CN103601178B - Method for synthesizing graphene from solid organic acid - Google Patents
Method for synthesizing graphene from solid organic acid Download PDFInfo
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- CN103601178B CN103601178B CN201310577471.4A CN201310577471A CN103601178B CN 103601178 B CN103601178 B CN 103601178B CN 201310577471 A CN201310577471 A CN 201310577471A CN 103601178 B CN103601178 B CN 103601178B
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Abstract
The invention relates to a method for synthesizing graphene from solid organic acid, 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 method of synthesizing graphite alkene, be specifically related to a kind of method of solid organic acid synthesizing graphite alkene.
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.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 become restriction Graphene obtain one of problem demanding prompt solution of further investigation and application.
Early stage preparation method mainly uses adhesive tape or micromechanics method to peel off graphite and obtains Graphene.This process cost is high, and efficiency is low, is difficult to obtain a large amount of Graphenes, is only limitted to laboratory scale investigation and application.The surface of Thermal desorption monocrystalline silicon carbide (0001) wafer also can obtain Graphene, and adopts lithography process to be directly applied to electron device.But need high temperature in this process, energy consumption is high; In order to the thickness controlling Graphene needs strictly to control temperature of reaction; The area of gained Graphene is limited to used wafer size simultaneously, be difficult to realize macroscopic preparation of graphene [Graphene and the application in fuel cell catalyst 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 Graphene in a large number, namely uses strong oxidizer by graphite oxidation and further ultrasonic stripping acquisition graphene oxide, and then is reduced into Graphene with reductive agent.The use havoc of the strong oxidizer conjugated structure of Graphene, produces defect, causes the property loss of energies such as its intrinsic electricity, need to carry out follow-up reduction treatment to repair its electric property [multi-functional ultralight azepine Graphene network structure, " German applied chemistry ", 2012,51st volume, 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 uses of strong oxidizer and reductive agent simultaneously can cause very large harm to environment.
Chemical Vapor deposition process (CVD) with monocrystalline or polycrystalline transition metal for substrate, to deposit in metal base obtain Graphene [multi-functional rollable or folding large-area graphene containing carbon matrix precursor pyrolytic decomposition, " nature material ", 2013, 12nd volume, 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, high-quality minority layer even single-layer graphene can be formed, but experiment condition is harsh, in order to avoid π-π acts on the accumulation caused, strictly must control reactant concn and depositing time, high-quality Graphene could be obtained.In addition, in subsequent applications, need Graphene to shift from substrate, or use strong acid etc. to remove template, be difficult to realize preparation in macroscopic quantity.
Summary of the invention
The object of this invention is to provide the method for synthesizing graphite alkene that a kind of pollution-free, low cost, technique are simple, can prepare on a large scale.
Present method with solid organic acid and sodium carbonate for raw material, without the need to carrying out pre-treatment to raw material, one-step synthesis Graphene.Gained Graphene is three-dimensional net structure, while effectively suppressing Graphene to be reunited, maintains 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 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 graphene product.
Described solid organic acid comprises propanedioic acid, succinic acid, methylene-succinic acid, hexanodioic acid, butene dioic acid, gluconic acid, tartrate, phenylformic acid, citric acid, lauric acid, styracin or stearic acid etc.
Described catalyzer is sodium carbonate.
Described inert atmosphere is argon gas or nitrogen; Reducing atmosphere is hydrogen etc.
The mol ratio of described solid organic acid and catalyzer sodium carbonate is 1:0.1-24.
Described mixing comprises mechanical mill mixing, pickling process mixing is (by wherein a kind of solid impregnating in the solution of another kind of solid, then remove solvent and obtain solid mixture), the modes such as solution mixing (after solid 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.
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 sodium carbonate 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) Graphene synthesized can keep its pattern and not reunite.
(4) the recyclable Posterior circle of sodium carbonate utilizes.
(5) a large amount of synthesizing graphite alkene of mass-producing is convenient to.
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 6 Graphene.
Fig. 3 is scanning electron microscope (SEM) photo of the embodiment of the present invention 12 Graphene.
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 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 oxygen level is 7.0%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 4.5 nm.
Embodiment 2
Adopting solution hybrid mode, is 1:1 by succinic acid and sodium carbonate mol ratio, and succinic acid and sodium carbonate are made after solution mixes respectively, removal solvent obtains solid mixture, gets 2g and is positioned in the reactor of nitrogen atmosphere protection.At 700 DEG C of reaction 120min.After product 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 propanedioic acid and sodium carbonate in molar ratio 1:0.1 mix, 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 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 succinic acid and sodium carbonate in molar ratio 1:24 mix, 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 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 methylene-succinic acid and sodium carbonate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 DEG C of reaction 100min.After product 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
Adopt pickling process, be 1:12 by hexanodioic acid and sodium carbonate mol ratio, hexanodioic acid is mixed with sodium carbonate solution, then remove solvent and obtain solid mixture.Get 2g to 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 oxygen level is 6.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 4.0 nm.
Embodiment 7
Adopt mechanical mill mode by tartrate and sodium carbonate in molar ratio 1:8 mix, 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 oxygen level is 8.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene film layer thickness ~ 3.5 nm.
Embodiment 8
Adopt mechanical mill mode by gluconic acid and sodium carbonate the mixing 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 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 butene dioic acid and sodium carbonate in molar ratio 1:0.5 mix, 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 oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 5.5 nm.
Embodiment 10
Adopt mechanical mill mode by citric acid and sodium carbonate in molar ratio 1:2 mix, 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 oxygen level is 6.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 3.0 nm.
Embodiment 11
Adopt mechanical mill mode by phenylformic acid and sodium carbonate in molar ratio 1:0.5 mix, 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 oxygen level is 7.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 2.8nm.
Embodiment 12
Adopt impregnation method, be 1:2 by stearic acid and sodium carbonate mol ratio, sodium carbonate impregnated in stearic solution, then remove solvent and obtain solid mixture.Get 2g to be positioned in the reactor of argon atmospher protection.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 oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 3.5nm.
Embodiment 13
Adopt mechanical mill mode by styracin and sodium carbonate in molar ratio 1:4 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 700 DEG C of reaction 120min.After product 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 14
Adopting pickling process, is 1:1 by lauric acid and sodium carbonate mol ratio, by lauric acid solid impregnating in the solution of sodium carbonate, then removes solvent and obtains solid mixture.Get 2g to 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 oxygen level is 7%(atomic percent), scanning electron microscope result show sample is network structure, graphene film layer thickness ~ 2.2nm.
Claims (8)
1. a method for solid organic acid synthesizing graphite alkene, is characterized in that comprising the steps:
(1) by 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 graphene product;
The mol ratio of described solid organic acid and catalyzer sodium carbonate is 1:0.1-24.
2. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described solid organic acid comprises propanedioic acid, succinic acid, methylene-succinic acid, hexanodioic acid, butene dioic acid, gluconic acid, tartrate, phenylformic acid, citric acid, lauric acid, styracin or stearic acid.
3. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, it is characterized in that described inert atmosphere is argon gas or nitrogen, reducing atmosphere is hydrogen.
4. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described mixing comprises mechanical mill mixing, pickling process mixing or solution mixing.
5. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 4, is characterized in that described pickling process mixing is that then removal solvent obtains solid mixture by wherein a kind of solid impregnating is in the solution of another kind of solid.
6. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 4, is characterized in that described solution mixing, after solid organic acid and sodium carbonate being made respectively solution mixing, is removed solvent and obtain solid mixture.
7. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that described temperature of reaction is 700-1500 DEG C.
8. the method for a kind of solid organic acid synthesizing graphite alkene as claimed in claim 1, is characterized in that the described reaction times is 0.1-120min.
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| CN103601177B (en) * | 2013-11-19 | 2015-04-29 | 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 |
| CN104876217B (en) * | 2015-06-01 | 2017-10-10 | 北京理工大学 | A kind of preparation method of graphene |
| 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 |
| CN110577214B (en) * | 2018-06-08 | 2022-08-02 | 中国科学院宁波材料技术与工程研究所 | Liquid-phase automatic dispersion graphene solid, and preparation method and application thereof |
| 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 |
| CN112194119A (en) * | 2020-10-13 | 2021-01-08 | 河北医科大学 | Method for synthesizing three-dimensional graphene from solid sugar |
| 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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| KR101462401B1 (en) * | 2008-06-12 | 2014-11-17 | 삼성전자주식회사 | Method for exfoliating carbonization catalyst from graphene sheet, method for transferring graphene sheet where carbonization catalyst is exfoliated to device, graphene sheet and device according to the methods |
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| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
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