CN104108708B - A kind of nitrogen-doped graphene and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene and preparation method thereof Download PDFInfo
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- CN104108708B CN104108708B CN201410361251.2A CN201410361251A CN104108708B CN 104108708 B CN104108708 B CN 104108708B CN 201410361251 A CN201410361251 A CN 201410361251A CN 104108708 B CN104108708 B CN 104108708B
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Abstract
The present invention relates to a kind of nitrogen-doped graphene and preparation method thereof, described preparation method comprises: 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.The present invention, by heating the mixture of imdazole derivatives and mineral alkali in non-oxidizing atmosphere, utilizes imdazole derivatives pyrolysis to produce activated carbon and nitrogen-atoms and base catalysis and promotes the theory that carbon two-dimensional directional grows to prepare nitrogen-doped graphene.It is simple that the method 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; obtained nitrogen-doped graphene has the adjustable feature of nitrogen content, and N doping amount generally up to 14%, can be applicable to the every field such as lithium ion battery, ultracapacitor, electrocatalysis.
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 planar monolayer carbon atom be closely linked formed bi-dimensional cellular lattice material.After Geim group in 2004 obtains single-layer graphene first, Graphene is subject to extensive concern with the structure of its uniqueness and excellent physicals.But because Graphene does not have band gap to make its electric conductivity not controlled completely as traditional semi-conductor, and graphenic surface is smooth and be unfavorable for the compound of other materials thus hinder the application of Graphene in inertia.Graphene nitrating can be opened band gap and adjust the electronic structure that conduction type changes Graphene and improves the free carrier density of Graphene thus improve the conductivity of Graphene and stability.The main method of current Graphene nitrating has: 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 N doping amount; Although liquid phase nitriding N doping amount can reach 16.4%, relate to hazardous materials 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 be to provide a kind of technique simple, can the nitrogen-doped graphene preparation method of 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 imidazole, 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; obtained nitrogen-doped graphene has the adjustable feature of nitrogen content; N doping amount up to 14%, can be applicable to the every field such as lithium ion battery, ultracapacitor, electrocatalysis.
Accompanying drawing explanation
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, realized object and effect, accompanying drawing is coordinated to be explained in detail below in conjunction with embodiment.
The design of most critical of the present invention is: by heating 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 grows, 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, obtained nitrogen-doped graphene has the adjustable feature of nitrogen content, N doping amount 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 imidazole, 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-oxygenated property atmosphere, active nitrogen-atoms and carbon atom is produced through pyrolysis, carbon atom is reset at alkaline metal oxide surface nucleation, reset the growth presenting two-dimensional directional according to oxide surface template, and continuity is good, thus obtain Graphene.Meanwhile, the growth of the in-situ doped Graphene of the activated nitrogen atom of generation.Metal hydroxides has the advantages that to be dissolved in acid, and therefore mixture is 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 heating imdazole derivatives and mineral alkali in non-oxidizing atmosphere, the mixture of nitrogen-doped graphene and metal oxide can be prepared, follow-uply can remove metal oxide in mixture to obtain the higher nitrogen-doped graphene of purity by conventional impurity removal process such as pickling, 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, obtained nitrogen-doped graphene has the adjustable feature of nitrogen content, N doping amount 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, be easy to oxidized because nitrogen-doped graphene at high temperature contacts with air, the problems such as the product purity caused in order to avoid oxidation and Quality Down, the present invention is when removing the metal oxide in mixture, preferably in the following ways: under the condition of isolated air and/or mixture temperature remove metal oxide in mixture lower than adopting the mode of pickling under the condition of 100 DEG C, described acid be selected from hydrochloric acid and acetic acid one or more.Preferred, adopt in 37% concentrated hydrochloric acid and 30% acetic acid one or both, pickling 4-8 hour under the temperature condition of 40-60 DEG C.After having washed, can further suction filtration to dry to obtain highly purified nitrogen-doped graphene.
Preferably, the speed of described heating is 0.5-15 DEG C/min.When heating rate is too fast, the productive rate of nitrogen-doped graphene is lower, and excessively slow heating rate, greatly can 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, after the mixture of described nitrogenous source and mineral alkali is heated to 400-800 DEG C under non-oxidizing atmosphere, be incubated 1-6h.
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, mixed in mortar, and put into magnetic boat, 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, mixed in mortar, and put into magnetic boat, 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 imidazole and 1 gram of sodium hydroxide respectively, mixed in mortar, and put into magnetic boat, 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, mixed in mortar, and put into magnetic boat, 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, mixed in mortar, and put into magnetic boat, 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 37% concentrated hydrochloric acid of 10 milliliters and 30% acetic acid of 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 the potassium hydroxide of 0.5 gram of 2-undecyl imidazole, 1.0 grams of lithium hydroxides and 0.3 gram respectively, mixed in mortar, and put into magnetic boat, 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, mixed in mortar, and put into magnetic boat, 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%.
By the nitrogen-doped graphene that above-described embodiment 1-7 prepares, carry out electron-microscope scanning, the scanning electron microscope (SEM) photograph obtained can refer 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 about 4nm.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; 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 imidazole, 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: be incubated 1-6h after the mixture of described imdazole derivatives and mineral alkali is heated to 400-800 DEG C under non-oxidizing atmosphere.
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 remove metal oxide in mixture lower than adopting the mode of pickling under the condition of 100 DEG C, described pickling acid used be selected from hydrochloric acid and acetic acid one or both.
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 prepared by the preparation method described in claim 1 to 7 any one.
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| CN106582767B (en) * | 2016-12-28 | 2019-04-05 | 山东理工大学 | The preparation of cobalt and nitrogen co-doped three-dimensional grapheme |
| CN106744846B (en) * | 2016-12-28 | 2019-07-30 | 山东理工大学 | A kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing |
| CN106744852B (en) * | 2016-12-28 | 2019-07-23 | 山东理工大学 | The preparation method of iron and nitrogen co-doped three-dimensional grapheme |
| CN106582817B (en) * | 2016-12-28 | 2019-05-28 | 山东理工大学 | A kind of short-cut method preparing N doping three-dimensional grapheme |
| CN108467038A (en) * | 2018-05-30 | 2018-08-31 | 安徽工业大学 | A kind of preparation method of ultracapacitor nitrogen-doped carbon nano net |
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| JPH0790588A (en) * | 1993-09-24 | 1995-04-04 | Res Dev Corp Of Japan | Production of nitrigen containing carbon film |
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
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