CN103601177A - Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst - Google Patents
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Abstract
The invention relates to a method for preparing graphene from solid organic acid by using an alkali metal salt as a catalyst, which comprises the following steps: mixing solid organic acid and a catalyst, putting the mixture in a reactor in an inert or protective atmosphere, reacting, and cooling to room temperature in the same protective atmosphere to obtain a solid product, and washing the solid product, filtering, and drying to obtain the graphene product. The method has the advantages of no pollution, low cost and simple technique, and can implement large-scale preparation.
Description
Technical field
The invention belongs to a kind of preparation method of Graphene, be specifically related to a kind of method that an alkali metal salt catalytic solid organic acid is prepared Graphene.
Background technology
Graphene be success first in 2004 obtain by individual layer sp
2the two-dimentional carbonaceous crystal that hydridization carbon forms, has the specific surface area of excellent electroconductibility, mechanical property, superelevation and to good the passing through and transporting etc. of guest molecule/ion, at numerous areas, all has potential using value.Along with going deep into of research, the demand that magnanimity obtains Graphene is day by day strong.Therefore, how to realize mass-producing preparation and become one of problem demanding prompt solution that restriction Graphene further studied and apply.
Early stage preparation method uses adhesive tape or micromechanics method to peel off graphite to obtain Graphene.This process cost is high, and efficiency is low, is difficult to obtain a large amount of Graphenes, only limits to laboratory scale research and application.The surface that monocrystalline silicon carbide (0001) wafer is analysed in pyrolysis also can obtain Graphene, and adopts lithography process can be directly applied to electron device.But in this process, need high temperature, energy consumption is high; In order to control the bed thickness of Graphene, need the strict temperature of reaction of controlling; The area of gained Graphene is limited to used wafer size simultaneously, be difficult to realize macroscopic preparation of graphene [Graphene and the application aspect fuel cell catalytic material thereof: summary, < < Asia-Pacific chemical engineering > >, 2013, the 8th volume, the 218th page of (Graphene and its application in fuel cell catalysis:a review, Asia-Pac. J. Chem. Eng., 2013, Vol. 8,218)].
Graphite oxide stripping method is considered to the current effective ways that can obtain in a large number Graphene, uses strong oxidizer by graphite oxidation and further ultrasonicly peels off acquisition graphene oxide, and then being reduced into Graphene with reductive agent.The use havoc of strong oxidizer the conjugated structure of Graphene, produce defect, cause the property loss of energies such as its intrinsic electricity, need to carry out follow-up reduction and process to repair its electric property [multi-functional ultralight azepine Graphene network structure, < < Germany applied chemistry > >, 2012, the 51st volume, the 11371st page of (A Versatile, Ultralight, Nitrogen-Doped Graphene Framework, Angew. Chem. Int. Ed., 2012, Vol. 51, 11371)], and preparation process is loaded down with trivial details, consume a large amount of energy, a large amount of use meetings of strong oxidizer and reductive agent simultaneously cause very large harm to environment.
It is substrate that chemical Vapor deposition process (CVD) be take monocrystalline or polycrystalline transition metal, to and deposit to containing carbon matrix precursor pyrolytic decomposition and in metal base, obtain Graphene [multi-functional big area Graphene that can be curling or folding, < < nature material > >, 2013, the 12nd volume, the 321st page of (Multifunctionality and Control of the Crumpling and Unfolding of Large-Area Graphene, Nat. Mater., 2013, Vol. 12, 321)], in process carbon under the guide effect of metal base along two-dimensional directional oriented growth, can form even single-layer graphene of high-quality minority layer, but requirement for experiment condition is harsh, the accumulation causing for fear of π-π effect, must strictly control reactant concn and depositing time, could obtain high-quality Graphene.In addition, in subsequent applications, need Graphene to shift from substrate, or use the removal templates such as strong acid, be difficult to realize preparation in macroscopic quantity.
Summary of the invention
The object of this invention is to provide that a kind of pollution-free, low-cost, technique is simple, the method for the synthesizing graphite alkene that can prepare on a large scale.
It is raw material that present method be take solid organic acid and an alkali metal salt, without raw material is carried out to pre-treatment, and one-step synthesis Graphene.Gained Graphene is three-dimensional net structure, when effectively suppressing Graphene reunion, has kept its excellent performance.Simultaneously in mass-producing, there is clear superiority aspect preparing.
Preparation method of the present invention is as follows:
(1) by solid organic acid and catalyst mix.
(2) mixture is positioned in the reactor with the protection of inertia or reducing gas and reacts, after reaction under identical atmosphere protection cool to room temperature, obtain solid product.
(3) by above-mentioned solid product washing, filtration, the dry Graphene product that obtains.
Described solid organic acid comprises that all solids organic acid is as succinic acid, hexanodioic acid, tartrate, phenylformic acid, citric acid or lauric acid etc.
Described catalyzer is an alkali metal salt, comprises Repone K, sodium-chlor, salt of wormwood, sodium carbonate, sodium sulfate, potassium sulfate, trisodium phosphate, Sodium hexametaphosphate 99, potassiumphosphate, Sodium Tetraborate, sodium metaborate, sodium aluminate, sodium metaaluminate, sodium metasilicate, sodium wolframate, potassium wolframate, Sodium orthomolybdate or potassium molybdate etc.
Described inert atmosphere is argon gas or nitrogen, and reducing atmosphere is hydrogen etc.
Described solid organic acid and the mol ratio of catalyzer are 1:0.1-24.
Described mixing comprises that mechanical mill mixes, pickling process is mixed (by a kind of solid impregnating wherein in the solution of another kind of solid, then remove solvent and obtain solid mixture), solution mixes modes such as (solid organic acid and catalyzer are made respectively after solution mixing, removed solvent and obtain solid mixture).
Described temperature of reaction is 700-1500 ℃.
The described reaction times is 0.1-120min.
Tool of the present invention has the following advantages:
(1) raw material such as solid organic acid used and an alkali metal salt is cheap and easy to get, without pre-treatment, is conducive to reduce costs.
(2) synthesis technique flow process is simple, easy and simple to handle, and influence factor is few, is convenient to control, reproducible.
(3) synthetic Graphene can keep its pattern and not reunite.
(4) the recyclable rear recycle of metal-salt.
(5) be convenient to a large amount of synthesizing graphite alkenes of mass-producing.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the embodiment of the present invention 1 Graphene.
Fig. 2 is scanning electron microscope (SEM) photo of the embodiment of the present invention 5 Graphenes.
Fig. 3 is scanning electron microscope (SEM) photo of the embodiment of the present invention 12 Graphenes.
Embodiment
Embodiment 1
Adopt mechanical mill mode, by succinic acid and sodium carbonate in molar ratio 1:4 mix, get 1.5g and be positioned in the reactor that argon atmospher protects.At 800 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.0%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～4.5nm.
Embodiment 2
Adopting solution hybrid mode, is 1:1 by succinic acid and salt of wormwood mol ratio, and after succinic acid and salt of wormwood are made respectively to solution and mixed, removal solvent obtains solid mixture, gets in the reactor that 2g is positioned over nitrogen atmosphere protection.At 700 ℃ of reaction 120min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～4nm
Embodiment 3
Adopt mechanical mill mode, by hexanodioic acid and sodium-chlor in molar ratio 1:0.1 mix, get in the reactor that 1.5g is positioned over nitrogen atmosphere protection.At 1300 ℃ of reaction 0.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7%(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 tartrate and sodium sulfate in molar ratio 1:24 mix, get 1.5g and be positioned in nitrogen atmosphere protection reactor.At 750 ℃ of reaction 30min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(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 hexanodioic acid and Sodium hexametaphosphate 99 in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 ℃ of reaction 100min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 9.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～3.5nm.
Embodiment 6
Adopting pickling process, is 1:12 by hexanodioic acid and potassium sulfate mol ratio, and hexanodioic acid be impregnated in potassium sulfate solution, then removes solvent and obtains solid mixture.Get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 1000 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 6.5%(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 tartrate and trisodium phosphate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 ℃ of reaction 50min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level 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 phenylformic acid and potassiumphosphate mixing of 1:16 in molar ratio, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 900 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.8%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 5.5 nm.
Embodiment 9
Adopt mechanical mill mode, by citric acid and sodium metasilicate in molar ratio 1:0.5 mix, get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 1050 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～5.5nm.
Embodiment 10
Adopting solution hybrid mode, is 1:4 by phenylformic acid and sodium aluminate mol ratio, and after phenylformic acid and sodium aluminate are made respectively to solution and mixed, removal solvent obtains solid mixture, gets 1.5g and is positioned in the reactor that argon atmospher protects.At 1000 ℃ of reaction 2min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.0%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～4.5nm.
Embodiment 11
Adopt mechanical mill mode, by succinic acid and sodium metaborate in molar ratio 1:1 mix, get in the reactor that 2g is positioned over nitrogen atmosphere protection.At 700 ℃ of reaction 120min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～4nm
Embodiment 12
Adopt mechanical mill mode, by lauric acid and sodium aluminate in molar ratio 1:0.1 mix, get in the reactor that 1.5g is positioned over nitrogen atmosphere protection.At 1300 ℃ of reaction 0.5min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～2.2nm.
Embodiment 13
Adopt mechanical mill mode, by citric acid and sodium metaaluminate in molar ratio 1:24 mix, get 1.5g and be positioned in nitrogen atmosphere protection reactor.At 750 ℃ of reaction 30min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～5nm.
Embodiment 14
Adopt mechanical mill mode, by tartrate and sodium wolframate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 ℃ of reaction 40min.After product is cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 9.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness～3.5nm.
Embodiment 15
Adopting impregnation method, is 1:2 by lauric acid and potassium molybdate mol ratio, and potassium molybdate be impregnated in lauric acid solution, then removes solvent and obtains solid mixture.Get in the reactor that 2g is positioned over argon atmospher protection.At 1500 ℃ of reaction 0.1min.After product is cooling, product is taken out, with deionized water wash, filter, 60 ℃ of vacuum-drying 24h, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness～3.5nm.
Claims (11)
1. an alkali metal salt catalytic solid organic acid is prepared a method for Graphene, it is characterized in that comprising the steps:
By solid organic acid and catalyst mix;
Mixture is positioned in the reactor with the protection of inertia or reducing gas and is reacted, after reaction under identical atmosphere protection cool to room temperature, obtain solid product;
By above-mentioned solid product washing, filtration, the dry Graphene product that obtains.
2. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described solid organic acid comprises that organic acid is as succinic acid, hexanodioic acid, tartrate, phenylformic acid, citric acid or lauric acid.
3. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described catalyzer is an alkali metal salt.
4. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 3 is prepared the method for Graphene, it is characterized in that described an alkali metal salt comprises Repone K, sodium-chlor, salt of wormwood, sodium carbonate, sodium sulfate, potassium sulfate, trisodium phosphate, Sodium hexametaphosphate 99, potassiumphosphate, Sodium Tetraborate, sodium metaborate, sodium aluminate, sodium metaaluminate, sodium metasilicate, sodium wolframate, potassium wolframate, Sodium orthomolybdate or potassium molybdate.
5. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described solid organic acid and the mol ratio of catalyzer are 1:0.1-24.
6. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described inert atmosphere is argon gas or nitrogen, and reducing atmosphere is hydrogen.
7. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described mixing comprises that mechanical mill mixes, and pickling process is mixed or solution hybrid mode.
8. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 7 is prepared the method for Graphene, it is characterized in that it is that a kind of solid impregnating wherein, in the solution of another kind of solid, is then removed to solvent and obtained solid mixture that described pickling process is mixed.
9. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that it is that solid organic acid and catalyzer are made respectively after solution mixing that described solution mixes, and removes solvent and obtains solid mixture.
10. a kind of an alkali metal salt catalytic solid organic acid as claimed in claim 1 is prepared the method for Graphene, it is characterized in that described temperature of reaction is 700-1500 ℃.
11. a kind of an alkali metal salt catalytic solid organic acids as claimed in claim 1 are prepared the method for Graphene, it is characterized in that the described reaction times is 0.1-120min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108707A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Sulfur-doped graphene and preparation method thereof |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
| CN104925795A (en) * | 2015-06-16 | 2015-09-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aza-graphene through solid nitrogenous organic acid |
| CN110139896A (en) * | 2016-09-12 | 2019-08-16 | 阿德莱德大学 | Multipurpose graphene composite material |
| 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 |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102498061A (en) * | 2009-07-27 | 2012-06-13 | 达勒姆大学 | Production of graphene from metal alkoxide |
| CN102942179A (en) * | 2012-11-27 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Preparation method of partially reduced network structure oxidized graphene |
| WO2013066474A2 (en) * | 2011-08-15 | 2013-05-10 | Purdue Research Foundation | Methods and apparatus for the fabrication and use of graphene petal nanosheet structures |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| 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 |
-
2013
- 2013-11-19 CN CN201310577452.1A patent/CN103601177B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102498061A (en) * | 2009-07-27 | 2012-06-13 | 达勒姆大学 | Production of graphene from metal alkoxide |
| WO2013066474A2 (en) * | 2011-08-15 | 2013-05-10 | Purdue Research Foundation | Methods and apparatus for the fabrication and use of graphene petal nanosheet structures |
| CN102942179A (en) * | 2012-11-27 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Preparation method of partially reduced network structure oxidized graphene |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| JINMING CAI ET AL.: "Atomically precise bottom-up fabrication of graphene nanoribbons", 《NATURE》 * |
| LONG CHEN ET AL.: "Porous Graphitic Carbon Nanosheets as a High-Rate Anode Material for Lithium-Ion Batteries", 《ACS APPL. MATER. INTERFACES》 * |
| XIN-HAO LI ET AL.: "Synthesis of Monolayer-Patched Graphene from Glucose", 《ANGEW. CHEM. INT. ED.》 * |
| ZONGPING CHEN ET AL.: "Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition", 《NATURE MATERIALS》 * |
| ZONGPING CHEN ET AL.: "Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition", 《NATURE MATERIALS》, vol. 10, 10 April 2011 (2011-04-10), pages 424 - 428 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108707A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Sulfur-doped graphene and preparation method thereof |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN104108707B (en) * | 2014-07-25 | 2016-03-02 | 深圳新宙邦科技股份有限公司 | A kind of sulfur doping Graphene and preparation method thereof |
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
| CN104925795A (en) * | 2015-06-16 | 2015-09-23 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aza-graphene through solid nitrogenous organic acid |
| CN110139896A (en) * | 2016-09-12 | 2019-08-16 | 阿德莱德大学 | Multipurpose graphene composite material |
| CN110139896B (en) * | 2016-09-12 | 2021-12-31 | 阿德莱德大学 | Multipurpose graphene-based composite material |
| 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 |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
| CN115321525B (en) * | 2022-08-19 | 2024-02-27 | 河南师范大学 | Preparation method of graphene nano-network with macroporous structure |
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