CN103601177B - Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst - Google Patents
Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst Download PDFInfo
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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 Graphene prepared by alkali metal salt catalytic solid organic acid.
Background technology
Graphene be 2004 first success obtain by individual layer sp
2the two-dimentional carbonaceous crystal that hydridization carbon is formed, have excellent electric conductivity, mechanical property, superelevation specific 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 scale 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 electronic device.But need high temperature in this process, energy consumption is high; In order to the thickness controlling Graphene needs strictly to control reaction temperature; 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 reducing agent.The use heavy damage 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 reducing agent simultaneously can cause very large harm to environment.
Chemical vapour deposition technique (CVD) with monocrystalline or polycrystalline transition metal for substrate, to deposit in metallic substrates obtain Graphene [multi-functional rollable or folding large-area graphene containing carbon matrix precursor pyrolytic, " 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 metallic substrates along two-dimensional directional oriented growth, high-quality minority layer even single-layer graphene can be formed, but requirement for experiment condition is harsh, in order to avoid π-π acts on the accumulation caused, strictly must control reactant concentration and sedimentation 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.
This method with solid organic acid and alkali metal salt for raw material, without the need to carrying out pretreatment 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 scale, 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 reducibility 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 all solids organic acid as succinic acid, adipic acid, tartaric acid, benzoic acid, citric acid or laurate etc.
Described catalyst is alkali metal salt, comprises potassium chloride, sodium chloride, potash, sodium carbonate, sodium sulphate, potassium sulfate, sodium pyrophosphate, calgon, potassium phosphate, Boratex, kodalk, sodium aluminate, sodium metaaluminate, sodium metasilicate, sodium tungstate, potassium tungstate, sodium molybdate 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 catalyst are 1:0.1-24.
Described mixing comprises mechanical lapping mixing, infusion 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 catalyst being made respectively solution mixing, remove solvent and obtain solid mixture).
Described reaction temperature is 700-1500 DEG C.
The described reaction time is 0.1-120min.
Tool of the present invention has the following advantages:
(1) raw material such as solid organic acid used and alkali metal salt is cheap and easy to get, without the need to pretreatment, 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 slaine utilizes.
(5) a large amount of synthesizing graphite alkene of scale is convenient to.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) photo of the embodiment of the present invention 1 Graphene.
Fig. 2 is ESEM (SEM) photo of the embodiment of the present invention 5 Graphene.
Fig. 3 is ESEM (SEM) photo of the embodiment of the present invention 12 Graphene.
Detailed description of the invention
Embodiment 1
Adopt mechanical lapping 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 DEG C of reaction 2min.After product cooling, product is taken out, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 7.0%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 4.5nm.
Embodiment 2
Adopting solution hybrid mode, is 1:1 by succinic acid and potash mol ratio, and succinic acid and potash 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 10%(atomic percent), ESEM result show sample is network structure, graphene film layer thickness ~ 4nm
Embodiment 3
Adopt mechanical lapping mode, by adipic acid and sodium chloride 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 7%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 2.2nm.
Embodiment 4
Adopt mechanical lapping mode, by tartaric acid and sodium sulphate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 10%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 5nm.
Embodiment 5
Adopt mechanical lapping mode, by adipic acid and calgon 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 9.5%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 3.5nm.
Embodiment 6
Adopt infusion process, be 1:12 by adipic acid and potassium sulfate mol ratio, adipic acid impregnated in potassium sulfate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 6.5%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 4.0nm.
Embodiment 7
Adopt mechanical lapping mode, by tartaric acid and sodium pyrophosphate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 8.5%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 3.5nm.
Embodiment 8
Adopt mechanical lapping mode, by benzoic acid and potassium phosphate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 8.8%(atomic percent), ESEM result show sample is network structure, graphene film layer thickness ~ 5.5 nm.
Embodiment 9
Adopt mechanical lapping mode, by citric acid and sodium metasilicate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 8.5%(atomic percent), ESEM result show sample is network structure, graphene film layer thickness ~ 5.5nm.
Embodiment 10
Adopting solution hybrid mode, is 1:4 by benzoic acid and sodium aluminate mol ratio, and benzoic acid and sodium aluminate are made after solution mixes respectively, removal solvent obtains solid mixture, gets 1.5g and is positioned in the reactor that argon atmospher protects.At 1000 DEG C of reaction 2min.After product cooling, product is taken out, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 7.0%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 4.5nm.
Embodiment 11
Adopt mechanical lapping mode, by succinic acid and kodalk in molar ratio 1:1 mix, get 2g and be positioned in the reactor of nitrogen atmosphere protection.At 700 DEG C of reaction 120min.After product cooling, product is taken out, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 10%(atomic percent), ESEM result show sample is network structure, graphene film layer thickness ~ 4nm
Embodiment 12
Adopt mechanical lapping mode, by laurate and sodium aluminate 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, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 7%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 2.2nm.
Embodiment 13
Adopt mechanical lapping 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 DEG C of reaction 30min.After product cooling, product is taken out, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 10%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 5nm.
Embodiment 14
Adopt mechanical lapping mode, by tartaric acid and sodium tungstate in molar ratio 1:8 mix, get 2g and be positioned in the reactor that nitrogen atmosphere protects.At 800 DEG C of reaction 40min.After product cooling, product is taken out, spends deionized water, filter, dry, collect product.XPS analysis result shows that oxygen content is 9.5%(atomic percent), the network-like structure of ESEM result show sample, graphene film layer thickness ~ 3.5nm.
Embodiment 15
Adopt impregnation method, be 1:2 by laurate and potassium molybdate mol ratio, potassium molybdate impregnated in laurate 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, spends deionized water, filter, 60 DEG C of vacuum drying 24h, collect product.XPS analysis result shows that oxygen content is 8.5%(atomic percent), ESEM result show sample is network structure, graphene film layer thickness ~ 3.5nm.
Claims (8)
1. a method for Graphene prepared by alkali metal salt catalytic solid organic acid, it is characterized in that comprising the steps:
(1) by solid organic acid and catalyst mix;
(2) mixture is positioned over inertia or reducibility 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 organic acid that described solid organic acid comprises is succinic acid, adipic acid, tartaric acid, benzoic acid, citric acid or laurate;
Described catalyst is alkali metal salt;
Described solid organic acid and the mol ratio of catalyst are 1:0.1-24.
2. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 1, it is characterized in that described alkali metal salt comprises potassium chloride, sodium chloride, potash, sodium carbonate, sodium sulphate, potassium sulfate, sodium pyrophosphate, calgon, potassium phosphate, Boratex, kodalk, sodium aluminate, sodium metaaluminate, sodium metasilicate, sodium tungstate, potassium tungstate, sodium molybdate or potassium molybdate.
3. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 1, and it is characterized in that described inert atmosphere is argon gas or nitrogen, reducing atmosphere is hydrogen.
4. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 1, it is characterized in that described mixing comprises mechanical lapping mixing, infusion process mixing or solution hybrid mode.
5. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 4, it is characterized in that the mixing of described infusion process 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 Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 4, it is characterized in that the mixing of described solution, after solid organic acid and catalyst being made respectively solution mixing, is removed solvent and obtain solid mixture.
7. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 1, it is characterized in that described reaction temperature is 700-1500 DEG C.
8. the method for Graphene prepared by a kind of alkali metal salt catalytic solid organic acid as claimed in claim 1, it is characterized in that the described reaction time is 0.1-120min.
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| 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 |
| CN104445177B (en) * | 2014-12-16 | 2016-09-28 | 中国科学院宁波材料技术与工程研究所 | The preparation method of a kind of Graphene and Graphene |
| 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 |
| CA3039985A1 (en) * | 2016-09-12 | 2018-03-15 | The University Of Adelaide | Multipurpose graphene-based composite |
| 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 |
| 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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