CN110015656A - A kind of preparation method of single-layer graphene film - Google Patents
A kind of preparation method of single-layer graphene film Download PDFInfo
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- CN110015656A CN110015656A CN201910353510.XA CN201910353510A CN110015656A CN 110015656 A CN110015656 A CN 110015656A CN 201910353510 A CN201910353510 A CN 201910353510A CN 110015656 A CN110015656 A CN 110015656A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
The present invention provides a kind of preparation method of single-layer graphene film.Firstly, preparing single side selective oxidation grapheme material, has oxygen-containing group on one side, on one side without oxygen-containing group, i.e. hydrophilic, the face hydrophobic of one side；Then, lipophilicity is carried out to single side selective oxidation graphene using oleyl amine or oleic acid to be modified, obtain single side selectivity oleophylic graphite alkene；Finally, preparing single-layer graphene film in gas-liquid interface self assembly using the oleophobic oleophylic difference of single side selectivity oleophylic graphite alkene material.Using the single side selectivity oleophylic graphite alkene for having oleophylic oleophobic sex differernce, the self assembly at gas-liquid interface prepares single-layer graphene film to the method for the invention, it can be used for further fine structure construction, the preparation of molecular device, be conducive to compound with organic matter, three-dimensional aeroge be may be alternatively configured applied to superpower oil absorption material, method prepares simple process, and the requirement to equipment is lower, suitable for industry or laboratory operation, there is huge application prospect.
Description
Technical field
The present invention relates to graphene film preparation field, especially a kind of mono-layer single-face oleophylic graphite alkene gas-liquid interface is from group
Fill the preparation method of film.
Background technique
Graphene has excellent optics, electricity, mechanical characteristic, it is considered to be a kind of future revolutionary material.In recent years
Come, graphene film touch screen, conductive film, solar battery and in terms of show numerous potential advantages,
Such as high sensitivity, high conductivity, high-photoelectric transformation efficiency and high light transmittance, in such as smart phone, tablet computer, film point
It is with a wide range of applications from the fields such as, sewage treatment and recycling, sea water desalination, proton conduction, energy stores and conversion.
But graphene is one kind completely by sp2The thickness that the carbon atom of hydridization is constituted is only monoatomic layer or several lists
The quasi- two dimensional crystal material of atomic layer, chemical stability are high, the inert state in surface, the interaction with other media compared with
It is weak, and have stronger Van der Waals force between graphene film and piece, it is easy to produce aggregation.In addition, due to graphene i.e. not oleophylic
Also not hydrophilic, it is difficult to dissolve in usual vehicle, this causes greatly tired to the further research and application of graphene film
It is difficult.
Summary of the invention
The present invention provides a kind of preparation method of single-layer graphene film.Firstly, preparing single side selective oxidation graphene
Material has oxygen-containing group on one side, on one side without oxygen-containing group, i.e. hydrophilic, the face hydrophobic of one side；Then, oleyl amine or oil are utilized
Acid carries out lipophilicity to single side selective oxidation graphene and is modified, and obtains single side selectivity oleophylic graphite alkene；Finally, utilizing single side
The oleophobic oleophylic difference of selective oleophylic graphite alkene material prepares single-layer graphene film in gas-liquid interface self assembly.
The present invention adopts the following technical scheme:
A kind of preparation method of single-layer graphene film, includes the following steps:
(1) anhydrous ferric trichloride and graphite Hybrid Heating are prepared into second order graphite intercalation compound with molte-salt synthesis, adopted
Oxidation intercalation is carried out to second order graphene intercalation compound with oxidant and concentrated acid, after cleaning, excessive hydrogen peroxide is added and removes carbon
Layer, obtains single side selective oxidation graphene；
(2) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, by oleyl amine or oil
Acid is added, and heats and keeps stirring, obtains single side selectivity oleophylic graphite alkene；
(3) single side selectivity oleophylic graphite alkene material is put into organic solvent, using its distinctive oleophylic oleophobic property, is dredged
The upward ingress of air of pasta, oleophylic contact solution downwards, and single side selectivity oleophylic graphite alkene is dispersed in gas-liquid interface, self assembly
At single-layer graphene film.
Molten-salt growth method reaction temperature in step (1) is 400 DEG C, and the reaction time is 4-6 hours, anhydrous ferric trichloride and graphite
Mass ratio is 5: 1.
Oxidant in step (1) includes chlorate, perchlorate, permanganate, bichromate, sodium peroxide, concentrated acid
For the concentrated sulfuric acid or the mixture of the concentrated sulfuric acid and concentrated nitric acid, the oxidation intercalation time is 4-48h, and temperature is 0-80 DEG C.
The reaction time of hydrogen peroxide and ferric trichloride in step (1) is 1-4h, and reaction temperature is room temperature.
The ratio of water and alcohol is the matter of arbitrary proportion, single side selective oxidation graphene and oleyl amine or oleic acid in step (2)
Amount is than being 50: 1-1: 50, and heating temperature is 90-200 DEG C, time 0.5-24h.
The organic solvent of step (3) is hexamethylene, acetone, toluene, chloroform, and gas-liquid interface area can be controlled freely, but
Need to control the amount that single side selective oxidation graphene is added, in order to avoid form multilayered structure.
The present invention has the advantage that
(1) self drive that the present invention is generated using the single side selectivity oleophylic graphite alkene for having oleophylic oleophobic sex differernce,
Self assembly prepares single-layer graphene film at gas-liquid interface, extends the scope of application of graphene film self-assembling method.
(2) single side selectivity oleophylic graphite alkene film can be used for further fine structure construction, the system of molecular device
It is standby, be conducive to compound with organic matter, may be alternatively configured three-dimensional aeroge applied to superpower oil absorption material.
(3) present invention prepares film and can be controlled in monoatomic layer thickness, and uniformity is good, and area can freely regulate and control, can be with
Small to one beaker, also can be large enough to a pond.
(4) the method for the invention preparation process is simple, and the requirement to equipment is lower, is suitable for industry or laboratory operation,
With huge application prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the method for the present invention prepares second order graphite intercalation compound.
Fig. 2 is the method for the present invention oxidant and concentrated acid to FeCl3- GIC carries out the structural schematic diagram of oxidation intercalation.
Fig. 3 is that the method for the present invention removes material structure schematic diagram after oxide layer.
Fig. 4 shows for the single side selective oxidation graphene-structured prepared after the method for the present invention hydrogen peroxide and ferric chloride reaction
It is intended to.
Fig. 5 is the structural schematic diagram that the method for the present invention prepares single side oleophylic graphite alkene self-assembled film.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg sodium chlorate is put into solution, is stirred 12 hours at room temperature, by product eccentric cleaning.
(3) product is added in the hydrogen peroxide that excessive mass fraction is 30%, reaction time 1h, obtains single side choosing
Selecting property graphene oxide.
(4) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, by excessive oleyl amine
It is added, 100 DEG C of heating 4h keep stirring, obtain single side selectivity oleophylic graphite alkene.
(5) single side selectivity oleophylic graphite alkene material is put into chloroform and is stirred evenly, stood after stopping stirring, self assembly
At single-layer graphene film.
Embodiment 2
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg potassium permanganate is put into solution, is stirred 12 hours at room temperature, by product eccentric cleaning.
(3) product is added in the hydrogen peroxide that excessive mass fraction is 30%, reaction time 1h, obtains single side choosing
Selecting property graphene oxide.
(4) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, by excessive oleic acid
It is added, 100 DEG C of heating 4h keep stirring, obtain single side selectivity oleophylic graphite alkene.
(5) single side selectivity oleophylic graphite alkene material is put into chloroform and is stirred evenly, stood after stopping stirring, self assembly
At single-layer graphene film.
Embodiment 3
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20L concentrated sulfuric acid and the concentrated nitric acid of 10mL, (0 in ice water
DEG C) stirring 0.5 hour, 360mg sodium chlorate is put into solution, is stirred 12 hours at room temperature, by product eccentric cleaning.
(3) product is added in the hydrogen peroxide that excessive mass fraction is 30%, reaction time 1h, obtains single side choosing
Selecting property graphene oxide.
(4) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, by excessive oleyl amine
It is added, 180 DEG C of heating 1h keep stirring, obtain single side selectivity oleophylic graphite alkene.
(5) single side selectivity oleophylic graphite alkene material is put into chloroform and is stirred evenly, stood after stopping stirring, self assembly
At single-layer graphene film.
Embodiment 4
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg sodium chlorate is put into solution, is stirred 12 hours at room temperature, by product eccentric cleaning.
(3) product is added in the hydrogen peroxide that excessive mass fraction is 30%, reaction time 1h, obtains single side choosing
Selecting property graphene oxide.
(4) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, by excessive oleyl amine
It is added, 100 DEG C of heating 4h keep stirring, obtain single side selectivity oleophylic graphite alkene.
(5) single side selectivity oleophylic graphite alkene material is put into hexamethylene and is stirred evenly, stood after stopping stirring, from group
Dress up single-layer graphene film.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (6)
1. a kind of preparation method of single-layer graphene film, includes the following steps:
(1) anhydrous ferric trichloride and graphite Hybrid Heating are prepared into second order graphite intercalation compound with molte-salt synthesis, using oxygen
Agent and concentrated acid carry out oxidation intercalation to second order graphene intercalation compound, after cleaning, excessive hydrogen peroxide are added and removes carbon-coating, obtains
To single side selective oxidation graphene；
(2) by single side selective oxidation grapheme material ultrasonic disperse Yu Shuiyu alcohol mixed solution, oleyl amine or oleic acid are added
Enter, heat and keep stirring, obtains single side selectivity oleophylic graphite alkene；
(3) single side selectivity oleophylic graphite alkene material is put into organic solvent, utilizes its distinctive oleophylic oleophobic property, oleophobic face
Upward ingress of air, oleophylic contact solution downwards, and single side selectivity oleophylic graphite alkene is dispersed in gas-liquid interface, is self-assembled into list
Layer graphene film.
2. preparation method according to claim 1, which is characterized in that the molten-salt growth method reaction temperature in step (1) is 400
DEG C, the reaction time is 4-6 hours, and anhydrous ferric trichloride and graphite quality ratio are 5: 1.
3. preparation method according to claim 1, which is characterized in that the oxidant in step (1) includes chlorate, high chlorine
Hydrochlorate, permanganate, bichromate, sodium peroxide, concentrated acid are the mixture of the concentrated sulfuric acid or the concentrated sulfuric acid and concentrated nitric acid, and oxidation is inserted
The layer time is 4-48h, and temperature is 0-80 DEG C.
4. preparation method according to claim 1, which is characterized in that hydrogen peroxide and ferric trichloride in step (1) it is anti-
It is 1-4h between seasonable, reaction temperature is room temperature.
5. preparation method according to claim 1, which is characterized in that the ratio of water and alcohol in step (2) is any ratio
The mass ratio of example, single side selective oxidation graphene and oleyl amine or oleic acid is 50: 1-1: 50, and heating temperature is 90-200 DEG C, when
Between be 0.5-24h.
6. preparation method according to claim 1, which is characterized in that the organic solvent in step (3) is hexamethylene, third
Ketone, toluene, chloroform, gas-liquid interface area can be controlled freely, but need to control the amount that single side selective oxidation graphene is added,
In order to avoid forming multilayered structure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910353510.XA CN110015656A (en) | 2019-04-23 | 2019-04-23 | A kind of preparation method of single-layer graphene film |
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| CN201910353510.XA CN110015656A (en) | 2019-04-23 | 2019-04-23 | A kind of preparation method of single-layer graphene film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540353A (en) * | 2021-06-21 | 2021-10-22 | 复旦大学 | Oriented gas-liquid interface polymer semiconductor film and construction method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113540353A (en) * | 2021-06-21 | 2021-10-22 | 复旦大学 | Oriented gas-liquid interface polymer semiconductor film and construction method and application thereof |
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Application publication date: 20190716 |