CN103553027B - Fluorinated graphene is utilized to prepare the method for high content nitrogen doped graphene - Google Patents
Fluorinated graphene is utilized to prepare the method for high content nitrogen doped graphene Download PDFInfo
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Abstract
Fluorinated graphene is utilized to prepare the method for high content nitrogen doped graphene, be starting material with fluorinated graphene, take ammonia as nitrogenous source, fluorinated graphene is placed in tube furnace, pass to ammonia and isothermal reaction 2-7 hour at being heated to 500 ± 50 DEG C, naturally cool to room temperature.For the tube furnace that 3-5 rises, ammonia flow keeps 20sccm.Raw material fluorinated Graphene preparation: be starting material with fluorographite, utilizes liquid phase ethylene glycol to peel off fluorographite and obtains fluorinated graphene.With nitrogen-doped graphene prepared by method of the present invention, nitrogen content is higher, and its nitrogen-atoms number percentage composition reaches 13.90%; And oxygen level is lower, its atom number percentage composition is only 6.56%.
Description
One, technical field
The present invention relates to a kind of method and apparatus utilizing fluorinated graphene to prepare high content nitrogen doped graphene.Especially the nitrogen-doped graphene of high-content can be realized.
Two, background technology
Since nitrogen-doped graphene is found, because it has unique electronics, photoelectronic property, nitrogen-doped graphene has been widely used in bio-imaging, luminescence and photoelectricity aspect, is widely used in many fields such as solar cell, lithium cell, super capacitor.Particularly there is huge potential application in blue extremely infrared fluorescent material in light emission, bioluminescence demarcation, Organic Light Emitting Diode and solid state optoelectronic devices.The applicant study group has reported increasing along with nitrogen content in nitrogen-doped graphene not long ago, and its band gap can broaden, and the local magnetic moment simultaneously introduced also can increase.[1,2]
Nitrogen-doped graphene or the graphene oxide of current report adopt vapour deposition process usually, and its starting material are generally graphene oxide or the graphene oxide of reduction.[3] the applicant study group has reported the method that nitrogen mixes redox graphene and graphene oxide not long ago.The inventive method is that the strong of this method supplements, and the nitrogen content of nitrogen-doped graphene is high; And oxygen level is few after reaction, purity is higher, and it is more complete that gained nitrogen-doped graphene structure compares pyroreaction gained sample structure, can expand the application of nitrogen-doped graphene in photoelectric material and spin transport.The method utilizing fluorinated graphene to prepare high content nitrogen doped graphene of the application is the great discovery that nitrogen mixes Graphene research.
Reference
1.Liu,Y.,Feng,Q.,Tang,N.J.,Wan,X.G.,Liu,F.C.,Lv,L.Y.&Du,Y.W.Increased magnetization of reduced graphene oxide by nitrogen-doping.Carbon60,549-551(2013).
2.Liu,Y.,Feng,Q.,Xu,Q.H.,Li,M.,Tang,N.J.&Du,Y.W.Synthesis andphotoluminescence of F and N co-doped reduced graphene oxide.Carbon61,436-440(2013).
3.Liu,Y.,Tang,N.,Wan,X.,Feng,Q.,Li,M.,Xu,Q.,Liu,F.&Du,Y.Realization of ferromagnetic graphene oxide with high magnetization by dopinggraphene oxide with nitrogen.Sci.Rep.3,2566(2013).
Three, summary of the invention
The object of the invention is to, propose a kind of preparation method of simpler and easy, faster and more effective nitrogen-doped graphene.The present invention is by being starting material with fluorinated graphene, and ammonia is nitrogenous source, using tube furnace as reaction chamber, at 500 DEG C, nitrogen-doped graphene is prepared in reaction.Compared with traditional method, the nitrogen content of nitrogen-doped graphene is high; And oxygen level is few after reaction, purity is higher.
Technical scheme of the present invention is: utilize fluorinated graphene to prepare the method for high content nitrogen doped graphene, it is characterized in that taking fluorinated graphene as starting material, take ammonia as nitrogenous source, fluorinated graphene is placed in tube furnace, pass to ammonia and isothermal reaction 2-7 hour at being heated to 500 ± 50 DEG C, naturally cool to room temperature.For the tube furnace that 3-5 rises, ammonia flow of the present invention keeps 20sccm to obtain best effect.
Prepared by fluorinated graphene: be starting material with fluorographite, utilizes liquid phase ethylene glycol to peel off fluorographite and obtains fluorinated graphene.Take ethylene glycol as solvent, fluorographite is put into the ethylene glycol of more than 100 times weight, profit sonic oscillation 6-15 hour, recycling supercentrifuge centrifugal 2-15 minute under rotating speed more than 5000 rpms, gets supernatant liquid and dries obtained fluorinated graphene sample.
The method being better than the synthesis fluorinated graphene of prior art report with this intermediate adopts the fluorizating agents such as xenon difluoride to fluoridize Graphene to form.
Further, 100mg fluorographite puts into 400ml ethylene glycol, utilizes the ultrasonic shake of 160 watts of power to wash machine ultrasonic 9 hours, utilizes supercentrifuge under the rotating speed of 5000 rpms centrifugal 5 minutes, gets supernatant liquid and dries obtained fluorinated graphene sample.
The nitrogen-doped graphene product prepared with the present invention carries out stuctures and properties sign by following means: the Dimension V atomic force microscope (AFM) utilizing Veeco company of the U.S. to produce directly observes shape and the thickness of product; Adopt the N doping situation of x-ray Electron Energy Disperse Spectroscopy analytic sample.
The invention has the beneficial effects as follows: be at present reaction chamber using fluorinated graphene as starting material, with tube furnace about 500 DEG C with higher ammonia flow under prepare high content nitrogen doped graphene (and there is low oxygen content) method and apparatus never appear in the newspapers.Not in the then high content nitrogen difficulty acquisition of this temperature range; With nitrogen-doped graphene prepared by method of the present invention, nitrogen content is higher, and its nitrogen-atoms number percentage composition reaches 13.90%; And oxygen level is lower, its atom number percentage composition is only 6.56%.
Four, accompanying drawing explanation
Fig. 1 is the atomic force microscope observed result of fluorinated graphene in example, and product has the two-dimentional membrane structure of opposed flattened as seen from the figure.Its thickness distribution is less than 5nm mostly, and mean thickness is 2.92nm.
Fig. 2 is the N doping atomic force microscope observed result preparing gained in example, and product has the membrane structure of the two dimension of opposed flattened equally as seen from the figure, but its thickness declines to some extent, and mean thickness is 1.84nm.
Fig. 3 is fluorinated graphene and N doping fluorinated graphene x-ray electronic energy spectrum in example, there is obvious carbon peak and fluorine peak in fluorinated graphene (GF) 284.6eV and 685 original as seen from the figure, and nitrogen-doped graphene (NG) has more at 400eV place and showed an obvious nitrogen peak, illustrate that nitrogen-atoms has successfully been mixed into fluorinated graphene.
Five, embodiment
Below embodiments of the invention (in embodiment, agents useful for same is chemical pure).Take ammonia as nitrogenous source, 10mg fluorinated graphene is placed in tube furnace, pass to ammonia and isothermal reaction 3 hours at being heated to 500 DEG C, naturally cool to room temperature.Ammonia flow keeps 20sccm.Finally obtain required high content nitrogen and mix Graphene.
At 530 DEG C, isothermal reaction obtains and upper routine similar results for 5 hours.
At 480 DEG C, isothermal reaction obtains and upper routine similar results for 6 hours.
Special conversion unit tube furnace of the present invention comprises hollow quartz tube, heating source, thermocouple temperature control meter and air flow controller.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described.
Take ethylene glycol as solvent, 100mg fluorographite is put into 400ml ethylene glycol, utilize the ultrasonic shake of 160 watts of power to wash machine ultrasonic 9 hours, utilize supercentrifuge under the rotating speed of 5000 rpms centrifugal 5 minutes, get supernatant liquid and dry obtained fluorinated graphene sample.Be starting material with fluorinated graphene, take ammonia as nitrogenous source, 10mg fluorinated graphene is placed in tube furnace, pass to ammonia and drain air in silica tube, to prevent the reaction of air and fluorinated graphene.Keep the ammonia flow of 20sccm, react 3 hours at 500 DEG C, naturally cool to room temperature, namely obtain required nitrogen and mix Graphene.Fluorinated graphene and the nitrogen-doped graphene preparing gained are carried out the observation of atomic force microscope, result is shown in Fig. 1 and Fig. 2 respectively.
Fluorinated graphene and the N doping fluorinated graphene x-ray Electron Energy Disperse Spectroscopy preparing gained are analyzed, and the electronic spectrum of sample the results are shown in Figure 3.
Although prior art scheme of the present invention and preferred embodiment statement as above, so itself and be not used to limit the present invention.Persond having ordinary knowledge in the technical field of the present invention, without departing from the spirit and scope of the present invention, when doing various changes, substitute and retouching.Therefore, protection scope of the present invention is when being as the criterion depending on those as defined in claim.
Claims (5)
1.
fluorinated graphene is utilized to prepare the method for high content nitrogen doped graphene, it is characterized in that with fluorinated graphene being starting material, take ammonia as nitrogenous source, is placed on by fluorinated graphene in tube furnace, pass to ammonia and isothermal reaction 2-7 hour at being heated to 500 ± 50 DEG C, naturally cool to room temperature.
2. according to claim
the fluorinated graphene that utilizes described in 1 prepares the method for high content nitrogen doped graphene, and it is characterized in that the tube furnace risen for 3-5, ammonia flow keeps 20 sccm.
3. according to claim
the fluorinated graphene that utilizes described in 1 or 2 prepares the method for high content nitrogen doped graphene, it is characterized in that prepared by raw material fluorinated Graphene, is starting material with fluorographite, utilizes liquid phase ethylene glycol to peel off fluorographite and obtains fluorinated graphene; Take ethylene glycol as solvent, fluorographite is put into the ethylene glycol of more than 100 times weight, sharp sonic oscillation 6-15 hour, recycling supercentrifuge centrifugal 2-15 minute under rotating speed more than 5000 revs/min, get supernatant liquid and dry obtained fluorinated graphene.
4. according to claim
the fluorinated graphene that utilizes described in 3 prepares the method for high content nitrogen doped graphene, it is characterized in that 100 mg fluorographites put into 400 ml ethylene glycol, the ultrasonic shake of 160 watts of power is utilized to wash machine ultrasonic 9 hours, utilize supercentrifuge under the rotating speed of 5000 rpms centrifugal 5 minutes, get supernatant liquid and dry obtained fluorinated graphene sample.
5. according to claim
the fluorinated graphene that utilizes described in 1 prepares the method for high content nitrogen doped graphene, it is characterized in that being starting material with fluorinated graphene and be nitrogenous source with ammonia, fluorinated graphene is placed in tube furnace, pass to ammonia and isothermal reaction 3 hours at being heated to 500 DEG C, naturally cool to room temperature, ammonia flow keeps 20 sccm.
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| CN109534332A (en) * | 2018-12-26 | 2019-03-29 | 中国科学院福建物质结构研究所 | A kind of amidized fluorinated graphene and preparation method thereof |
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| CN104876218B (en) * | 2015-06-10 | 2017-06-20 | 北京化工大学 | A kind of room temperature preparation method of water-soluble functionalized graphite's alkene |
| CN106276885B (en) * | 2016-10-21 | 2018-07-13 | 兰州理工大学 | The fast preparation method of high conductivity nitrogen-doped graphene |
| CN106698410B (en) * | 2016-12-05 | 2019-11-26 | 四川大学 | The preparation method of nitrogen atom doping carbon nanomaterial |
| CN106587020B (en) * | 2016-12-21 | 2018-12-18 | 兰州理工大学 | A kind of fast preparation method of high conductivity sulfur doping graphene |
| CN108313999A (en) * | 2018-01-31 | 2018-07-24 | 华南理工大学 | A kind of preparation method of nitrogen, sulphur, phosphorus heteroatoms doping carbon material |
| CN108862258B (en) * | 2018-08-13 | 2022-06-17 | 深圳南科新材科技有限公司 | Fluorinated graphene, preparation method and application thereof, and epoxy resin composite material containing fluorinated graphene |
| CN111573659B (en) * | 2020-05-12 | 2023-01-24 | 曲靖师范学院 | Preparation method of nitrogen-doped graphene |
| CN115141673B (en) * | 2022-07-07 | 2023-09-22 | 杭州小拇指汽车科技服务有限公司 | Lubricating oil composition with high cleaning and self-cooling capacity suitable for automobile engine |
| CN114956063A (en) * | 2022-07-27 | 2022-08-30 | 湘潭大学 | Preparation method of nitrogen-doped fluorinated modified graphene potassium electrical anode material and battery |
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| CN103153848A (en) * | 2010-12-22 | 2013-06-12 | 海洋王照明科技股份有限公司 | Fluorographene and preparation method thereof |
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| CN103153848A (en) * | 2010-12-22 | 2013-06-12 | 海洋王照明科技股份有限公司 | Fluorographene and preparation method thereof |
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| AthanasiosB.Bourlinos,et al..The production of chemically converted graphenes from graphite fluoride.《CARBON》.2011,第50卷(第3期),1425-1428. * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109534332A (en) * | 2018-12-26 | 2019-03-29 | 中国科学院福建物质结构研究所 | A kind of amidized fluorinated graphene and preparation method thereof |
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