CN103204496A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103204496A CN103204496A CN2013100791681A CN201310079168A CN103204496A CN 103204496 A CN103204496 A CN 103204496A CN 2013100791681 A CN2013100791681 A CN 2013100791681A CN 201310079168 A CN201310079168 A CN 201310079168A CN 103204496 A CN103204496 A CN 103204496A
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Abstract
The invention discloses a preparation method of graphene. Anhydrous aluminum chloride and tetra (triphenylphosphine) palladium are proportioned to form catalyst, the catalyst is used for catalyzing halogenated benzene reaction in an inert environment to generate crude graphene, the crude graphene is soaked by ethanol and hydrochloric acid, washed by deionized water and subjected to vacuum drying to obtain the finished graphene. The method is low in catalyst us amount, mild in reaction condition, short in reaction time, and high in yield.
Description
Technical field
The present invention relates to the Graphene technical field, relate in particular to a kind of preparation method of graphene.
Background technology
2004, single-layer graphene is peeled off and observed to a kind of very simple method of the usefulness such as physics professor Geim of Britain graceful Chester university, caused " carbon " upsurge of scientific circles' new rounds.The theoretical specific surface area of Graphene has outstanding heat conductivility and mechanical property up to 2600m2/g, and at a high speed electronic mobility under the room temperature.These particular performances make it have broad application prospects in Materials science and person in electronics.
Preparation method of graphene mainly contains following several at present: one, graphite oxide-reduction method, these class methods make graphite layers contain a large amount of functional groups by long-time oxidation, obtain Graphene through reduction, ultra-sonic dispersion then.These class methods not only the reflection cycle long, yield poorly, need a large amount of severe corrosive acid and oxygenant simultaneously, bigger to the structure deteriorate of Graphene.Two, chemical gaseous phase deposition method places the decomposable carbon containing of high temperature (as methane, ethene etc.) atmosphere with planar substrates (as metallic film, metal single crystal etc.), makes carbon atom be deposited on substrate surface and forms Graphene.By the control temperature, proportioning raw materials, gas flow process etc. can be regulated and control the growth of Graphene.The Graphene purity that makes is higher, thinner thickness, but process of industrialization higher owing to temperature of reaction, that need factor restriction this method such as substrate.Three, machinery is deprived rule to the equipment requirements strictness, complicated operation, and controllability is low, is difficult to scale operation, only suitable laboratory study.Be equipped with Graphene by catalysis catalysis processed, the reaction conditions gentleness, reaction time is fast.But in the method for existing catalytic preparation Graphene, catalyst consumption is big, aftertreatment difficulty when carrying out scale operation.As the disclosed preparation method of graphene of Chinese patent CN101462719B, with sodium Metal 99.5 as catalyzer, the consumption of sodium Metal 99.5 is big, and sodium Metal 99.5 reaches 1-100:1 with the ratio of the amount of substance of halohydrocarbon, and a large amount of sodium Metal 99.5s that use can increase the danger of reaction and the difficulty of post-reaction treatment in the reaction.
Summary of the invention
The objective of the invention is to for overcoming the defective of prior art, and a kind of reaction conditions gentleness, the method for preparing Graphene that catalyst levels is few are provided.
For achieving the above object, the present invention is by the following technical solutions: a kind of preparation method of graphene may further comprise the steps:
(1), takes by weighing halogeno-benzene, Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium and place reactor respectively, in reactor, add solvent, under nitrogen or inert gas atmosphere, temperature rises to 100-200 ℃, stirring reaction 1-5h, wherein the ratio of the amount of substance of halogeno-benzene, Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium is 1:0.1-0.5:0.001-0.005, is preferably 1:0.3:0.003;
(2), the material in the described reactor of step (1) is cooled to the room temperature after-filtration filter cake of winning, first filter cake is scattered in the ethanol, stir the 0.5-1h after-filtration and get second filter cake, second filter cake is scattered in the hydrochloric acid, stir the 0.5-1h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings;
(3), with step (2) gained the 3rd filter cake at 50-80 ℃ of following vacuum-drying 8-12h.
Preferably, described halogeno-benzene is any in phenyl-monohalide, phenyl-dihalide and the trihalogenated benzene.
Preferably, described halogeno-benzene is 1,3,5-trichlorobenzene.
Compared with prior art, the invention has the beneficial effects as follows: the present invention forms the reaction of catalyst halogeno-benzene according to a certain ratio by Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium and generates Graphene, and catalyst levels is few, the reaction conditions gentleness, reaction times is short, the productive rate height.
Embodiment
In order to more fully understand technology contents of the present invention, below in conjunction with specific embodiment technical scheme of the present invention is further introduced and explanation.
Embodiment 1
In round-bottomed flask, add 1 respectively, 3,5-trichlorobenzene 18.1g, Aluminum chloride anhydrous 4g, tetrakis triphenylphosphine palladium 0.3467g and 500mL dimethylbenzene, in round-bottomed flask, feed nitrogen 10min to discharge the air in the round-bottomed flask then, under agitation heat temperature raising is to 130-140 ℃, back flow reaction 4h.Material in the round-bottomed flask naturally cools to after the room temperature elimination reaction solution filter cake of winning, first filter cake is scattered in the ethanol of 500mL, stir the 0.5h after-filtration and obtain second filter cake, second filter cake is scattered in the hydrochloric acid of 500mL1mol/L, stir the 0.5h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings.The 3rd filter cake after washing is put at 50 ℃ of following vacuum-drying 12h and is namely got Graphene product 5.9g, productive rate 79%.Testing this graphene film electric conductivity with four electrode method is 210S/m.
Embodiment 2
In round-bottomed flask, add 1 respectively, 3,5-trichlorobenzene 18.1g, Aluminum chloride anhydrous 5g, tetrakis triphenylphosphine palladium 0.55g and 500mL dimethylbenzene, in round-bottomed flask, feed nitrogen 10min to discharge the air in the round-bottomed flask then, under agitation heat temperature raising is to 110-120 ℃, back flow reaction 3h.Material in the round-bottomed flask naturally cools to after the room temperature elimination reaction solution filter cake of winning, first filter cake is scattered in the ethanol of 500mL, stir the 0.5h after-filtration and obtain second filter cake, second filter cake is scattered in the hydrochloric acid of 500mL1mol/L, stir the 0.5h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings.The 3rd filter cake after washing is put at 70 ℃ of following vacuum-drying 8h and is namely got Graphene product 6.1g, productive rate 82%.Testing this graphene film electric conductivity with four electrode method is 198S/m.
Embodiment 3
In round-bottomed flask, add 1 respectively, 4-dichlorobenzene 14.7g, Aluminum chloride anhydrous 4g, tetrakis triphenylphosphine palladium 0.3467g and 500mL dimethylbenzene, in round-bottomed flask, feed nitrogen 10min to discharge the air in the round-bottomed flask then, under agitation heat temperature raising is to 130-140 ℃, back flow reaction 4h.Material in the round-bottomed flask naturally cools to after the room temperature elimination reaction solution filter cake of winning, first filter cake is scattered in the ethanol of 500mL, stir the 0.5h after-filtration and obtain second filter cake, second filter cake is scattered in the hydrochloric acid of 500mL1mol/L, stir the 0.5h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings.The 3rd filter cake after washing is put at 50 ℃ of following vacuum-drying 12h and is namely got Graphene product 5.7g, productive rate 75%.Testing this graphene film electric conductivity with four electrode method is 189S/m.
Embodiment 4
In round-bottomed flask, add chlorobenzene 18.1g, Aluminum chloride anhydrous 4g, tetrakis triphenylphosphine palladium 0.3467g and 500mL pyridine respectively, in round-bottomed flask, feed nitrogen 10min to discharge the air in the round-bottomed flask then, under agitation heat temperature raising is to 170-180 ℃, back flow reaction 4h.Material in the round-bottomed flask naturally cools to after the room temperature elimination reaction solution filter cake of winning, first filter cake is scattered in the ethanol of 500mL, stir the 0.5h after-filtration and obtain second filter cake, second filter cake is scattered in the hydrochloric acid of 500mL1mol/L, stir the 0.5h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings.The 3rd filter cake after washing is put at 80 ℃ of following vacuum-drying 8h and is namely got Graphene product 5.4g, productive rate 70%.Testing this graphene film electric conductivity with four electrode method is 203S/m.
The above only further specifies technology contents of the present invention with embodiment, so that the reader is more readily understood, does not only limit to this but do not represent embodiments of the present invention, and any technology of doing according to the present invention is extended or recreation, all is subjected to protection of the present invention.
Claims (4)
1. preparation method of graphene is characterized in that: may further comprise the steps,
(1), takes by weighing halogeno-benzene, Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium and place reactor respectively, in reactor, add solvent, under nitrogen or inert gas atmosphere, temperature rises to 100-200 ℃, stirring reaction 1-5h, wherein the ratio of the amount of substance of halogeno-benzene, Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium is 1:0.1-0.5:0.001-0.005;
(2), the material in the described reactor of step (1) is cooled to the room temperature after-filtration filter cake of winning, first filter cake is scattered in the ethanol, stir the 0.5-1h after-filtration and get second filter cake, second filter cake is scattered in the hydrochloric acid, stir the 0.5-1h after-filtration and get the 3rd filter cake, the 3rd filter cake is neutral with deionized water wash to washings;
(3), with step (2) gained the 3rd filter cake at 50-80 ℃ of following vacuum-drying 8-12h.
2. according to the described a kind of preparation method of graphene of claim 1, it is characterized in that: the ratio of the amount of substance of halogeno-benzene, Aluminum chloride anhydrous and tetrakis triphenylphosphine palladium is 1:0.3:0.003 in the described step (1).
3. according to the described a kind of preparation method of graphene of claim 1, it is characterized in that: described halogeno-benzene is any in phenyl-monohalide, phenyl-dihalide and the trihalogenated benzene.
4. according to the described a kind of preparation method of graphene of claim 1, it is characterized in that: described halogeno-benzene is 1,3,5-trichlorobenzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285139A (en) * | 2017-12-11 | 2018-07-17 | 昆明理工大学 | A kind of preparation method and application of nitrogen-doped graphene carbon material |
| CN110937593A (en) * | 2018-09-21 | 2020-03-31 | 湖北大学 | Nano-pore graphene and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
| CN102320597A (en) * | 2011-07-15 | 2012-01-18 | 天津大学 | A kind of preparation method of graphene |
| CN102408107A (en) * | 2010-09-26 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
| CN102408107A (en) * | 2010-09-26 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene |
| CN102320597A (en) * | 2011-07-15 | 2012-01-18 | 天津大学 | A kind of preparation method of graphene |
Non-Patent Citations (2)
| Title |
|---|
| YANG XIAOYIN ET AL: "Two-dimensional graphene nanoribbons", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 130, no. 13, 7 March 2008 (2008-03-07), pages 4216 - 4217, XP055025794, DOI: doi:10.1021/ja710234t * |
| 朱洪法等: "《催化剂手册》", 31 August 2008, article "无水氯化铝", pages: 73 - 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108285139A (en) * | 2017-12-11 | 2018-07-17 | 昆明理工大学 | A kind of preparation method and application of nitrogen-doped graphene carbon material |
| CN108285139B (en) * | 2017-12-11 | 2021-06-18 | 昆明理工大学 | Preparation method and application of nitrogen-doped graphene carbon material |
| CN110937593A (en) * | 2018-09-21 | 2020-03-31 | 湖北大学 | Nano-pore graphene and preparation method and application thereof |
| CN110937593B (en) * | 2018-09-21 | 2021-09-24 | 湖北大学 | Nano-pore graphene and preparation method and application thereof |
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Application publication date: 20130717 |