CN104108708A - Nitrogen-doped graphene and preparation method thereof - Google Patents
Nitrogen-doped graphene and preparation method thereof Download PDFInfo
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- CN104108708A CN104108708A CN201410361251.2A CN201410361251A CN104108708A CN 104108708 A CN104108708 A CN 104108708A CN 201410361251 A CN201410361251 A CN 201410361251A CN 104108708 A CN104108708 A CN 104108708A
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Abstract
The invention relates to a nitrogen-doped graphene and a preparation method thereof. The preparation method comprises the following steps: heating a mixture of imidazole derivatives and inorganic base to 400-800 DEG C under a non-oxidizing atmosphere so as to obtain a nitrogen-doped graphene and metal oxide mixture; removing the metal oxide in the mixture to obtain the nitrogen-doped graphene. The nitrogen-doped graphene can be prepared by heating the mixture of imidazole derivatives and inorganic base under non-oxidizing atmosphere through utilizing conception that imidazole derivatives are pyrolyzed to generate activated carbon and nitrogen atoms and carry out base catalysis on accelerate the growth in two-dimension direction. The method has the characteristics of being simple in technology, short in production period, easy for mass production, free from dangerous and toxic raw materials, and capable of doping nitrogen in situ, and according to the selected different nitrogen sources, the prepared nitrogen-doped graphene has the characteristic of being adjustable in nitrogen content, the content of doped nitrogen can be up to 14% generally, and the nitrogen-doped graphene can be applied in the fields of lithium ion batteries, super capacitors, electric catalysis and the like.
Description
Technical field
The present invention relates to carbon material technical field, particularly a kind of nitrogen-doped graphene and preparation method thereof.
Background technology
Graphene be plane monolayer carbon atom be closely linked form bi-dimensional cellular lattice material.Make first after single-layer graphene from Geim group in 2004, Graphene is subject to extensive concern with its unique structure and excellent physicals.But, because Graphene does not have band gap, its electric conductivity can not be controlled by complete quilt as traditional semi-conductor, thus and Graphene smooth surface and be inertia and be unfavorable for and the compound application that hinders Graphene of other materials.Thereby Graphene nitrating can be opened band gap and adjust conduction type the conductivity and the stability that change the free carrier density raising Graphene of the electronic structure raising Graphene of Graphene.The main method of Graphene nitrating has at present: chemical Vapor deposition process, the pyrolysis of ammonia source, nitrogen plasma discharge method, arc discharge method, ammonia electrothermal reaction method and liquid phase nitriding etc.At present there is following shortcoming in these methods: chemical Vapor deposition process, ammonia source pyrolysis method, nitrogen plasma discharge method, arc discharge method etc. exist the not high and many preparation procedures of nitrogen doping; Although liquid phase nitriding nitrogen doping can reach 16.4%, relates to dangerous raw material Li
3n, reaction conditions is relatively harsh.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, technical problem to be solved by this invention is to provide that a kind of technique is simple, nitrogen-doped graphene preparation method that can in-situ doped nitrogen.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of nitrogen-doped graphene preparation method, comprising:
The mixture of imdazole derivatives and mineral alkali is heated to 400-800 DEG C under non-oxidizing atmosphere, obtains the mixture of nitrogen-doped graphene and metal oxide;
Remove the metal oxide in mixture, obtain nitrogen-doped graphene;
Wherein, described imdazole derivatives is selected from one or more in benzoglyoxaline, first mercaptobenzimidazole, mercaptobenzimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-butyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 1 benzyl 2 methyl imidazole;
Wherein, described mineral alkali is selected from one or more in the oxyhydroxide of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium or barium.
Beneficial effect of the present invention is: technique is simple, with short production cycle, be easy to large-scale production; not containing dangerous toxic raw materials; can in-situ doped nitrogen; and according to the difference of selected nitrogenous source; the nitrogen-doped graphene making has the adjustable feature of nitrogen content; nitrogen doping can be up to 14%, can be applicable to the every field such as lithium ion battery, ultracapacitor, electrocatalysis.
Brief description of the drawings
Figure 1 shows that the scanning electron microscope (SEM) photograph of nitrogen-doped graphene prepared by the embodiment of the present invention 1.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, being realized object and effect, below in conjunction with embodiment and coordinate accompanying drawing to be explained in detail.
The design of most critical of the present invention is: by heat the mixture of imdazole derivatives and mineral alkali in non-oxidizing atmosphere, utilize imdazole derivatives pyrolysis to produce activated carbon and nitrogen-atoms and base catalysis and promote the theory that carbon two-dimensional directional is grown, prepare nitrogen-doped graphene, the method technique is simple, with short production cycle, be easy to large-scale production, not containing dangerous toxic raw materials, can in-situ doped nitrogen, and according to the difference of selected nitrogenous source, the nitrogen-doped graphene making has the adjustable feature of nitrogen content, nitrogen doping generally can reach 14% (weight ratio), can be applicable to lithium ion battery, ultracapacitor, the every field such as electrocatalysis.
Nitrogen-doped graphene preparation method provided by the invention, comprising:
The mixture of imdazole derivatives and mineral alkali is heated to 400-800 DEG C under non-oxidizing atmosphere, obtains the mixture of nitrogen-doped graphene and metal oxide;
Remove the metal oxide in mixture, obtain nitrogen-doped graphene;
Wherein, described nitrogenous source is selected from one or more in benzoglyoxaline, first mercaptobenzimidazole, mercaptobenzimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-butyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 1 benzyl 2 methyl imidazole;
Wherein, described mineral alkali is selected from one or more in the oxyhydroxide of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium or barium.
The mechanism that the present invention prepares nitrogen-doped graphene is as follows:
In the mixed system containing imdazole derivatives and mineral alkali, imdazole derivatives as carbon and nitrogenous source in high temperature non-oxidizing atmosphere, produce active nitrogen-atoms and carbon atom through pyrolysis, carbon atom is reset at alkaline metal oxide surface nucleation, reset the growth that presents two-dimensional directional according to oxide surface template, and continuity is good, thereby obtain Graphene.Meanwhile, the growth of the in-situ doped Graphene of activated nitrogen atom of generation.Metal hydroxides has the sour feature that is dissolved in, and therefore mixture, after cleanup acid treatment, can obtain pure Graphene.
From foregoing description, beneficial effect of the present invention is:
Because the present invention only needs by heat imdazole derivatives and mineral alkali in non-oxidizing atmosphere, can prepare the mixture of nitrogen-doped graphene and metal oxide, the follow-up metal oxide that can remove in mixture by conventional impurity removal process such as pickling obtains the nitrogen-doped graphene that purity is higher, therefore compared to existing technologies, it is simple that the present invention has technique, with short production cycle, be easy to large-scale production, not containing dangerous toxic raw materials, can in-situ doped nitrogen, and according to the difference of selected nitrogenous source, the nitrogen-doped graphene making has the adjustable feature of nitrogen content, nitrogen doping generally can reach 14%, can be applicable to lithium ion battery, ultracapacitor, the every field such as electrocatalysis.
Preferably, the weight ratio of described imdazole derivatives and mineral alkali is nitrogenous source: mineral alkali=0.1: 100-2: 1.
Preferably, described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
Preferably, due to nitrogen-doped graphene at high temperature contact with air be easy to oxidized, the problem such as product purity and Quality Down causing for fear of oxidation, the present invention is in the time of the metal oxide of removing in mixture, preferably in the following ways: under the condition of isolated air and/or mixture temperature adopt the mode of pickling to remove the metal oxide in mixture under lower than the condition of 100 DEG C, described acid is selected from one or more in hydrochloric acid and acetic acid.Preferred, one or both in employing 37% concentrated hydrochloric acid and 30% acetic acid, pickling 4-8 hour under the temperature condition of 40-60 DEG C.After having washed, further suction filtration is to being dried to obtain highly purified nitrogen-doped graphene.
Preferably, the speed of described heating is 0.5-15 DEG C/min.In the time that heating rate is too fast, the productive rate of nitrogen-doped graphene is lower, and excessively slow heating rate, can greatly extend again the production cycle of product.Preferred, the speed of described heating is 2-10 DEG C/min.
Preferably, in order to improve the quality product of nitrogen-doped graphene, the mixture of described nitrogenous source and mineral alkali is incubated 1-6h be heated to 400-800 DEG C under non-oxidizing atmosphere after.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, take 0.7 gram of benzoglyoxaline and 1.5 grams of lithium hydroxides respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of nitrogen atmosphere, be heated to 600 DEG C, keep 2 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, obtains nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 14%.
Embodiment 2, take 0.5 gram of benzoglyoxaline and 1.5 grams of strontium hydroxides respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of argon gas atmosphere, be heated to 800 DEG C, keep 2 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 10.3%.
Embodiment 3, take 2 grams of heptadecyl imidazoles and 1 gram of sodium hydroxide respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of argon gas atmosphere, be heated to 750 DEG C, keep 1 hour, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 12.4%.
Embodiment 4, take 0.5 gram of benzoglyoxaline and 1.5 grams of lithium hydroxides respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of ammonia atmosphere, be heated to 600 DEG C, keep 6 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 13.9%.
Embodiment 5, take 0.5 gram of benzoglyoxaline, 0.5 gram of first mercaptobenzimidazole and 3 grams of lithium hydroxides respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of ammonia atmosphere, be heated to 600 DEG C, keep 6 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with the mixed acid solution of 30% acetic acid of 37% concentrated hydrochloric acids of 10 milliliters and 5 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 13.85%.
Embodiment 6, take respectively the potassium hydroxide of 0.5 gram of 2-undecyl imidazole, 1.0 grams of lithium hydroxides and 0.3 gram, in mortar, mixed, and put into magnetic boat, and in the tube furnace of ammonia atmosphere, be heated to 600 DEG C, keep 6 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 13.1%.
Embodiment 7, take 0.01 gram of 2-undecyl imidazole, the potassium hydroxide of 10 grams respectively, in mortar, mixed, and put into magnetic boat, and in the tube furnace of ammonia atmosphere, be heated to 700 DEG C, keep 6 hours, treat that furnace temperature is down to room temperature, obtain nitrogen-doped graphene and calcium oxide composite, with 37% concentrated hydrochloric acids of 10 milliliters at room temperature, wash 4 hours, suction filtration, to dry, can obtain nitrogen-doped graphene.Through ultimate analysis, the nitrogen content of this nitrogen-doped graphene is 11.8%.
The nitrogen-doped graphene that above-described embodiment 1-7 is prepared, carries out electron-microscope scanning, and the scanning electron microscope (SEM) photograph obtaining can be with reference to shown in Fig. 1.Known as shown in Figure 1, the nitrogen-doped graphene that the present invention finally prepares is made up of the thin nanometer sheet of fold, and the thickness of nitrogen-doped graphene is 4nm left and right.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes specification sheets of the present invention and accompanying drawing content to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. a nitrogen-doped graphene preparation method, is characterized in that, comprising:
The mixture of imdazole derivatives and mineral alkali is heated to 400-800 DEG C under non-oxidizing atmosphere, obtains the mixture of nitrogen-doped graphene and metal oxide;
Remove the metal oxide in mixture, obtain nitrogen-doped graphene;
Wherein, described imdazole derivatives is selected from one or more in benzoglyoxaline, first mercaptobenzimidazole, mercaptobenzimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-butyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 1 benzyl 2 methyl imidazole;
Wherein, described mineral alkali is selected from one or more in the oxyhydroxide of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium or barium.
2. nitrogen-doped graphene preparation method according to claim 1, is characterized in that: the mixture of described imdazole derivatives and mineral alkali is incubated 1-6h be heated to 400-800 DEG C under non-oxidizing atmosphere after.
3. nitrogen-doped graphene preparation method according to claim 1, it is characterized in that: under the condition of isolated air and/or mixture temperature adopt the mode of pickling to remove the metal oxide in mixture under lower than the condition of 100 DEG C, described acid is selected from one or both in hydrochloric acid and acetic acid.
4. nitrogen-doped graphene preparation method according to claim 1, is characterized in that: described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
5. nitrogen-doped graphene preparation method according to claim 1, is characterized in that: the speed of described heating is 0.5-15 DEG C/min.
6. nitrogen-doped graphene preparation method according to claim 1, is characterized in that: the speed of described heating is 2-10 DEG C/min.
7. nitrogen-doped graphene preparation method according to claim 1, is characterized in that: the weight ratio of described imdazole derivatives and mineral alkali is imdazole derivatives: mineral alkali=0.1: 100-2: 1.
8. the nitrogen-doped graphene being prepared by the preparation method described in claim 1 to 7 any one.
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| CN106477566A (en) * | 2016-12-28 | 2017-03-08 | 山东理工大学 | A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing |
| CN106582818A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Method of preparing three-dimensional nitrogen-doped graphene from polybenzimidazole with pyrazinyl |
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| CN106582767A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Preparation of 3D graphene co-doped with cobalt and nitrogen |
| CN106582817A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Simple and convenient method for preparing three-dimensional nitrogen-doped graphene |
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| US10730752B2 (en) | 2016-05-03 | 2020-08-04 | Virginia Commonwealth University | Heteroatom-doped porous carbons for clean energy applications and methods for their synthesis |
| CN106744847A (en) * | 2016-12-28 | 2017-05-31 | 山东理工大学 | With poly-（2,5 benzimidazoles）The method for preparing three-dimensional nitrogen-doped graphene |
| CN106582767A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Preparation of 3D graphene co-doped with cobalt and nitrogen |
| CN106477566B (en) * | 2016-12-28 | 2019-01-29 | 山东理工大学 | A kind of preparation method of the three-dimensional nitrogen-doped graphene of high nitrogen-containing |
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