CN113213465A - Single-layer graphene and preparation method thereof - Google Patents
Single-layer graphene and preparation method thereof Download PDFInfo
- Publication number
- CN113213465A CN113213465A CN202110328880.5A CN202110328880A CN113213465A CN 113213465 A CN113213465 A CN 113213465A CN 202110328880 A CN202110328880 A CN 202110328880A CN 113213465 A CN113213465 A CN 113213465A
- Authority
- CN
- China
- Prior art keywords
- layer graphene
- preparation
- graphene
- reaction
- graphene according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 239000002356 single layer Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011173 large scale experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
Classifications
-
- 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
- C01B32/194—After-treatment
-
- 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
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
Abstract
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method of single-layer graphene, which comprises the following steps: s1, dispersing Cu in an ultrasonic mode2+And In3+Dissolving in graphene oxide ethanol solution, and adding CS (NH)2)2Fully and uniformly stirring; s2, reacting for 9-11 h in a high-pressure reaction kettle at 170-190 ℃, and after the reaction is completed and the reaction is cooled, centrifugally separating and washing the obtained crude product; s3, placing the crude product in hydrochloric acid, performing ultrasonic treatment at 60 ℃ for 20-50 min, and performing suction filtration to obtain a black product; and S4, washing the black product for several times by using an organic solvent to obtain the single-layer graphene. The preparation method has the advantages of environmental friendliness, no pollution, simple preparation equipment, simplicity and convenience in operation and the like, can be used for carrying out macroscopic synthesis in a high-pressure reaction kettle, and also provides the single-layer graphene obtained based on the preparation method.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to single-layer graphene and a preparation method thereof.
Background
Graphene is a carbon material which has been developed rapidly in recent years and has sp carbon atoms2The hybridized six-membered rings are arranged to have a honeycomb lattice structure. Graphene earliestThe preparation method is to prepare graphite by a physical method, and the obtained graphene cannot be widely popularized due to small amount. Therefore, subsequent researchers have developed large-scale experiments to find large-scale production methods. The most classical is a wet chemical method using potassium permanganate, concentrated sulfuric acid and other high oxidizing agents as raw materials. However, the graphene obtained by the method has a great defect that the obtained graphene has a thick lamellar structure, and is generally of a multilayer structure, which affects many applications of the graphene to a certain extent.
At present, the application of graphene is mainly in the fields of electrochemical sensing, energy devices, adsorbents, catalysis and the like, and has wide application prospects. The applications in these fields put new requirements on graphene, that is, light weight, large specific surface area, good conductivity, etc., which provides more challenges for the preparation of graphene. Currently, a single layer of graphene substantially meets these requirements. Therefore, how to adopt chemical methods to obtain single-layer graphene on a large scale becomes an important challenge at present.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of single-layer graphene, which has the advantages of environmental friendliness, no pollution, simple preparation equipment, simplicity and convenience in operation and the like, can be used for carrying out mass synthesis in a high-pressure reaction kettle, and also provides the single-layer graphene obtained based on the preparation method.
The invention is realized by adopting the following technical scheme:
a preparation method of single-layer graphene comprises the following steps:
s1, dispersing Cu in an ultrasonic mode2+And In3+Dissolving in graphene oxide ethanol solution, and adding CS (NH)2)2Fully and uniformly stirring; s2, reacting for 9-11 h in a high-pressure reaction kettle at 170-190 ℃, and after the reaction is completed and the reaction is cooled, centrifugally separating and washing the obtained crude product; s3, placing the crude product in hydrochloric acid, performing ultrasonic treatment at 60 ℃ for 20-50 min, and performing suction filtration to obtain a black product; s4, washing the black product for a plurality of times by using an organic solvent to obtain the single-layer stoneGraphene.
Preferably, said Cu is present in a molar ratio2+，In3+And CS (NH)2)2The ratio of (1): 1: (3.9-4.1).
In a preferred embodiment, the Cu2+The source is CuCl2In of said3+The source is InCl3。
Preferably, in step S1, the ultrasonic dispersion time is 25-40 min.
Preferably, in step S2, the reaction temperature in the autoclave is 180 ℃.
Preferably, in step S2, the reaction time in the autoclave is 10 hours.
Preferably, in step S2, the detergent used in the washing is water.
Preferably, in the step S3, the mass fraction of the hydrochloric acid is 5 to 20%.
Preferably, in the step S3, the temperature of the ultrasound is 55-65 ℃.
Preferably, in step S4, the organic solvent is absolute ethanol.
The single-layer graphene is prepared by any one of the above methods, and further, the thickness of a lamellar structure of the single-layer graphene is less than 1 nm.
The invention has the beneficial effects that:
1. the invention relates to a preparation method of single-layer graphene, which is prepared by mixing Cu2+And In3+Accelerating the micro-layer into the interlayer space of the graphene lamellar structure by using an ultrasonic method, and introducing CS (NH)2)2Bringing Cu in graphene layer spacing2+、In3+Rapidly crystallized to CuInS under high temperature condition2Crystals, this growth process is very fast, with CuInS2The growth of the crystal enlarges the distance between the carbon atom layers, so that the gaps of the graphene sheet layer structure are opened, and finally, the CuInS is treated by hydrochloric acid2And dissolving and removing the crystals to obtain a pure single-layer graphene product.
2. The preparation method of the single-layer graphene disclosed by the invention is disclosed for the first time at present, and the graphene lamellar structure is processed by utilizing the dynamic expansion principle of growth in the chemical reaction process of metal ions, so that the preparation method has obvious difference from the method for processing the graphene lamellar structure in a surface adsorption mode.
3. The preparation method of the single-layer graphene has the advantages of environmental friendliness, no pollution, simple preparation equipment, simplicity and convenience in operation and the like, and can be used for carrying out macro synthesis in a high-pressure reaction kettle.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a transmission electron microscope image of graphene prepared in comparative example 1.
Fig. 2 is a transmission electron microscope photograph of single-layer graphene prepared in example 1.
Fig. 3 is an atomic force microscope image of single-layer graphene prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The traditional graphene preparation method comprises the following preparation steps:
at 0 deg.C, 0.5g graphite and 0.5g NaNO3Adding the mixture into a 250mL beaker, fully stirring, slowly adding 23mL of concentrated sulfuric acid with the mass fraction of 95-98%, fully stirring for 15-20 minutes, adding 4g of potassium permanganate into the system, and reacting for 2 hours at 35-40 DEG CObtaining a green suspension, adding 40 ml of deionized water into the green suspension, stirring and reacting for 1-2 hours at 90 ℃ to obtain a brown yellow suspension; to the brown yellow suspension was added 5 ml of H2O2To reduce the remaining KMnO4(ii) a And after the reaction liquid is cooled to room temperature, carrying out centrifugal separation, cleaning and collecting a product to obtain the graphene oxide.
Comparative example 1
A graphene preparation method comprises the following preparation steps:
at 0 deg.C, 0.5g graphite and 0.5g NaNO3Adding the mixture into a 250mL beaker, fully stirring, slowly adding 23mL of concentrated sulfuric acid with the mass fraction of 97%, fully stirring for 20 minutes, adding 4g of potassium permanganate into the system, reacting for 2 hours at 38 ℃ to obtain a green suspension, adding 40 mL of deionized water into the green suspension, stirring and reacting for 2 hours at 90 ℃ to obtain a brown yellow suspension; to the brown yellow suspension was added 5 ml of H2O2To reduce the remaining KMnO4(ii) a And after the reaction liquid is cooled to room temperature, carrying out centrifugal separation, cleaning and collecting a product to obtain the graphene oxide.
Referring to fig. 1, fig. 1 is a Transmission Electron Microscope (TEM) image of graphene prepared by a conventional method, and it can be seen from fig. 1 that graphene obtained by a conventional chemical method has a multilayer structure and a graphene lamellar structure is thick.
Example 1
A preparation method of single-layer graphene comprises the following steps:
s1, mixing 0.01moL of CuCl in an ultrasonic dispersion mode2Crystals and 0.01moL of InCl3Dissolving the crystal in 0.1g of ethanol solution of graphene oxide to form uniform dispersion liquid, wherein the preparation steps of the graphene oxide refer to the traditional graphene preparation method, in the embodiment, the specific preparation steps refer to comparative example 1, the ultrasonic dispersion time is 30min, and then 0.04moL of CS (NH) is added2)2Adding into the dispersion liquid, and stirring thoroughly;
s2, reacting for 10 hours in a high-pressure reaction kettle at 180 ℃, after the reaction is completed and the reaction is cooled, centrifugally separating and washing the obtained crude product, wherein the washing agent is water;
s3, placing the crude product in 17% hydrochloric acid by mass, performing ultrasonic treatment at 60 ℃ for 30min, and performing suction filtration to obtain a black product;
and S4, washing the black product for several times by using absolute ethyl alcohol to obtain the single-layer graphene.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the single-layer graphene prepared in this example, and it can be seen from fig. 2 that the graphene has a very thin transparent lamellar structure; fig. 3 is an Atomic Force Microscope (AFM) image of the single-layer graphene prepared according to the present invention, and it can be known from fig. 3 that the thickness of the lamellar structure of the graphene is less than 1nm, normally, the distance between graphene layers is 0.335nm, and the bond length of the C-C atom of the graphene is approximately 0.142 nm.
The above results show that: the single-layer graphene prepared by the invention has a lamellar structure of about 1-2 layers, and can be basically considered as a single-layer structure.
Example 2
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S1, the ultrasonic dispersion time is 25 min.
Example 3
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S1, the ultrasonic dispersion time is 40 min.
Example 4
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S2, the reaction temperature in the high-pressure reaction kettle is 170 ℃, and the reaction time is 11 h.
Example 5
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S2, the reaction temperature in the high-pressure reaction kettle is 190 ℃ and the reaction time is 9 h.
Example 6
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S3, the mass fraction of hydrochloric acid is 22%.
Example 7
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S3, the mass fraction of hydrochloric acid is 5%.
Example 8
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S3, the hydrochloric acid is present in an amount of 12% by mass.
Example 9
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S3, the temperature of the ultrasonic wave is 55 ℃, and the ultrasonic time is 50 min.
Example 10
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S3, the temperature of the ultrasonic wave is 65 ℃, and the ultrasonic time is 20 min.
Example 11
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S1, the CS (NH)2)2Was added in an amount of 0.039 moL.
Example 12
A method for preparing single-layer graphene, which is different from that in example 1 in preparation steps of: in step S1, the CS (NH)2)2The amount of addition of (1) was 0.041 moL.
The invention is not limited to the above-described examples, and various modifications or alterations without inventive work may be made by those skilled in the art within the scope of the invention defined by the claims appended hereto.
Claims (10)
1. A preparation method of single-layer graphene is characterized by comprising the following steps: the method comprises the following steps:
s1, dispersing Cu in an ultrasonic mode2+And In3+Dissolving in graphene oxide ethanol solution, and adding CS (NH)2)2Fully and uniformly stirring;
s2, reacting for 9-11 h in a high-pressure reaction kettle at 170-190 ℃, and after the reaction is completed and the reaction is cooled, centrifugally separating and washing the obtained crude product;
s3, placing the crude product in hydrochloric acid, performing ultrasonic treatment at 60 ℃ for 20-50 min, and performing suction filtration to obtain a black product;
and S4, washing the black product for several times by using an organic solvent to obtain the single-layer graphene.
2. The method for preparing single-layer graphene according to claim 1, wherein: in terms of mole ratio, the Cu2+，In3+And CS (NH)2)2The ratio of (1): 1: (3.9-4.1).
3. The method for preparing single-layer graphene according to claim 1, wherein: in the step S1, the ultrasonic dispersion time is 25-40 min.
4. The method for preparing single-layer graphene according to claim 1, wherein: in step S2, the reaction temperature in the autoclave was 180 ℃.
5. The method for preparing single-layer graphene according to claim 1, wherein: in step S2, the reaction time in the autoclave is 10 hours.
6. The method for preparing single-layer graphene according to claim 1, wherein: in the step S3, the mass fraction of the hydrochloric acid is 5-20%.
7. The method for preparing single-layer graphene according to claim 1, wherein: in the step S3, the temperature of the ultrasound is 55-65 ℃.
8. The method for preparing single-layer graphene according to claim 1, wherein: in step S4, the organic solvent is absolute ethanol.
9. A single-layer graphene, comprising: the preparation method is as claimed in any one of claims 1 to 8.
10. The single-layer graphene according to claim 9, wherein: the thickness of the lamellar structure of the single-layer graphene is less than 1 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110328880.5A CN113213465A (en) | 2021-03-27 | 2021-03-27 | Single-layer graphene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110328880.5A CN113213465A (en) | 2021-03-27 | 2021-03-27 | Single-layer graphene and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113213465A true CN113213465A (en) | 2021-08-06 |
Family
ID=77084255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110328880.5A Pending CN113213465A (en) | 2021-03-27 | 2021-03-27 | Single-layer graphene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113213465A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965105A (en) * | 2012-11-21 | 2013-03-13 | 中国科学院等离子体物理研究所 | Graphene-CuInS2 quantum dot compound and preparation method thereof |
| CN104609397A (en) * | 2014-12-09 | 2015-05-13 | 尹争艳 | Preparation method for reduced graphene-CuInS2 composite material |
| CN108676182A (en) * | 2018-02-27 | 2018-10-19 | 北京理工大学 | A kind of polymer matrix function film and preparation method thereof |
-
2021
- 2021-03-27 CN CN202110328880.5A patent/CN113213465A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965105A (en) * | 2012-11-21 | 2013-03-13 | 中国科学院等离子体物理研究所 | Graphene-CuInS2 quantum dot compound and preparation method thereof |
| CN104609397A (en) * | 2014-12-09 | 2015-05-13 | 尹争艳 | Preparation method for reduced graphene-CuInS2 composite material |
| CN108676182A (en) * | 2018-02-27 | 2018-10-19 | 北京理工大学 | A kind of polymer matrix function film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FENG GAO ET AL.: "Efficiency enhancement of perovskite solar cells based on graphene-CuInS2 quantum dots composite: The roles for fast electron injection and light harvests", 《APPLIED SURFACE SCIENCE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102275908B (en) | Preparation method of graphene material | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| WO2017084561A1 (en) | Preparation method for large-size graphene oxide or graphene | |
| Wang et al. | Fabrication of boron nitride nanosheets by exfoliation | |
| CN102153077A (en) | Method for preparing single-layer graphene with high carbon-oxygen ratio | |
| CN106882796B (en) | Preparation method of three-dimensional graphene structure/high-quality graphene | |
| CN102126720B (en) | Method for synthesizing graphene | |
| US9017638B2 (en) | Graphene prepared by using edge functionalization of graphite | |
| CN111252760B (en) | Preparation method of graphene oxide nano roll and composite material thereof | |
| CN103833008A (en) | Method for preparing graphene at normal temperature | |
| CN104058399B (en) | Direct preparation method of high-purity high-quality graphene | |
| CN112758950A (en) | Boron alkene nanosheet and preparation method thereof | |
| CN104386677A (en) | Micro-oxidized graphene and preparation method thereof | |
| CN108557813B (en) | Method for preparing oversized single-layer graphene oxide by one-step method | |
| CN107890861B (en) | Preparation method of titanium dioxide lamella/graphene composite film with {001} crystal face | |
| WO2017206579A1 (en) | Graphene micro-sheet having mesh structure and preparation method therefor | |
| CN113213465A (en) | Single-layer graphene and preparation method thereof | |
| RU2511613C1 (en) | Method of production of fluorographene layer | |
| KR102072914B1 (en) | A method for eco-friendly production of oxidized graphite and oxidized graphene using a hydroxylation reaction | |
| KR101308629B1 (en) | Method for preparation of nitrogen-containing graphene | |
| JP5447049B2 (en) | Method for producing graphene film | |
| CN114477148B (en) | Graphene microchip aggregate, preparation method thereof and preparation method of high-concentration graphene aqueous solution | |
| CN114368745A (en) | Graphene oxide, preparation method and application | |
| CN112093823A (en) | Auxiliary dispersion method of nano sheet material | |
| CN102659097A (en) | Preparation method of single-layer graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210806 |