CN102718206A - A macroscopic quantity preparation method for a nitrogen-doped graphene - Google Patents
A macroscopic quantity preparation method for a nitrogen-doped graphene Download PDFInfo
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- CN102718206A CN102718206A CN2011100768065A CN201110076806A CN102718206A CN 102718206 A CN102718206 A CN 102718206A CN 2011100768065 A CN2011100768065 A CN 2011100768065A CN 201110076806 A CN201110076806 A CN 201110076806A CN 102718206 A CN102718206 A CN 102718206A
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Abstract
The invention discloses a macroscopic quantity preparation method for a nitrogen-doped graphene. Specifically, the method is a method based on a solvothermal principle, producing a nitrogen-doped graphene by directly reacting a nitrogen-containing precursor with a carbon-containing precursor at a low temperature. Kind and content of nitrogen species can be adjusted and controlled by changing the kind and the content of the nitrogen-containing precursor and controlling conditions such as post-treatment temperature. The method has characteristics of simplicity, easy operation and control.
Description
Technical field
The present invention relates to adulterated graphene nano material of a kind of nitrogen and magnanimity preparation method thereof.
Background technology
Graphene is by individual layer sp
2The two-dimentional xln that the carbon of hydridization is formed, it is many allotropic substances such as zero dimension soccerballene, the one dimension carbon nanotube of carbon, the basic structural unit of three-dimensional graphite.Discover that Graphene has big specific surface area, high thermal conductivity and specific conductivity, high charge carrier mobility.Therefore, it be with a wide range of applications in fields such as energy storage material, nano field-effect transistor, chemical sensor, opto-electronic devices [A. K. Geim, K. S. Novoselov,
Nat. Mater. 6, 183 (2007); M. J. Allen, V. C. Tung, R. B. Kaner,
Chem. Rev. 110, 132 (2010)].Yet Graphene has certain chemically reactive except the edge defect position, and the unreactiveness of self structure has limited its application at catalytic field.Theoretical Calculation shows; Because the electronegativity of nitrogen is higher than carbon, and the lone-pair electron of nitrogen can form conjugated structure with the π system of Graphene, therefore through nitrogen the doping characteristic electron and chemically reactive [the F. Cervantes-Sodi of modulation Graphene effectively; G. Csanyi; S. Piscanec, A. C. Ferrari, Phys. Rev. B
77, 165427 (2008)].In addition; Because nitrogen-atoms can be entrained in the different positions in the Graphene skeleton; According to its position and different with the one-tenth key mode of carbon atom; Can be divided into the nitrogen of graphite mould, the nitrogen of pyridine type and the nitrogen of pyrroles's type, therefore not the nitrogen species of isomorphism type to the promotor action of Graphene physico-chemical property also with difference, and then be expected to expand the application of Graphene in catalysis and other association area.
Yet the research of nitrogen-doped graphene and application-dependent are in its large-scale preparation.Therefore, many investigators are devoted to the development of nitrogen-doped graphene.At present, the method for preparing nitrogen-doped graphene mainly comprises following several kinds: nitrogen species [X. L. Li, H. J. Dai, et al. J. Am. Chem. Soc. are introduced through thermal treatment Graphene or graphite oxide under the atmosphere of ammonia in (1)
131, 15939 (2009)], this method can obtain the adulterated Graphene of nitrogen, yet the nitrogen species of being introduced often on the limit of Graphene, adulterated nitrogen species is stablized in very difficult formation.(2) under the atmosphere of ammonia, utilize epitaxially grown method at the adulterated Graphene of Cu/Si single-crystal surface growth nitrogen.This method can obtain large stretch of Graphene, but the single-crystal surface utilization ratio is very low, and price is also relatively more expensive, is difficult to realize magnanimity production [D. C. Wei, G. Yu, et al. Nano Lett.
9, 1752 (2009)].(3) method through the arc-over Graphite Electrodes prepares the adulterated Graphene of nitrogen [L. S. Panchokarla, C. N. R. Rao, et al. Adv. Mater. under the atmosphere of pyridine, hydrogen and helium
21, 4726 (2009)].This method is often higher to equipment requirements, and reaction conditions is relatively harsher.Therefore, magnanimity prepares the adulterated Graphene of nitrogen and is still a challenge so far, also is the bottleneck of its application of restriction.
Summary of the invention
The invention discloses a kind of method of mass preparation high quality Graphene.
The present invention utilizes nitrogenous precursor and carbon containing precursor under relatively mild temperature, and single step reaction generates the adulterated Graphene of nitrogen.Kind of nitrogen species (comprising the nitrogen of graphite mould, the nitrogen of pyridine type and the nitrogen of pyrroles's type) and content can carry out modulation through adding other nitrogenous precursor and post-treatment condition.Add different nitrogenous precursors as passing through, the content of nitrogen can carry out modulation in the 2%-18% scope.
According to the present invention, the preparation process of nitrogen-doped graphene is following:
(1) with nitrogenous precursor and carbon containing precursor at the protection of inert gas lower seal to autoclave;
(2) autoclave in (1) was kept 1-20 hour in 150-500 ℃;
(3) sample of (2) gained was handled 3-5 hour in mass concentration 5-37.5% hydrochloric acid soln; Water and ethanol wash respectively and filter then, are neutral until solution;
(4), promptly obtain the adulterated Graphene of nitrogen with (3) gained sample drying.
Said nitrogenous precursor is a kind of in lithium nitride, sodiumazide, the Cynuric Chloride or more than two kinds;
Said carbon containing precursor is a kind of in tetracol phenixin, ethanol, methyl alcohol, the acetone or more than two kinds;
The mass ratio of nitrogenous precursor and carbon containing precursor is 1:40-1:1;
Above-mentioned raw materials prepares the adulterated Graphene of nitrogen through solvent thermal reaction.
Rare gas element is nitrogen, argon gas or helium.
Temperature of reaction also can be 200-450 ℃, is generally 250-400 ℃, is preferably 250-300 ℃; Keep temperature also to can be 2-15 hour, be generally 3-12 hour, be preferably 6-8 hour.
Drying temperature is 60-120 ℃, and be 6-12 hour time of drying.
With the thermal treatment of the adulterated Graphene of the nitrogen of gained through differing temps under the different atmosphere, further nitrogen content and the nitrogen species in the modulation gained Graphene comprises the nitrogen of graphite mould, the nitrogen of pyridine type and the nitrogen of pyrroles's type.Said different atmosphere is meant in rare gas element or in reducing atmosphere; Rare gas element comprises a kind of in nitrogen, argon gas or the helium or more than two kinds, reducing atmosphere is to contain the reducing atmosphere that constitutes in the rare gas element of volume 1-90% hydrogen.Said heat treated temperature is between 150-1000 ℃.
Analytical test shows that the nitrogen-doped graphene that the present invention obtains is nano-sheet and distributes, and the content of nitrogen can carry out modulation between 2%-18%.
The present invention has following advantage:
1. containing carbon matrix precursor can be tetracol phenixin, ethanol, methyl alcohol or acetone etc., and its wide material sources are cheap.
2. adopt the solvent thermal process of single step reaction, method is simple.Temperature of reaction is relatively low, easy handling.
3. utilizing the laboratory volume is 40 milliliters reaction kettle, and the single reaction yield of nitrogen-doped graphene can reach the rank of gram, and therefore the volume through changing reaction kettle etc. can be realized the magnanimity preparation of nitrogen-doped graphene.
4. resulting Graphene is unsupported.
5. the content of nitrogen species and kind can be regulated and control, and are expected to expand the application of Graphene in different field.
Description of drawings
Fig. 1 is the transmission electron microscope of embodiment 1 sample;
Fig. 2 is the x-ray photoelectron power spectrum of embodiment 1 sample and embodiment 4 samples;
Fig. 3 is the Raman spectrum of embodiment 1 sample and embodiment 2 samples;
Fig. 4 is the scanning tunnel microscope of embodiment 2 samples.
Embodiment
Through embodiment whole process is done a detailed explanation below, but claim scope of the present invention does not receive the restriction of these embodiment.Simultaneously, embodiment has just provided the partial condition of realizing this purpose, but and does not mean that must satisfy these conditions just can reach this purpose.
With 1.0 g lithium nitrides and 20.0 mL tetracol phenixin in nitrogen protection lower seal to 40 mL autoclave.
2. the autoclave in (1) was kept 10 hours in 250 ℃.
3. the sample of (2) gained was handled 3 hours in 18% (mass concentration) hydrochloric acid soln.Water and washing with alcohol be repeatedly and filter respectively then.
4. (3) gained sample was promptly obtained the adulterated Graphene of nitrogen in 12 hours in 120 ℃ of dryings.
Primary first-order equation can obtain adulterated Graphene sample 1.2 grams of pure nitrogen.The transmission electron microscope (see figure 1) shows that the gained Graphene distributes in the form of sheets, and the number of plies is the 1-6 layer; X-ray photoelectron power spectrum (see figure 2) shows gained Graphene nitrogen content at 4.5% (N/C %, down together), and nitrogen species is main with graphite nitrogen mainly; Raman spectrum (seeing NG-1 among Fig. 3) shows that there is remarkable enhancing at the D peak of the adulterated Graphene of gained nitrogen than pure Graphene, shows that the doping of nitrogen has caused more defects.
With 2.0 g lithium nitrides, 0.5 g Cynuric Chloride and 20.0 mL tetracol phenixin in nitrogen protection lower seal to 40 mL autoclave.
2. the autoclave in (1) was kept 6 hours in 350 ℃.
3. with the step 3 of embodiment 1.
4. with the step 4 of embodiment 1.
The scanning tunnel microscope (see figure 4) has been showed because the electronics twisted phenomena of the caused Graphene of doping of nitrogen.Raman spectrum (seeing NG-2 among Fig. 3) shows that there is remarkable enhancing at the D peak of the adulterated Graphene of gained nitrogen than pure Graphene, shows that the doping of nitrogen has caused more defects.X-ray photoelectron spectroscopic analysis test (seeing table 2) shows gained Graphene nitrogen content 16.4%, and nitrogen species is main with pyridine nitrogen mainly.
Embodiment 3
With 2.0 g sodiumazide and 20.0 mL tetracol phenixin in argon shield lower seal to 40 mL autoclave.
2. the autoclave in (1) was kept 6 hours in 350 ℃.
3. with the step 3 of embodiment 1.
4. with the step 4 of embodiment 1.
Analytical test shows that the gained Graphene distributes in the form of sheets, and nitrogen content is 4.8%, and nitrogen species is main with pyrroles's nitrogen and pyridine nitrogen mainly.
Embodiment 4
1. resulting three parallel sample of step 4 of getting embodiment 1 place the temperature programming stove of argon shield respectively.
2. the parallel sample in (1) was handled 2 hours respectively at 250 ℃, 400 ℃, 600 ℃.
Analytical test shows that the gained Graphene distributes in the form of sheets, and X-ray photoelectron spectroscopic analysis (seeing Fig. 2 and table 1) shows: along with the increase of treatment temp, the content of nitrogen reduces gradually; Through different treatment temps, the content of nitrogen can be regulated and control between 4.5%-3.0%; Graphite nitrogen and pyridine nitrogen are stable at the sample intensive amount, and pyrroles's nitrogen reduces under pyroprocessing obviously.
Table 1
Embodiment 5
1. resulting three parallel sample of step 4 of getting embodiment 2 place the temperature programming stove of argon shield respectively.
2. the parallel sample in (1) was handled 2 hours respectively at 250 ℃, 400 ℃, 600 ℃.
Analytical test shows that the gained Graphene distributes in the form of sheets, and X-ray photoelectron spectroscopic analysis (seeing table 2) shows: along with the increase of treatment temp, the content of nitrogen reduces gradually; Through different treatment temps, the content of nitrogen can be regulated and control between 16.4%-10.5%; Graphite nitrogen and pyridine nitrogen are stable at the sample intensive amount, and pyrroles's nitrogen reduces under pyroprocessing obviously.
Table 2
The present invention is a kind of based on solvent thermal method, utilizes nitrogenous precursor and carbon containing precursor direct reaction at low temperatures, generates the adulterated Graphene of nitrogen.The kind of nitrogen species and content can be regulated and control through kind and content that changes nitrogenous precursor and the conditions such as temperature of controlling aftertreatment.The characteristics that present method has simply, is easy to operate and control.
Claims (8)
1. a magnanimity prepares the method for nitrogen-doped graphene, it is characterized in that:
(1) with nitrogenous precursor and carbon containing precursor at the protection of inert gas lower seal to autoclave;
(2) autoclave in (1) was kept 1-20 hour in 150-500 ℃;
(3) sample of (2) gained was handled 3-5 hour in mass concentration 5-37.5% hydrochloric acid soln; Water and ethanol wash respectively and filter then, are neutral until solution;
(4), promptly obtain the adulterated Graphene of nitrogen with (3) gained sample drying.
2. according to (1) described method in the claim 1, it is characterized in that:
Said nitrogenous precursor is a kind of in lithium nitride, sodiumazide, the Cynuric Chloride or more than two kinds;
Said carbon containing precursor is a kind of in tetracol phenixin, ethanol, methyl alcohol, the acetone or more than two kinds;
The mass ratio of nitrogenous precursor and carbon containing precursor is 1:40-1:1;
Above-mentioned raw materials prepares the adulterated Graphene of nitrogen through solvent thermal reaction.
3. according to (1) described method in the claim 1, it is characterized in that:
Rare gas element is nitrogen, argon gas or helium.
4. according to (2) described method in the claim 1, it is characterized in that:
Temperature of reaction also can be 200-450 ℃, is generally 250-400 ℃, is preferably 250-300 ℃; Keep temperature also to can be 2-15 hour, be generally 3-12 hour, be preferably 6-8 hour.
5. according to (4) described method in the claim 1, it is characterized in that:
Drying temperature is 60-120 ℃, and be 6-12 hour time of drying.
6. method according to claim 1 is characterized in that:
With the thermal treatment of the adulterated Graphene of the nitrogen of gained through differing temps under the different atmosphere, further nitrogen content and the nitrogen species in the modulation gained Graphene comprises the nitrogen of graphite mould, the nitrogen of pyridine type and the nitrogen of pyrroles's type.
7. method according to claim 6 is characterized in that: said different atmosphere is meant in rare gas element or in reducing atmosphere; Rare gas element comprises a kind of in nitrogen, argon gas or the helium or more than two kinds, reducing atmosphere is to contain the reducing atmosphere that constitutes in the rare gas element of volume 1-90% hydrogen.
8. method according to claim 6 is characterized in that: said heat treated temperature is between 150-1000 ℃.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058177A (en) * | 2013-01-05 | 2013-04-24 | 张家港市东大工业技术研究院 | Preparation method for realizing N-doped grapheme by high-energy microwave vacuum irradiation |
| CN103539102A (en) * | 2013-10-14 | 2014-01-29 | 南京大学 | Method and device for preparing nitrogen-doped graphene oxide |
| CN105384163A (en) * | 2015-11-26 | 2016-03-09 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped graphene with solvent heat |
| CN105731443A (en) * | 2016-03-30 | 2016-07-06 | 青岛科技大学 | Method for preparing high-ratio graphite-type nitrogen-doped graphene tube in template-free one-step method |
| CN105800571A (en) * | 2016-02-26 | 2016-07-27 | 浙江大学 | Preparation method for two-dimensional nanosheet carbon nitride material |
| CN105810530A (en) * | 2016-03-30 | 2016-07-27 | 青岛科技大学 | Preparation method and application of nitrogen-doped graphene@SiO2 coaxial nanotube |
| CN108168992A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of method of the concentration and separation glycopeptide based on two-dimentional porous crystalline nitrogen-doped carbon material |
| CN108221088A (en) * | 2017-12-19 | 2018-06-29 | 同济大学 | A kind of preparation method for preparing high nitrogen-containing, the adjustable nitrogen-doped carbon nano-fiber of nitrating type |
| CN108914251A (en) * | 2018-07-09 | 2018-11-30 | 杭州高烯科技有限公司 | A kind of azepine graphite fibre and preparation method thereof |
| WO2019119460A1 (en) * | 2017-12-23 | 2019-06-27 | 深圳大学 | Method for preparing nitrogen-doped graphene from furazan derivatives as nitrogen source |
-
2011
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Non-Patent Citations (2)
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| DEHUI DENG,ET.AL.: "Toward N-Doped Graphene via Solvothermal Synthesis", 《CHEMISTRY OF MATERIALS 》 * |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058177B (en) * | 2013-01-05 | 2014-05-07 | 张家港市东大工业技术研究院 | Preparation method for realizing N-doped grapheme by high-energy microwave vacuum irradiation |
| CN103058177A (en) * | 2013-01-05 | 2013-04-24 | 张家港市东大工业技术研究院 | Preparation method for realizing N-doped grapheme by high-energy microwave vacuum irradiation |
| CN103539102A (en) * | 2013-10-14 | 2014-01-29 | 南京大学 | Method and device for preparing nitrogen-doped graphene oxide |
| CN105384163A (en) * | 2015-11-26 | 2016-03-09 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped graphene with solvent heat |
| CN105800571A (en) * | 2016-02-26 | 2016-07-27 | 浙江大学 | Preparation method for two-dimensional nanosheet carbon nitride material |
| CN105810530A (en) * | 2016-03-30 | 2016-07-27 | 青岛科技大学 | Preparation method and application of nitrogen-doped graphene@SiO2 coaxial nanotube |
| CN105731443A (en) * | 2016-03-30 | 2016-07-06 | 青岛科技大学 | Method for preparing high-ratio graphite-type nitrogen-doped graphene tube in template-free one-step method |
| CN105731443B (en) * | 2016-03-30 | 2018-01-26 | 青岛科技大学 | The method that graphite mould nitrogen-doped graphene pipe at high proportion is prepared without template one-step method |
| CN105810530B (en) * | 2016-03-30 | 2018-05-25 | 青岛科技大学 | Nitrogen-doped graphene@SiO2The preparation method and application of Coaxial Nanotubes |
| CN108168992A (en) * | 2016-12-07 | 2018-06-15 | 中国科学院大连化学物理研究所 | A kind of method of the concentration and separation glycopeptide based on two-dimentional porous crystalline nitrogen-doped carbon material |
| CN108221088A (en) * | 2017-12-19 | 2018-06-29 | 同济大学 | A kind of preparation method for preparing high nitrogen-containing, the adjustable nitrogen-doped carbon nano-fiber of nitrating type |
| CN108221088B (en) * | 2017-12-19 | 2020-12-11 | 同济大学 | Preparation method for nitrogen-doped carbon nanofiber with high nitrogen content and adjustable nitrogen doping type |
| WO2019119460A1 (en) * | 2017-12-23 | 2019-06-27 | 深圳大学 | Method for preparing nitrogen-doped graphene from furazan derivatives as nitrogen source |
| CN108914251A (en) * | 2018-07-09 | 2018-11-30 | 杭州高烯科技有限公司 | A kind of azepine graphite fibre and preparation method thereof |
| CN108914251B (en) * | 2018-07-09 | 2020-10-30 | 杭州高烯科技有限公司 | Nitrogen-doped graphite fiber and preparation method thereof |
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Application publication date: 20121010 |