CN113998695B - Rapid preparation method of graphene-based suspension ultrathin film - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000725 suspension Substances 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 99
- 238000003756 stirring Methods 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 28
- 238000012546 transfer Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 238000001338 self-assembly Methods 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- KIDBBTHHMJOMAU-UHFFFAOYSA-N propan-1-ol;hydrate Chemical compound O.CCCO KIDBBTHHMJOMAU-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- Chemical & Material Sciences (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a quick preparation method of a graphene-based suspension ultrathin film, which comprises the steps of firstly preparing a graphene oxide alcohol solution with water content less than 0.1vol% by adopting a separation substitution process, and then mixing the graphene oxide alcohol solution with water to prepare a graphene/alcohol water solution with higher alcohol concentration; heating and evaporating the graphene oxide/alcohol aqueous solution in a vacuum environment to form a suspended graphene oxide film; and finally, reducing and drying to obtain the graphene-based suspension ultrathin film. The method can realize the interface self-assembly of the graphene-based suspension ultrathin film and the one-step separation of the graphene-based suspension ultrathin film and the graphene oxide solution, and effectively gets rid of the dependence of the existing graphene film preparation on the film transfer technology; the preparation method is simple, the film is formed rapidly, the environment is friendly, the production cost of the graphene film can be greatly reduced, and the industrial production of the graphene film is facilitated.
Description
Technical Field
The invention belongs to the technical field of functional materials and preparation thereof, and particularly relates to a rapid preparation method of a graphene-based suspension ultrathin film.
Background
The graphene film has become a research hot spot in the fields of selective transmission films, high heat conduction films, nano mechanical sensors and the like by virtue of the advantages of a monomolecular layer structure, excellent electric conduction and heat conduction properties, high flexibility and the like. The current method for preparing the graphene film mainly comprises a vacuum filtration method, a chemical vapor deposition method, a spin coating method, an interface self-assembly method and the like. The interface self-assembly method has the advantages of simple method and low cost, and the prepared film microstructure is highly ordered, so that the interface self-assembly method is focused by more and more scientific researches and engineering personnel, and important scientific value and application value are shown.
However, the existing methods for preparing the graphene film all need to use a film transfer technology, namely, the graphene film needs to be further peeled off from the load substrate; in the interfacial self-assembly method, although the conventional solid substrate support is not required to be introduced, the self-assembled film still floats on the liquid surface (active separation of the self-assembled film and the reaction solution cannot be realized), and the self-assembled film needs to be further taken out from the liquid surface by means of Dip-coating film transfer technology and the like (Dip-coating). For the graphene ultrathin film with limited strength, the film transfer technology not only increases the damage risk of the film and seriously affects the quality of the graphene film, but also further increases the production cost of the graphene film due to the complex operation of the film transfer process and high technical requirement, so that the film transfer technology becomes one of the main factors which hinder the industrialized popularization of the graphene film.
Further research and development of a simple and efficient rapid preparation method without a film transfer technology is one of important means for promoting scientific research and engineering application of graphene films.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides a rapid preparation method of a graphene-based suspension ultrathin film, which utilizes the unique thermodynamic characteristics of an alcohol-water binary solution system to adjust the interaction between solvent molecules and graphene oxide nano sheets, so as to improve the film forming property of the graphene oxide solution, realize the interface self-assembly of the graphene-based suspension ultrathin film and the one-step separation of the graphene-based suspension ultrathin film and the graphene oxide solution for the first time, and further get rid of the dependence of the preparation of the existing graphene film on a film transfer technology; the preparation method is simple, the film is formed rapidly, the environment is friendly, the production cost of the graphene film can be greatly reduced, and the industrial production of the graphene film is facilitated.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a quick preparation method of a graphene-based suspension ultrathin film comprises the following steps:
1) Preparation of graphene oxide/alcohol aqueous solution:
carrying out centrifugal separation on the graphene oxide aqueous solution, removing supernatant, adding an alcohol solvent, uniformly stirring, carrying out secondary centrifugal separation, and removing supernatant; repeating the steps of adding the alcohol solvent and centrifuging until a graphene oxide alcohol solution with the water content of less than 0.1vol% is obtained; adding water to prepare graphene oxide/alcohol water solution, and performing ultrasonic treatment for later use;
2) Preparation and reduction of a suspended graphene oxide ultra-thin film:
heating and evaporating the obtained graphene oxide/alcohol water solution in a vacuum environment, self-assembling the graphene oxide at the interface of the solution and air to form a film, gradually separating from the liquid surface along with the descending of the liquid surface, and forming a graphene oxide film suspended above the liquid surface; and then taking out the graphene oxide film, carrying out reduction reaction, and drying to obtain the graphene-based suspension ultrathin film.
In the above scheme, the alcohol solvent may be one or more of methanol, ethanol, propanol, etc.
In the scheme, the centrifugal separation rotating speed in the step 1) is 9000-11000 r/min, and the time is 30-50 min.
In the scheme, the concentration of graphene oxide in the graphene oxide alcohol solution in the step 1) is 0.5-5 mg/ml.
In the above-mentioned scheme, the volume ratio of the graphene oxide alcohol solution to water in the step 1) is (7-9.5): 1.
In the scheme, the ultrasonic treatment time in the step 1) is 1-2 h, and the ultrasonic frequency is 40-80 KHz.
In the scheme, the temperature adopted in the heating and evaporating step in the step 2) is 50-70 ℃, and the vacuum degree is minus 0.06-minus 0.08MPa.
In the above-mentioned scheme, the time required for forming the suspension film is 20 minutes or more, preferably 20 to 50 minutes.
Preferably, the heating evaporation step adopts a temperature of 60 ℃ and a vacuum degree of-0.08 MPa.
In the above scheme, the reduction reaction in step 2) includes: placing the mixture into saturated steam of hydrogen iodide, and reacting for 2 to 4 hours at the temperature of 75 to 85 ℃.
In the scheme, the drying step in the step 2) adopts a vacuumizing drying process, the adopted temperature is 110-130 ℃, the time is 10-12 h, and the vacuum degree is-0.06-0.08 Mpa.
In the above scheme, the graphene oxide aqueous solution is prepared by adopting a Hummers method.
Preferably, the preparation method of the graphene oxide aqueous solution comprises the following steps:
1) Ice on concentrated sulfuric acidWater bath treatment, adding natural graphite into concentrated sulfuric acid, stirring, and adding KMnO 4 Carrying out secondary stirring treatment;
2) And (3) heating and stirring the dispersion liquid obtained in the step (1) twice under the water bath condition, sequentially adding water and hydrogen peroxide solution in the second heating and stirring process, uniformly stirring, and finally performing centrifugal separation and washing until the pH value is 6-7 to obtain the graphene oxide aqueous solution.
In the scheme, the ice water bath time is 15-25 min.
In the scheme, the stirring treatment rate in the step 1) is 500-600 r/min, the time is 25-35 min, and the temperature is-1-5 ℃.
Preferably, KMnO in step 1) 4 Is added in 5 times within 30 min.
In the scheme, the secondary stirring speed in the step 1) is 1200-1300 r/min, the stirring time is 2.5-3 h, and the temperature is-1-5 ℃.
In the scheme, the stirring speed adopted for the first heating and stirring supplement in the step 2) is 200-300 r/min, the stirring time is 20-30 min, and the temperature is 35-45 ℃.
In the scheme, the stirring speed adopted for the secondary heating and stirring supplement in the step 2) is 200-300 r/min, the stirring time is 10-15 min, and the stirring temperature is 75-80 ℃.
In the scheme, the specific steps of the distilled water added in the step 2) are as follows: adding part of water, stirring for 20-25 min at a stirring rate of 200-300 r/min, and adding the rest of water.
In the above scheme, the natural graphite introduced in step 2), KMnO 4 Concentrated sulfuric acid, water and H 2 O 2 The mass ratio of (1) (42-45) (5.9-6.1) (205-210) (3-4).
In the scheme, in the step 2), distilled water is used for washing the graphene oxide aqueous solution until the pH value is 6-7.
The graphene-based suspension ultrathin film prepared according to the scheme has the thickness of 300 nm-1.3 mu m, and can rapidly realize self-assembly of the ultrathin graphene oxide-based film and one-step separation of the ultrathin graphene oxide-based film and a reaction solution. The edge part of the formed ultrathin graphene oxide film is attached to the inner wall of the reaction container, the obtained ultrathin graphene oxide film can be rapidly taken out on the premise of not damaging the film quality by adopting means of simple circular cutting, cutting and the like, and finally reduction treatment is carried out, so that the graphene-based suspension ultrathin film is obtained.
Further, by adopting the preparation method provided by the invention, continuous heating and evaporation are carried out for more than 40min, so that the preparation of the multilayer graphene-based suspension ultrathin film can be realized in one step.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, the unique thermodynamic characteristics of an alcohol-water binary solution system are utilized for the first time, and the film forming property of the graphene oxide solution is improved by adjusting the interaction between solvent molecules and graphene oxide nano sheets, so that the interface self-assembly of the graphene-based suspension ultrathin film and the one-step separation of the graphene-based suspension ultrathin film from the graphene oxide solution are rapidly realized; the limitation that the existing graphene film technology needs to be realized by a film transfer technology can be effectively eliminated; the related process is simple, the reaction condition is mild, toxic chemical auxiliary agents are not required to be introduced, and the method is environment-friendly and suitable for popularization and application;
2) By adopting the preparation method, film can be formed rapidly, and the shortest film forming time is only 1min; the method is far lower than the traditional graphene film forming process, and can obviously shorten the synthesis period;
3) The multi-layer film can be formed at one time in a mode of prolonging the evaporation time, so that the production efficiency of the graphene-based film is greatly improved.
Drawings
FIG. 1 is a schematic diagram of the interface self-assembly process of graphene oxide based suspension ultrathin films described in example 1;
FIG. 2 is a morphology of the graphene oxide-based suspension ultrathin film obtained in example 1;
FIG. 3 is a topography of the multi-layered graphene oxide film of example 1 formed in one step;
FIG. 4 is a graph of the morphology of graphene-based ultrathin film obtained in example 1 (a) and SEM (b);
fig. 5 is an XRD pattern of graphene-based ultra-thin film obtained in example 1.
Detailed Description
For a better understanding of the present invention, the following description will further illustrate the present invention with reference to specific examples, but the present invention is not limited to the following examples.
In the following examples, the preparation method of the graphene oxide aqueous solution adopted includes the following steps:
1) Adding 23mL of 98% concentrated sulfuric acid into a beaker, carrying out ice water bath for 20min, adding natural graphite, stirring at 600r/min for 30min, and adding 6g of KMnO 4 (5 times of addition in 30 min), and stirring for 2.5h under the condition of 1200 r/min;
2) Placing the dispersion liquid obtained in the step 1) into a constant-temperature water bath at 40 ℃ and stirring for 25min at a stirring rate of 300 r/min; then placing the graphene oxide solution into a constant temperature water bath kettle at 80 ℃ and stirring for 15min at the stirring rate of 300r/min, then adding 80mL of distilled water and stirring for 20min at the stirring rate of 300r/min, then adding 60mL of distilled water, finally adding 60mL of distilled water and 10.81mL of hydrogen peroxide solution (the concentration is 30 wt%) and centrifuging for 10min at the condition of 8000r/min, and then washing until the pH is 6-7, thus obtaining the graphene oxide aqueous solution.
Example 1
A quick preparation method of a graphene-based suspension ultrathin film comprises the following steps:
1) Preparation of graphene oxide/ethanol-water binary solution:
filling the graphene oxide aqueous solution into a centrifuge tube, centrifuging at a speed of 10000r/min for 40min, and removing supernatant; adding absolute ethyl alcohol to fill the centrifuge tube, uniformly stirring, continuously centrifuging at 10000r/min for 40min, and removing supernatant; repeating the steps of adding absolute ethyl alcohol, stirring uniformly and centrifugally separating until a graphene oxide ethanol solution with the water content of less than 0.1vol% (wherein the concentration of graphene oxide is 3 mg/ml) is obtained; then distilled water is added into the mixture, the volume ratio of ethanol to distilled water in the obtained mixed system is controlled to be 9:1, and graphene oxide/ethanol-water binary solution is prepared, and the mixture is subjected to ultrasonic treatment for 2 hours (the ultrasonic frequency is 40 KHz) for later use;
2) Preparation and reduction of a suspended graphene oxide ultra-thin film:
placing the graphene oxide/alcohol aqueous solution obtained in the step 1) into a beaker, and evaporating for 40min in a vacuum environment at 60 ℃ (the vacuum degree is-0.08 MPa), wherein the graphene oxide is self-assembled to form a film at the interface of the solution and air in the process, so that a graphene oxide film with the edge attached to the inner wall of the beaker and suspended above the liquid level is formed; and then, circularly cutting out the formed graphene oxide film, placing the graphene oxide film in 80 ℃ hydrogen iodide saturated steam for reduction for 3 hours, and then, vacuumizing and drying the graphene oxide film for 12 hours at 120 ℃ to obtain the graphene-based suspension ultrathin film.
The photo of the interface self-assembly process of the graphene oxide film in the example is shown in fig. 1, and it can be seen that the graphene oxide film can be formed within 1min, and the film forming speed is high.
Fig. 2 is a morphology diagram of the graphene oxide film obtained after evaporation for 40min by the method described in this example, and it can be seen that the graphene oxide film obtained is suspended in a container, and does not depend on substrate support, and does not need to use a film transfer technology.
Fig. 3 is a morphology diagram of a product obtained by continuously evaporating a solution system in a beaker by the method in the embodiment, and it can be seen that the preparation method can be used for preparing a multi-layer graphene oxide film at one time, and the preparation efficiency is high.
The morphology diagram and the SEM diagram in the thickness direction of the graphene-based ultrathin film obtained by the embodiment are shown in fig. 4, and it can be seen that the graphene-based ultrathin film obtained by the invention has a complete structure and an average thickness of about 480nm; has a multilayer structure.
Fig. 5 is an XRD pattern of the graphene-based ultra-thin film obtained in this example, and the result shows that the obtained thin film is a graphene-based ultra-thin film.
Example 2
A quick preparation method of a graphene-based suspension ultrathin film comprises the following steps:
1) Preparation of graphene oxide/methanol-water binary solution:
filling the prepared graphene oxide aqueous solution into a centrifuge tube, centrifuging at a speed of 10000r/min for 40min, removing supernatant, adding methanol to fill the centrifuge tube, stirring uniformly, centrifuging at a speed of 10000r/min for 40min, and removing supernatant; repeating the steps of adding methanol, stirring uniformly and centrifugally separating until a graphene oxide methanol solution with the water content of less than 0.1vol% (wherein the concentration of graphene oxide is 3 mg/ml) is obtained, then adding distilled water into the graphene oxide methanol solution, controlling the volume ratio of methanol to distilled water in the obtained mixed system to be 8:1, preparing a graphene oxide/methanol-water binary solution, and carrying out ultrasonic treatment (with the frequency of 40 KHz) for 2 hours for later use;
2) Preparation and reduction of a suspended graphene oxide ultra-thin film:
evaporating the graphene oxide/methanol-water binary solution obtained in the step 1) in a vacuum environment with the temperature of 60 ℃ and the vacuum degree of-0.08 MPa, and self-assembling graphene oxide into a film at the interface of the solution and air in the process to form a suspended graphene oxide film; and taking down the graphene oxide film, then placing the graphene oxide film in 80 ℃ hydrogen iodide saturated steam for reduction for 3 hours, and then carrying out vacuum drying for 12 hours at 120 ℃ to obtain the graphene-based ultrathin film.
Example 3
A quick preparation method of a graphene-based suspension ultrathin film comprises the following steps:
1) Preparation of graphene oxide/propanol-water binary solution:
filling the prepared graphene oxide aqueous solution into a centrifuge tube, centrifuging at a speed of 10000r/min for 40min, removing supernatant, adding propanol into the centrifuge tube to fill the centrifuge tube, uniformly stirring, centrifuging at a speed of 10000r/min for 40min, and removing supernatant; repeating the steps of adding propanol, stirring uniformly and centrifugally separating until a graphene oxide propanol solution with the water content of less than 0.1vol% (wherein the concentration of graphene oxide is 3 mg/ml) is obtained, then adding distilled water into the solution, controlling the volume ratio of propanol to distilled water in the obtained mixed system to be 9.5:1, preparing a graphene oxide/propanol-water binary solution, and carrying out ultrasonic treatment (with the frequency of 40 KHz) for 2 hours for later use;
2) Preparation and reduction of a suspended graphene oxide ultra-thin film:
placing the graphene oxide/propanol-water binary solution obtained in the step 1) in a vacuum environment with the temperature of 60 ℃ and the vacuum degree of-0.08 MPa for evaporation, and forming a suspended graphene oxide film by self-assembling graphene oxide at the interface of the solution and air in the process; and taking down the graphene oxide film, then placing the graphene oxide film in 80 ℃ hydrogen iodide saturated steam for reduction for 3 hours, and then carrying out vacuum drying for 12 hours at 120 ℃ to obtain the graphene-based ultrathin film.
Comparative example 1
A method for preparing graphene-based ultrathin film, which is substantially the same as in example 1, except that: in the graphene oxide/ethanol-water binary solution prepared in the step 1), the volume ratio of water to ethanol is 10:0.
By adopting the solution system in the comparative example, the graphene oxide film can be formed after evaporation for 5 hours in the vacuum environment (the vacuum degree is-0.08 MPa) at the temperature of 60 ℃ in the step 2), but cannot be separated from the liquid level, and the effect of film transfer without a substrate cannot be achieved.
Comparative example 2
A method for preparing graphene-based ultrathin film, which is substantially the same as in example 1, except that: in the graphene oxide/ethanol-water binary solution prepared in the step 1), the volume ratio of water to ethanol is 0:10.
By adopting the solution system in the comparative example, after evaporating for 2 hours in the vacuum environment at 60 ℃ (the vacuum degree is-0.08 MPa) in the step 2), a complete graphene oxide film cannot be formed, and the film cannot be separated from the liquid level, so that the effect of film transfer without a substrate cannot be achieved.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (6)
1. The quick preparation method of the graphene-based suspension ultrathin film is characterized by comprising the following steps of:
1) Preparation of graphene oxide/alcohol aqueous solution:
preparing graphene oxide alcohol solution with water content less than 0.1 vol%; then adding water into the solution to prepare graphene oxide/alcohol water solution, and performing ultrasonic treatment;
2) Preparation and reduction of a suspended graphene oxide ultra-thin film:
heating and evaporating the graphene oxide/alcohol water solution obtained in the step 1) in a vacuum environment to form a suspended graphene oxide film; then taking out the graphene oxide film, carrying out reduction reaction, and drying to obtain the graphene suspension ultrathin film;
the concentration of graphene oxide in the graphene oxide alcohol solution in the step 1) is 0.5-5 mg/ml;
the volume ratio of the graphene oxide alcohol solution to water in the step 1) is (7-9.5): 1;
the heating evaporation step is carried out at a temperature of 50-70 ℃ and a vacuum degree of-0.06 to-0.08 MPa.
2. The rapid preparation method according to claim 1, wherein the alcohol solvent in the alcohol solution is one or more of methanol, ethanol and propanol.
3. The rapid preparation method according to claim 1, wherein the preparation step of the graphene oxide alcohol solution in step 1) comprises: carrying out centrifugal separation on the graphene oxide aqueous solution, removing supernatant, adding an alcohol solvent, uniformly stirring, carrying out secondary centrifugal separation, and removing supernatant; repeating the steps of adding the alcohol solvent and centrifuging until the graphene oxide alcohol solution with the water content of less than 0.1vol% is obtained.
4. The rapid preparation method according to claim 1, wherein the ultrasonic treatment time in step 1) is 1 to 2 hours.
5. The rapid manufacturing method according to claim 1, wherein the time required to form the suspended graphene oxide thin film is 20 minutes or more.
6. The rapid preparation method according to claim 1, wherein the reduction reaction of step 2) comprises: and (3) placing the mixture into saturated steam of hydrogen iodide, and reacting for 2-4 hours at the temperature of 75-85 ℃.
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| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
| CN103000245A (en) * | 2012-12-03 | 2013-03-27 | 京东方科技集团股份有限公司 | Graphene metal hybrid electrode material and preparation method and applications thereof |
| CN107032328A (en) * | 2016-02-02 | 2017-08-11 | 中国科学院理化技术研究所 | Preparation method of self-supporting reduced graphene oxide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513998A (en) * | 2009-02-11 | 2009-08-26 | 中国科学院山西煤炭化学研究所 | Method for preparing ordered graphene oxide films |
| CN103000245A (en) * | 2012-12-03 | 2013-03-27 | 京东方科技集团股份有限公司 | Graphene metal hybrid electrode material and preparation method and applications thereof |
| CN107032328A (en) * | 2016-02-02 | 2017-08-11 | 中国科学院理化技术研究所 | Preparation method of self-supporting reduced graphene oxide film |
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