CN115849359A - Preparation method of single-layer graphene oxide - Google Patents
Preparation method of single-layer graphene oxide Download PDFInfo
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- CN115849359A CN115849359A CN202211512904.3A CN202211512904A CN115849359A CN 115849359 A CN115849359 A CN 115849359A CN 202211512904 A CN202211512904 A CN 202211512904A CN 115849359 A CN115849359 A CN 115849359A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002356 single layer Substances 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 68
- 239000010439 graphite Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 238000009830 intercalation Methods 0.000 claims abstract description 10
- 230000002687 intercalation Effects 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of single-layer graphene oxide, which comprises the following steps: step one, uniformly mixing hydrogen peroxide and concentrated sulfuric acid, adding crystalline flake graphite when the mixed solution is cooled to room temperature, and soaking at room temperature; step two, after the soaking reaction is completed, washing and suction filtering are carried out by using deionized water, and after the washing and suction filtering are completed, drying is carried out to obtain expanded graphite; and step three, uniformly mixing the expanded graphite and the potassium permanganate, slowly dropwise adding concentrated sulfuric acid and concentrated phosphoric acid under an ice bath condition to perform secondary oxidation intercalation reaction, heating and stirring after the reaction is finished, adding ice water and hydrogen peroxide after the stirring is finished, performing centrifugal washing by using deionized water until the mixture is neutral, and performing freeze drying to obtain the single-layer graphene oxide with the sheet diameter of 438 microns. The method is characterized in that expanded graphite is prepared at room temperature, and oxidation intercalation treatment is carried out on the expanded graphite to obtain the large-sheet-diameter single graphene oxide, so that the problem that graphene oxide sheets prepared by the existing preparation process are easy to crack is solved.
Description
Technical Field
The invention relates to a preparation method of single-layer graphene oxide, and belongs to the technical field of materials.
Background
Graphene has excellent electrical, optical, mechanical and thermal properties and has received much attention in recent years. However, the wide use of graphene requires the development of a high-quality and low-cost graphene production process, and among many methods for preparing graphene, other methods than the redox method cannot meet the requirement for large-scale preparation of graphene.
The redox method based on Hummers method has been widely used to prepare graphene oxide, but graphene oxide prepared by the redox method generally has a smaller sheet diameter due to excessive use of an oxidant and sonication in its preparation. The quality requirement on raw materials is high. Taking a redox method as an example, graphite is required to be used as a raw material for preparing graphene oxide, and the purity, the sheet diameter and the like of common graphite cannot meet the requirements for preparing graphene oxide with an extra-large sheet diameter.
Meanwhile, the requirement on the preparation process is high, and the processing mode (such as ultrasonic oscillation) and the preparation conditions (such as high temperature and high pressure) used in the general preparation process of the graphene oxide can cause the change of the properties of the graphene oxide product, so that the sheet diameter size of the graphene oxide sample sheet after falling off from the graphite is remarkably reduced, and even the graphene oxide sample sheet is broken.
Disclosure of Invention
The invention designs and develops a preparation method of single-layer graphene oxide, which is characterized in that expanded graphite is prepared at room temperature, and the expanded graphite is subjected to oxidation intercalation treatment to obtain the single-layer graphene oxide with the sheet diameter of 438 mu m, and the problems that the graphene oxide sheet layer prepared by the existing preparation process is easy to crack and the single-layer large-sheet-diameter graphene oxide cannot be obtained are solved.
The technical scheme provided by the invention is as follows:
a preparation method of single-layer graphene oxide comprises the following steps:
step one, uniformly mixing hydrogen peroxide and concentrated sulfuric acid, adding crystalline flake graphite when the temperature of the mixed solution is reduced to room temperature, and soaking at room temperature;
step two, after the soaking reaction is completed, washing and suction-filtering the graphite by using deionized water, and drying the graphite after the soaking reaction is completed to obtain expanded graphite;
and step three, uniformly mixing the expanded graphite and potassium permanganate, slowly dropwise adding concentrated sulfuric acid and concentrated phosphoric acid under an ice bath condition to perform secondary oxidation intercalation reaction, heating and stirring after the reaction is finished, adding ice water and hydrogen peroxide after the stirring is finished, performing centrifugal washing by using deionized water until the mixture is neutral, and performing freeze drying to obtain the graphene oxide with the monolayer sheet diameter of 438 microns.
Preferably, the flake graphite is natural flake graphite with the granularity being more than or equal to 18 meshes.
Preferably, 1g of flake graphite is added to the mixed solution.
Preferably, the soaking time in the second step is 1.5 hours.
Preferably, in the third step, the heating and stirring process is to perform magnetic stirring for 2 hours in a water bath environment at 60 ℃.
The invention has the following beneficial effects: the preparation method of the single-layer graphene oxide with the extra-large flake diameter provided by the invention comprises the steps of firstly preparing expanded graphite by using extra-large flake graphite (18 meshes) as a raw material and adopting a secondary intercalation oxidation technology at room temperature, and then carrying out oxidation intercalation treatment on the expanded graphite to prepare the single-layer graphene oxide, wherein the maximum flake diameter is 438 mu m, and the average flake diameter is 220.99 mu m. A new process for preparing the large-sheet-diameter graphene oxide is developed, high-temperature and high-pressure reaction conditions are not needed, and the preparation process is simple to operate. The room temperature expanded graphite can completely maintain the original sheet diameter size of the graphite, almost has no fragmentation, and overcomes the problem of serious fragmentation degree of the graphite prepared by the existing preparation process. Breaks through the bottleneck of the existing large-sheet-diameter graphene oxide preparation process, and provides a new idea and method for preparing large-sheet-diameter graphene oxide.
Drawings
Fig. 1 (a) is a microscopic morphology of graphene oxide prepared by the room temperature graphite expansion method under a scanning electron microscope.
Fig. 1 (b) is a microscopic morphology of graphene oxide prepared by the room temperature graphite expansion method under a scanning electron microscope.
Fig. 1 (c) is a distribution diagram of the sheet diameter of graphene oxide prepared by the room temperature graphite expansion method according to the present invention.
Fig. 1 (d) is a microscopic morphology of graphene oxide prepared by the room temperature graphite expansion method under an atomic force microscope.
Fig. 1 (e) shows the average thickness of the graphene oxide prepared by the room temperature graphite expansion method according to the present invention under an atomic force microscope.
Fig. 2 (a) is a microscopic morphology of graphene oxide prepared by the rapid expansion graphite method according to the present invention under a scanning electron microscope.
Fig. 2 (b) is a distribution diagram of the sheet diameter of graphene oxide prepared by the rapid graphite expansion method according to the present invention.
Fig. 2 (c) is a microscopic morphology of graphene oxide prepared by the rapid graphite expansion method under an atomic force microscope.
Fig. 2 (d) shows the average thickness of the graphene oxide prepared by the rapid graphite expansion method according to the present invention under an atomic force microscope.
Fig. 3 (a) is a microscopic morphology of graphene oxide prepared by the slow expansion graphite method under a scanning electron microscope.
Fig. 3 (b) is a distribution diagram of the sheet diameter of graphene oxide prepared by the slow expansion graphite method according to the present invention.
Fig. 3 (c) is a microscopic morphology of graphene oxide prepared by the slow expansion graphite method under an atomic force microscope.
Fig. 3 (d) shows the average thickness of the graphene oxide prepared by the slow expansion graphite method according to the present invention under an atomic force microscope.
Detailed Description
The present invention is described in further detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
As shown in fig. 1-3, the present invention provides a method for preparing single-layer graphene oxide, which comprises, at room temperature, preparing expanded graphite by a secondary intercalation oxidation technique, and then performing oxidation intercalation treatment on the expanded graphite to obtain single-layer graphene oxide with a sheet diameter of 438 μm, including:
step one, uniformly mixing hydrogen peroxide and concentrated sulfuric acid, adding crystalline flake graphite when the mixed solution is cooled to room temperature, and soaking at room temperature;
step two, after the soaking reaction is completed, washing and suction filtering are carried out by using deionized water, and after the washing and suction filtering are completed, drying is carried out to obtain expanded graphite;
and step three, uniformly mixing the expanded graphite and potassium permanganate, slowly dropwise adding concentrated sulfuric acid and concentrated phosphoric acid under an ice bath condition to perform secondary oxidation intercalation reaction, heating and stirring after the reaction is finished, adding ice water and hydrogen peroxide after the stirring is finished, performing centrifugal washing by using deionized water until the mixture is neutral, and performing freeze drying to obtain the single-layer graphene oxide.
Examples
Preparation of room temperature expanded graphite:
uniformly mixing 1mL of hydrogen peroxide and 4mL of concentrated sulfuric acid to obtain a mixed solution, and adding 1g of crystalline flake graphite into the mixed solution when the temperature of the mixed solution is reduced to 20 ℃;
soaking for 1.5 hours at room temperature, washing with deionized water, and performing vacuum filtration;
after filtration, the obtained product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain room temperature expanded graphite.
Preparation of graphene oxide
Uniformly mixing 1g of room-temperature expanded graphite and 5g of potassium permanganate, and slowly dropwise adding 100mL of concentrated sulfuric acid and 33.3mL of concentrated phosphoric acid under the ice bath condition to obtain a mixture;
placing the obtained mixture in a water bath environment at 60 ℃, and carrying out magnetic stirring for 2 hours;
adding excessive ice water after the reaction is completed, stirring uniformly, and then dropwise adding hydrogen peroxide until the color of the solution becomes golden yellow;
and (4) carrying out centrifugal washing by using deionized water until the solution is neutral, and carrying out freeze drying to obtain a graphene oxide sample.
As shown in fig. 1 (a), 1 (b), 1 (c), 1 (d) and 1 (e), the graphene oxide prepared by the room-temperature expanded graphite method had a maximum sheet size of 438 μm, an average size of 220.99 μm and a thickness of 1.21nm, and thus it was judged that a single-layer graphene oxide was obtained.
Comparative example 1
Preparation of fast expansion graphite
Uniformly mixing 1g of natural crystalline flake graphite with 1g of potassium permanganate, and slowly dropwise adding 30mL of concentrated sulfuric acid under an ice bath condition to obtain a mixture;
placing the mixture in a water bath environment at 60 ℃, magnetically stirring for 2 hours, washing with deionized water after complete reaction, and carrying out vacuum filtration; drying in a 60 ℃ blast drying oven to obtain expandable graphite;
and (3) placing the expandable graphite in a muffle furnace at 1000 ℃ for expansion treatment for 1min to obtain the rapidly expanded graphite.
Preparation of graphene oxide
Uniformly mixing 1g of rapidly expanded graphite with 5g of potassium permanganate, and slowly dropwise adding 100mL of concentrated sulfuric acid and 33.3mL of concentrated phosphoric acid under the ice bath condition;
and (3) placing the mixture in a water bath environment at 60 ℃, magnetically stirring for 2 hours, adding excessive ice water after the reaction is completed, uniformly stirring, and dropwise adding hydrogen peroxide until the color of the solution becomes golden yellow.
And (4) carrying out centrifugal washing by using deionized water until the solution is neutral, and carrying out freeze drying to obtain a graphene oxide sample.
As shown in fig. 2 (a), 2 (b), 2 (c) and 2 (d), the graphene oxide prepared by the rapid expansion graphite method had a maximum sheet size of 202 μm, an average size of 105.82 μm and a thickness of 1.38nm, and thus it was judged that a single layer of graphene oxide was prepared.
Comparative example 2
Preparation of slowly-expanded graphite
Uniformly mixing 1g of natural crystalline flake graphite with 1g of potassium permanganate, and slowly dropwise adding 30mL of concentrated sulfuric acid under an ice bath condition to obtain a mixture;
placing the mixture in a water bath environment at 60 ℃, magnetically stirring for 2 hours, washing with deionized water after complete reaction, and carrying out vacuum filtration; drying in a 60 ℃ blast drying oven to obtain expandable graphite;
and (3) placing the expandable graphite in a tube furnace under the condition of argon protection, raising the temperature from room temperature to 1000 ℃ at the speed of 5 ℃/min, and then carrying out heat preservation treatment for 1 hour to obtain the slow-expansion graphite.
Preparation of graphene oxide
Uniformly mixing 1g of slowly expanded graphite and 5g of potassium permanganate, and slowly dropwise adding 100mL of concentrated sulfuric acid and 33.3mL of concentrated phosphoric acid under the ice bath condition; placing the mixture in a water bath environment at 60 ℃, and magnetically stirring for 2 hours;
adding excessive ice water after the reaction is completed, stirring uniformly, and then dropwise adding hydrogen peroxide until the color of the solution becomes golden yellow;
and (4) carrying out centrifugal washing by using deionized water until the solution is neutral, and carrying out freeze drying to obtain a graphene oxide sample.
As shown in fig. 3 (a), 3 (b), 3 (c) and 3 (d), the graphene oxide prepared by the slow expansion method had a maximum sheet size of 115 μm, an average size of 48.9 μm and a thickness of 1.25nm, and thus it was determined that a single layer of graphene oxide was prepared.
As can be seen from the examples and the comparative examples 1-2, in the examples, the graphene oxide is prepared from the expanded graphene prepared at room temperature, and the sheet diameter of the obtained single-layer graphene oxide is larger than that of the graphene oxide prepared by the rapid expansion process in the comparative example 1 and the slow expansion process in the comparative example 2; in example 1, the maximum sheet diameter of the single-layer graphene oxide prepared by the room temperature expansion process is 438 μm, and the average sheet diameter is 220.99 μm, which is much higher than that of the comparative example. The invention develops a new process for preparing the large-sheet-diameter graphene oxide, high-temperature and high-pressure reaction conditions are not needed, and the preparation process is simple to operate; the room-temperature expanded graphite can completely maintain the sheet diameter size of graphite and almost has no fragmentation, overcomes the problem of serious fragmentation degree of graphene oxide sheets prepared by the existing preparation process, breaks through the bottleneck of the existing large-sheet-diameter graphene oxide preparation process, and provides a new idea and method for preparing large-sheet-diameter graphene oxide.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (5)
1. A preparation method of single-layer graphene oxide is characterized by comprising the following steps:
step one, uniformly mixing hydrogen peroxide and concentrated sulfuric acid, adding crystalline flake graphite when the mixed solution is cooled to room temperature, and soaking at room temperature;
step two, after the soaking reaction is completed, washing and suction filtering are carried out by using deionized water, and after the washing and suction filtering are completed, drying is carried out to obtain expanded graphite;
and step three, uniformly mixing the expanded graphite and potassium permanganate, slowly dropwise adding concentrated sulfuric acid and concentrated phosphoric acid under an ice bath condition to perform secondary oxidation intercalation reaction, heating and stirring after the reaction is finished, adding ice water and hydrogen peroxide after the stirring is finished, performing centrifugal washing by using deionized water until the mixture is neutral, and performing freeze drying to obtain the single-layer graphene oxide with the sheet diameter of 438 microns.
2. The preparation method of single-layer graphene oxide according to claim 1, wherein the flake graphite is natural flake graphite with a particle size of 18 meshes or more.
3. The method for preparing single-layer graphene oxide according to claim 2, wherein in the first step, 1g of crystalline flake graphite is added to the mixed solution.
4. The method for preparing single-layer graphene oxide according to claim 3, wherein the soaking time in the second step is 1.5 hours.
5. The method for preparing single-layer graphene oxide according to claim 4, wherein in the third step, the heating and stirring process is magnetic stirring in a water bath environment at 60 ℃ for 2 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408000A (en) * | 2013-07-25 | 2013-11-27 | 黑龙江科技大学 | Preparation method for oxidized grapheme in large sheet |
| CN105293476A (en) * | 2015-11-16 | 2016-02-03 | 复旦大学 | Preparation method of large-size graphene oxide or graphene |
| CN106564893A (en) * | 2016-11-10 | 2017-04-19 | 电子科技大学 | Hundred micron-order graphene oxide and preparation method thereof |
| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
| CN113860295A (en) * | 2021-10-20 | 2021-12-31 | 华南理工大学 | Method for preparing graphene oxide by using large-particle-size flake graphite |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408000A (en) * | 2013-07-25 | 2013-11-27 | 黑龙江科技大学 | Preparation method for oxidized grapheme in large sheet |
| CN105293476A (en) * | 2015-11-16 | 2016-02-03 | 复旦大学 | Preparation method of large-size graphene oxide or graphene |
| US20180339906A1 (en) * | 2015-11-16 | 2018-11-29 | Fudan University | Preparation method for large-size graphene oxide or graphene |
| CN106564893A (en) * | 2016-11-10 | 2017-04-19 | 电子科技大学 | Hundred micron-order graphene oxide and preparation method thereof |
| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
| CN113860295A (en) * | 2021-10-20 | 2021-12-31 | 华南理工大学 | Method for preparing graphene oxide by using large-particle-size flake graphite |
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