphene prepared by the present embodiment is in Table 1.
Embodiment 3
Being prepared as follows of the nitrogen-doped graphene of the present embodiment:
(1) in the mixed solution that the concentrated nitric acid that the vitriol oil that 1g graphite (massfraction 99.5%) to be joined by 90 milliliters of massfractions be 98% and 30 milliliters of massfractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixing solutions.
(2) 12g potassium permanganate is slowly joined in mixing solutions, stir and within 1 hour, carry out intercalation, then be heated to 45 ℃ of insulation reaction 10 minutes, then the deionized water that adds 92ml, reheat to 95 ℃ of insulation reaction 10 minutes, obtain reaction solution, in reaction solution, add 10ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, filter residue through suction filtration is used the dilute hydrochloric acid of 100ml and the deionized water wash of 150ml totally three times successively, then in 80 ℃ of vacuum drying ovens, be dried 8 hours, obtain graphite oxide.
(3) according to mass volume ratio, be that 0.5mg:1ml joins graphite oxide in deionized water, supersound process 3 hours; Then according to the mass ratio of aniline and graphite oxide, be 0.5:0.5, add aniline solid granulates, ultrasonic mixing 1 hour, obtains suspension; In temperature, be under the condition of 5 ℃, in suspension, add hydrochloric acid until the pH value of suspension is 4, then according to the mass ratio of benzoyl peroxide and aniline, be 0.005:0.5, add benzoyl peroxide, stir and carry out polyreaction 15 hours, obtain reaction solution, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water wash, and then 80 ℃ of vacuum drying ovens are dried 8 hours, obtain graphene oxide-polyaniline mixture.
(4) graphene oxide-polyaniline mixture is placed in to argon gas (passing into speed is 400ml/ minute) atmosphere, pass into argon gas 30 minutes to remove air, then with the temperature rise rate of 10 ℃/min, be heated to 1000 ℃ of insulation reaction 30 hours, in argon gas (passing into speed is 400ml/ minute) atmosphere, be cooled to room temperature, obtain nitrogen-doped graphene.The quality percentage composition of each element of nitrogen-doped graphene prepared by the present embodiment is in Table 1.
Embodiment 4
Being prepared as follows of the nitrogen-doped graphene of the present embodiment:
(1) in the mixed solution that the concentrated nitric acid that the vitriol oil that 1g graphite (massfraction 99.5%) to be joined by 90 milliliters of massfractions be 98% and 25 milliliters of massfractions are 65% forms, and be placed in frozen water and mix to bathe and be uniformly mixed 20 minutes, form mixing solutions.
(2) 6g potassium permanganate is slowly joined in mixing solutions, stir and within 1 hour, carry out intercalation, then be heated to 35 ℃ of insulation reaction 30 minutes, then the deionized water that adds 92ml, reheat to 85 ℃ of insulation reaction 30 minutes, obtain reaction solution, in reaction solution, add 10ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, filter residue through suction filtration is used the dilute hydrochloric acid of 100ml and the deionized water wash of 150ml totally three times successively, then in 60 ℃ of vacuum drying ovens, be dried 12 hours, obtain graphite oxide.
(3) according to mass volume ratio, be that 0.5mg:1ml joins graphite oxide in deionized water, supersound process 2 hours; Then according to the mass ratio of aniline and graphite oxide, be 1:0.5, add aniline solid granulates, ultrasonic mixing 2 hours, obtains suspension; In temperature, be under the condition of 0 ℃, in suspension, add hydrochloric acid until the pH value of suspension is 3, then according to the mass ratio of benzoyl peroxide and aniline, be 0.01:1, add benzoyl peroxide, stirring reaction 20 hours, obtains reaction solution, obtain after filtering filter residue, filter residue is used and uses successively acetone and deionized water wash, and then 60 ℃ of vacuum drying ovens are dried 12 hours, obtain graphene oxide-polyaniline mixture.
(4) graphene oxide-polyaniline mixture is placed in to argon gas (passing into speed is 400ml/ minute) atmosphere, pass into argon gas 30 minutes to remove air, then with the temperature rise rate of 5 ℃/min, be heated to 700 ℃ of insulation reaction 2 hours, in argon gas (passing into speed is 400ml/ minute) atmosphere, be cooled to room temperature, obtain nitrogen-doped graphene.The quality percentage composition of each element of nitrogen-doped graphene prepared by the present embodiment is in Table 1.
Each element quality percentage composition of the nitrogen-doped graphene of the preparation of embodiment 1 ~ embodiment 4 that table 1 represents.
Table 1
| ? | Carbon (%) | Nitrogen element (%) | Oxygen element (%) |
| Embodiment 1 | 89.8 | 3.9 | 6.3 |
| Embodiment 2 | 91.1 | 3.4 | 5.5 |
| Embodiment 3 | 89.8 | 5.4 | 4.8 |
| Embodiment 4 | 84.1 | 7.8 | 8.1 |
As can be seen from Table 1, the nitrogen-doped graphene of embodiment 1 ~ embodiment 4 preparations all has higher nitrogen content, and the quality percentage composition of nitrogen is at least 3.4%, reaches as high as 7.8%.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. a preparation method for nitrogen-doped graphene, is characterized in that, comprises the steps:
Use graphite-made for graphite oxide;
According to mass volume ratio, be 0.5mg ~ 1mg:1ml, described graphite oxide is joined in deionized water, supersound process 1 hour ~ 3 hours, then adds the ultrasonic mixing of aniline, obtains suspension; In temperature, be under the condition of 0 ℃ ~ 10 ℃, in described suspension, add hydrochloric acid until the pH value of described suspension is 3 ~ 5, then add benzoyl peroxide, after stirring is carried out polyreaction 12 hours ~ 20 hours, after filtration, clean and dry, obtain graphene oxide-polyaniline mixture; Wherein, the mass ratio of described aniline and described graphite oxide is 0.5:1 ~ 1:0.4; The mass ratio of described benzoyl peroxide and described aniline is 0.005:0.5 ~ 0.001:0.4; And
In oxygen-free atmosphere, described graphene oxide-polyaniline mixture is heated to 750 ℃ ~ 1000 ℃ insulation reaction 0.5 hour ~ 2 hours, through cooling, obtain nitrogen-doped graphene.
2. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, uses described graphite-made to comprise for the step of described graphite oxide:
According to mass volume ratio, be 0.5 gram ~ 1.5 grams: 110ml ~ 120ml, described graphite is joined in the mixed solution being comprised of the vitriol oil and concentrated nitric acid, and be placed in frozen water and mix bathe and to be uniformly mixed, form mixing solutions; And
According to the mass ratio of described graphite and potassium permanganate, be 0.5 ~ 1.5:3 ~ 12, described potassium permanganate is joined in described mixing solutions, stir and within 0.5 hour ~ 3 hours, carry out intercalation, then be heated to 25 ℃ ~ 45 ℃ insulation reaction 10 minutes ~ 40 minutes, then add deionized water, reheat to 60 ℃ ~ 95 ℃ insulation reaction 10 minutes ~ 40 minutes, obtain reaction solution, in described reaction solution, add hydrogen peroxide, through suction filtration, and use successively dilute hydrochloric acid and deionized water wash, then drying, graphite oxide obtained; Wherein, described potassium permanganate is 1g:15ml ~ 50ml with the mass volume ratio of the described deionized water adding; And the described hydrogen peroxide adding and the mass ratio of described potassium permanganate are 0.352 ~ 1.407:1.
3. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, the time that adds the ultrasonic mixing of described aniline is 0.5 hour ~ 2 hours.
4. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, the reaction solution that described polyreaction obtains cleaning step is after filtering: the filter residue that the reaction solution of described polyreaction is obtained is after filtering used deionized water wash.
5. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, the drying conditions of the reaction solution that described polyreaction obtains after filtration and after cleaning is: 40 ℃ ~ 80 ℃ vacuum-drying 8 hours ~ 16 hours.
6. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, the temperature rise rate during by described graphene oxide-polyaniline mixture heating is 2 ℃/min ~ 10 ℃/min.
7. a nitrogen-doped graphene of preparing according to the preparation method of nitrogen-doped graphene claimed in claim 1, is characterized in that, in described nitrogen-doped graphene, the quality percentage composition of nitrogen is 3.4% ~ 7.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310054663.7A CN103991861A (en) | 2013-02-20 | 2013-02-20 | Nitrogen-doped graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310054663.7A CN103991861A (en) | 2013-02-20 | 2013-02-20 | Nitrogen-doped graphene and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103991861A true CN103991861A (en) | 2014-08-20 |
Family
ID=51306243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310054663.7A Pending CN103991861A (en) | 2013-02-20 | 2013-02-20 | Nitrogen-doped graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103991861A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229781A (en) * | 2014-09-09 | 2014-12-24 | 东莞市翔丰华电池材料有限公司 | Method for preparing nitrogen-doped graphene with high nitrogen doping amount |
| CN105668552A (en) * | 2014-12-08 | 2016-06-15 | 中国科学院成都有机化学有限公司 | Preparation method of easy-to-disperse nitrogen-doped graphene powder |
| CN111591981A (en) * | 2020-04-21 | 2020-08-28 | 东北大学 | Preparation method of low-layer gauze-shaped nitrogen-doped graphene |
| CN111606405A (en) * | 2020-06-03 | 2020-09-01 | 北京林业大学 | Method for degrading organic pollutants in water by activating peracetic acid through nitrogen-doped carbon material |
| CN111977645A (en) * | 2020-08-31 | 2020-11-24 | 合肥福纳科技有限公司 | Carbon quantum dot and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120149897A1 (en) * | 2010-12-10 | 2012-06-14 | Jeon In Yup | Method of preparing nitrogen-doped graphene and nitrogen-doped graphene prepared thereby |
| CN102712779A (en) * | 2009-12-22 | 2012-10-03 | 徐光锡 | Graphene dispersion and graphene-ionic liquid polymer compound material |
-
2013
- 2013-02-20 CN CN201310054663.7A patent/CN103991861A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712779A (en) * | 2009-12-22 | 2012-10-03 | 徐光锡 | Graphene dispersion and graphene-ionic liquid polymer compound material |
| US20120149897A1 (en) * | 2010-12-10 | 2012-06-14 | Jeon In Yup | Method of preparing nitrogen-doped graphene and nitrogen-doped graphene prepared thereby |
Non-Patent Citations (4)
| Title |
|---|
| ZIYIN LIN ET AL.: "Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction", 《PHYS. CHEM. CHEM. PHYS.》, vol. 14, 17 January 2012 (2012-01-17) * |
| ZIYIN LIN ET AL.: "Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions", 《CARBON》, vol. 53, 26 October 2012 (2012-10-26) * |
| 王俊生 等: "以过氧化苯甲酰为氧化剂合成聚苯胺纳米纤维", 《功能材料》, vol. 38, 31 December 2007 (2007-12-31) * |
| 郑水林: "《非金属矿加工与应用》", 31 January 2009, article "碳质非金属矿", pages: 171-172 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229781A (en) * | 2014-09-09 | 2014-12-24 | 东莞市翔丰华电池材料有限公司 | Method for preparing nitrogen-doped graphene with high nitrogen doping amount |
| CN104229781B (en) * | 2014-09-09 | 2016-01-27 | 东莞市翔丰华电池材料有限公司 | A kind of method preparing high itrogen content of getter with nitrogen doped nitrogen-doped graphene |
| CN105668552A (en) * | 2014-12-08 | 2016-06-15 | 中国科学院成都有机化学有限公司 | Preparation method of easy-to-disperse nitrogen-doped graphene powder |
| CN111591981A (en) * | 2020-04-21 | 2020-08-28 | 东北大学 | Preparation method of low-layer gauze-shaped nitrogen-doped graphene |
| CN111606405A (en) * | 2020-06-03 | 2020-09-01 | 北京林业大学 | Method for degrading organic pollutants in water by activating peracetic acid through nitrogen-doped carbon material |
| CN111977645A (en) * | 2020-08-31 | 2020-11-24 | 合肥福纳科技有限公司 | Carbon quantum dot and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103991860A (en) | Nitrogen-doped graphene and preparation method thereof | |
| CN105645403B (en) | A kind of preparation method of high-performance N doping three-dimensional grapheme | |
| CN103420352B (en) | A kind of high Oil repellent fluorinated graphene and preparation method thereof | |
| CN105552371B (en) | The preparation and application of nitrogen-doped graphene carbon nanohorn composite | |
| CN102568641B (en) | Preparation method for graphene composite material loaded with nano metal particles | |
| CN105460917B (en) | A kind of nitrogen-doped carbon nanometer pipe and preparation method with hierarchy | |
| CN102464313B (en) | Preparation method of graphene | |
| CN103466604A (en) | Preparation method of porous graphene | |
| CN103991861A (en) | Nitrogen-doped graphene and preparation method thereof | |
| CN102942177B (en) | Method for preparing graphene sheet | |
| CN110670107B (en) | Titanium carbide nanosheet/carbon nanotube electromagnetic shielding film and preparation method thereof | |
| KR101572671B1 (en) | Method of manufacturing of large-area graphene oxide and the large-area graphene oxide thereby | |
| CN105449214A (en) | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material | |
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN103787311A (en) | Preparation methods of graphene-carbon nanotube composite thin film and electrochemical capacitor | |
| CN104953103A (en) | Method for preparing Fe2O3 and expanded graphite composite material of lithium ion battery | |
| CN105197910B (en) | A kind of method that porous nano carbon material is prepared using biomass as carbon source | |
| CN103832996A (en) | Graphene/carbon nano-tube composite material, preparation method and application thereof | |
| CN105449210A (en) | Preparation method for porous graphene micro-sheet | |
| KR101670260B1 (en) | Method of manufacturing for graphene/carbon nanotube composite membrane | |
| CN110707328A (en) | Preparation method of graphene-coated aluminum foil | |
| CN112086297B (en) | Graphene nanocarbon electrode material, preparation method and lithium ion capacitor electrode | |
| CN103832997A (en) | Graphene/carbon black composite material, preparation method and application thereof | |
| CN104004496A (en) | Preparation method of reduced graphene oxide/nickel oxide composite wave absorbing material | |
| CN108047806A (en) | A kind of graphene/Ag- carbon microspheres aeroge coating and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140820 |