CN104925795A - Method for synthesizing aza-graphene through solid nitrogenous organic acid - Google Patents
Method for synthesizing aza-graphene through solid nitrogenous organic acid Download PDFInfo
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- CN104925795A CN104925795A CN201510333237.6A CN201510333237A CN104925795A CN 104925795 A CN104925795 A CN 104925795A CN 201510333237 A CN201510333237 A CN 201510333237A CN 104925795 A CN104925795 A CN 104925795A
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Abstract
The invention discloses a method for synthesizing aza-graphene through solid nitrogenous organic acid. According to the method, the solid nitrogenous organic acid is mixed with a catalyst; the mixture is placed in a reactor protected by inert gas or reducing gas to react, and after the reaction, the reaction product is cooled to the indoor temperature under the same atmosphere protection to obtain a solid product; the solid product is washed, filtered and dried to obtain the aza-graphene. The method has the advantages that no pollution is caused, the cost is low, the process is simple, and the aza-graphene can be produced on a large scale.
Description
Technical field
The present invention relates to the method for a kind of solid nitrogenous organic acid synthesis azepine Graphene.
Background technology
Graphene be 2004 first success obtain by individual layer sp
2the two-dimentional carbonaceous crystal that hydridization carbon is formed, have excellent electroconductibility, mechanical property, superelevation specific surface area and to guest molecule/ion good by and transporting etc., at numerous areas, all there is potential using value.Heteroatom doping effectively can regulate the level structure of semiconductor material, optics, electricity and surface chemical property.Theoretical and experimental study shows, nitrogen-doped graphene can effectively regulate its level structure and surface chemistry, expands its application in catalysis and the field such as energy conversion and storage.
Can the application of azepine Graphene realize, and depends on the development innovation of its extensive technology of preparing.The preparation method of azepine Graphene of early literatures report mainly contains chemical Vapor deposition process (CVD), and [azepine Graphene is applied to fuel cell oxygen reduction reaction as effective nonmetal eelctro-catalyst, " American Chemical Society's nanometer ", 2010,4th volume, 1321st page, (Nitrogen-Doped Graphene as EfficientMetal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells, ACS Nano, 2010, Vol.4,1321), co-continuous nanoporous azepine Graphene is used for oxygen reduction reaction, " advanced material ", 2014, 26th volume, 4151st page, (Bicontinuous Nanoporous N-doped Graphenefor the Oxygen Reduction Reaction, Adv.Mater., 2014, Vol.26, 4145)], arc discharge method [uses simple arc discharge method to synthesize minority layer azepine graphene film in a large number, " carbon material ", 2010, 48th volume, 225th page, (Large scale synthesis of N-doped multi-layeredgraphene sheets by simple arc-discharge method, Carbon, 2010, 48, 225)], NH
3electric heating annealing method [prepares azepine Graphene by ammonia electrothermal reaction, " science ", 2009, 324th volume, 768th page, (N-Doping of Graphene Through Electrothermal Reactions withAmmonia, Science, 2009, 324, 768)] with containing nitrogen molecule high temperature reduction graphite oxide method [the azepine Graphene of high oxygen reduction activity and stability, " energy environment science ", 2011, 4th volume, 760th page, (High oxygen-reduction activity and durability of nitrogen-dopedgraphene, Energy Environ.Sci., 2011, 4, 760)] etc.Wherein CVD and arc discharge method etc. can realize nitrogen-atoms face in doping, but be limited to harsh reaction conditions and operating process, be difficult to realize preparation in macroscopic quantity.Utilize nitrogenous substances to carry out electrothermal treatment to Graphene presoma and also can obtain nitrogen-doped graphene, wherein nitrogen element is all present in the edge of graphene film, does not enter in graphene sheet layer.
Summary of the invention
The object of this invention is to provide the method for synthesis azepine Graphene that a kind of pollution-free, low cost, technique are simple, can prepare on a large scale.
Present method with the nitrogenous organic acid plus carbonate of solid for raw material, without the need to carrying out pre-treatment to raw material, one-step synthesis azepine Graphene.Gained azepine Graphene is three-dimensional net structure, effectively can suppress the stacking again of Graphene, and maintain the performance of its excellence.In prepared by mass-producing, there is clear superiority simultaneously.
Preparation method of the present invention is as follows:
(1) by nitrogenous for solid organic acid and catalyst mix.
(2) mixture is positioned over inertia or reducing gas protection reactor in react, after reaction under identical atmosphere protection cool to room temperature, obtain solid product.
(3) above-mentioned solid product washing, filtration, drying are obtained azepine graphene product.
The nitrogenous organic acid of described solid comprises all solids organic acid as L-Ala, leucine, L-glutamic acid, Methionin, glycine, aspartic acid, Serine, Threonine, glutamine and l-asparagine etc.
Described catalyzer is sodium carbonate or salt of wormwood.
Described inertia or reducing atmosphere are argon gas, nitrogen and hydrogen etc.
The mol ratio of the nitrogenous organic acid of described solid and catalyzer sodium carbonate is 1:0.1-2, and the granularity of mixture is less than 100 μm etc.
The modes such as described mixing comprises mechanical mill mixing, solution mixing (after nitrogenous organic acid and sodium carbonate being made respectively solution mixing, remove solvent and obtain solid mixture).
Described temperature of reaction is 700-1500 DEG C etc.
The described reaction times is 0.1-90min etc.
Tool of the present invention has the following advantages:
(1) raw material such as the nitrogenous organic acid of solid used and sodium carbonate (salt of wormwood) is cheap and easy to get, without the need to pre-treatment, is conducive to reducing costs.
(2) synthesis technique flow process is simple, and easy and simple to handle, influence factor is few, is convenient to control, reproducible.
(3) the azepine Graphene synthesized can keep its pattern and not reunite.
(4) the recyclable Posterior circle of sodium carbonate (salt of wormwood) utilizes.
(5) be convenient to mass-producing and synthesize azepine Graphene in a large number.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the embodiment of the present invention 1 azepine Graphene.
Fig. 2 is scanning electron microscope (SEM) photo of the embodiment of the present invention 6 azepine Graphene.
Fig. 3 is scanning electron microscope (SEM) photo of the embodiment of the present invention 8 azepine Graphene.
Fig. 4 is scanning electron microscope (SEM) photo of the embodiment of the present invention 10 azepine Graphene.
Fig. 5 is scanning electron microscope (SEM) photo of the embodiment of the present invention 12 azepine Graphene.
Embodiment
Embodiment 1
Adopt mechanical mill mode by L-glutamic acid and sodium carbonate in molar ratio 1:4 mix (granularity 80-100 μm), get 1.5g and be positioned in the reactor that argon atmospher protects.At 1000 DEG C of reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 5.0% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 4.5nm.
Embodiment 2
Adopt solution hybrid mode by L-glutamic acid and sodium carbonate in molar ratio 1:1 mix (granularity is less than 10 μm), get 2g and be positioned in the reactor of nitrogen atmosphere protection.At 700 DEG C of reaction 90min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 4% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 4nm
Embodiment 3
Adopt mechanical mill mode by aspartic acid and sodium carbonate in molar ratio 1:0.1 mix (granularity 50-70 μm), get 1.5g and be positioned in the reactor of nitrogen atmosphere protection.At 1300 DEG C of reaction 0.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 4% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 2.2nm.
Embodiment 4
Adopt mechanical mill mode by L-glutamic acid and sodium carbonate in molar ratio 1:24 mix (granularity 10-30 μm), get 1.5g and be positioned in nitrogen atmosphere protection reactor.At 750 DEG C of reaction 30min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 8% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 5nm.
Embodiment 5
Adopt mechanical mill mode by glycine and sodium carbonate in molar ratio 1:8 mix (granularity 5-10 μm), get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 DEG C of reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 13.5% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 5.5nm.
Embodiment 6
Adopt solution method by L-Ala and sodium carbonate in molar ratio 1:12 mix (granularity is less than 5 μm), get 2g and be positioned in the reactor of nitrogen atmosphere protection.At 1000 DEG C of reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 5.5% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 4.0nm.
Embodiment 7
Adopt mechanical mill mode by leucine and sodium carbonate in molar ratio 1:8 mix (granularity 50-80 μm), get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 DEG C of reaction 50min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 8.5% (atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 3.5nm.
Embodiment 8
Adopt mechanical mill mode by Methionin and sodium carbonate the mixing (granularity 30-40 μm) of 1:16 in molar ratio, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 900 DEG C of reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 5.8% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 4.5nm.
Embodiment 9
Adopt mechanical mill mode by proline(Pro) and sodium carbonate in molar ratio 1:0.5 mix (granularity 80-100 μm), get 2g and be positioned in the reactor of nitrogen atmosphere protection.At 1050 DEG C of reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 6.5% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 5.5nm.
Embodiment 10
Adopt mechanical mill mode by Serine and salt of wormwood in molar ratio 1:2 mix (granularity 30-50 μm), get 2g and be positioned in the reactor that argon atmospher protects.At 1200 DEG C of reaction 1.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 7.5% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 3.0nm.
Embodiment 11
Adopt mechanical mill mode by Threonine and sodium carbonate in molar ratio 1:0.5 mix (granularity 15-30 μm), get 2g and be positioned in the reactor that argon atmospher protects.At 1100 DEG C of reaction 2.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 4.5% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 2.8nm.
Embodiment 12
Adopt solution hybrid mode by glutamine and salt of wormwood in molar ratio 1:2 mix (granularity is less than 2 μm), get 2g and be positioned in the reactor that argon atmospher protects.At 1500 DEG C of reaction 0.1min.After product cooling, product is taken out, with deionized water wash, filter, 60 DEG C of vacuum-drying 24h, collect product.XPS analysis result shows that nitrogen content is 6.5% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 3.5nm.
Embodiment 13
Adopt mechanical mill mode by l-asparagine and sodium carbonate in molar ratio 1:4 mix (granularity 20-30 μm), get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 DEG C of reaction 90min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that nitrogen content is 9% (atomic percent), and scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 4nm.
Claims (10)
1. a method for solid nitrogenous organic acid synthesis azepine Graphene, is characterized in that comprising the steps:
By nitrogenous for solid organic acid and catalyst mix;
Mixture is positioned over inertia or reducing gas protection reactor in react, after reaction under identical atmosphere protection cool to room temperature, obtain solid product;
Above-mentioned solid product washing, filtration, drying are obtained azepine graphene product.
2. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that the nitrogenous organic acid of described solid is L-Ala, leucine, L-glutamic acid, Methionin, glycine, aspartic acid, Serine, Threonine, glutamine or l-asparagine.
3. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that described catalyzer is sodium carbonate or salt of wormwood.
4. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that described inert atmosphere is argon gas or nitrogen.
5. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that described reducing atmosphere is hydrogen.
6. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that the mol ratio of the nitrogenous organic acid of described solid and catalyzer is 1:0.1-2.
7. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that the granularity that the nitrogenous organic acid of described solid and catalyst mix form mixture is less than 100 μm.
8. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, is characterized in that described mixing comprises mechanical mill mixing or solution mixing.
9. the method for a kind of solid as claimed in claim 8 nitrogenous organic acid synthesis azepine Graphene, after it is characterized in that nitrogenous for solid organic acid and catalyzer being made respectively solution mixes, removes solvent and obtains solid mixture.
10. the method for a kind of solid as claimed in claim 1 nitrogenous organic acid synthesis azepine Graphene, it is characterized in that the temperature of reaction of described reaction is 700-1500 DEG C, the reaction times is 0.1-90min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110422840A (en) * | 2019-09-04 | 2019-11-08 | 河北医科大学 | A kind of method of solid organic acid synthesis azepine graphene |
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| CN103159210A (en) * | 2013-04-10 | 2013-06-19 | 北京化工大学 | New method for preparing nitrogen doped graphene |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
| CN103601178A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene from solid organic acid |
| CN104108710A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped porous graphene and a preparation method thereof |
| WO2014176519A1 (en) * | 2013-04-25 | 2014-10-30 | University Of North Dakota | Graphene quantum dots and method of making |
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| CN103159210A (en) * | 2013-04-10 | 2013-06-19 | 北京化工大学 | New method for preparing nitrogen doped graphene |
| WO2014176519A1 (en) * | 2013-04-25 | 2014-10-30 | University Of North Dakota | Graphene quantum dots and method of making |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
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