CN115403038A - Preparation method of graphene oxide - Google Patents
Preparation method of graphene oxide Download PDFInfo
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- CN115403038A CN115403038A CN202211104584.8A CN202211104584A CN115403038A CN 115403038 A CN115403038 A CN 115403038A CN 202211104584 A CN202211104584 A CN 202211104584A CN 115403038 A CN115403038 A CN 115403038A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- 230000002687 intercalation Effects 0.000 claims abstract description 27
- 238000009830 intercalation Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 10
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000002186 photoelectron spectrum Methods 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
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- 239000004917 carbon fiber Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000027734 detection of oxygen Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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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
- C01B32/198—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
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention particularly relates to a preparation method of graphene oxide, and belongs to the technical field of graphene material preparation. A preparation method of graphene oxide comprises the steps of mixing crystalline flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquid; mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature and carrying out second stirring to obtain a premixed solution; introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays at the same time to obtain a treatment liquid; mixing the treatment solution with second deionized water, and precipitating to obtain supernatant; and centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide. The mixed gas and ultraviolet rays are used as oxidation means, so that the cost of the oxidant is reduced, and the stability of the oxidant is effectively improved, so that the oxidation degree of the graphene oxide product is controllable; by adopting a centrifugal and ultrasonic dispersion method, the sheet diameter size of the graphene oxide product can be effectively controlled.
Description
Technical Field
The invention belongs to the technical field of graphene material preparation, and particularly relates to a preparation method of graphene oxide.
Background
Graphene oxide is a novel two-dimensional material, has many excellent physicochemical characteristics, and can be applied to various fields such as pollutant adsorption, composite material preparation, corrosion prevention and energy. At present, the production mode of graphene oxide is mainly an improved Hummer method, and the method needs to use a large amount of concentrated sulfuric acid and strong oxidants such as potassium permanganate, potassium ferrate and the like, and has certain danger. Meanwhile, the reaction process is not easy to control, and the finally separated graphene oxide is in a mixed state of high or low oxidation degree and large or small sheet diameter size. In practical application, however, different requirements on the properties of graphene oxide are eliminated in different use scenes, for example, when a polymer is formed with chitosan and the like, graphene oxide needs to have oxygen-containing groups as much as possible, and when graphene oxide is used alone to adsorb heavy metal ions in water, the graphene oxide needs to have a few oxygen-containing functional groups; when the carbon fiber roughening agent is used in the field of anticorrosive coatings, the sheet diameter size is required to be larger, and when the carbon fiber roughening agent is used for roughening and modifying carbon fibers, the sheet diameter size is required to be smaller; therefore, the existing production mode can hardly meet the actual requirement.
Disclosure of Invention
The application aims to provide a preparation method of graphene oxide, and the technical problem that the oxidation degree and the sheet diameter size of a graphene oxide finished product cannot be effectively controlled by the preparation method in the prior art is solved.
The embodiment of the invention provides a preparation method of graphene oxide, which comprises the following steps:
mixing the flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquor;
mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature and carrying out second stirring to obtain a premixed solution;
introducing mixed gas into the premixed solution, and irradiating ultraviolet rays to obtain a treatment solution;
mixing the treatment solution with second deionized water, and then precipitating to obtain a supernatant;
centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide;
wherein:
the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98 percent.
Optionally, the preset reaction temperature is 60-80 ℃.
Optionally, the mixed gas comprises 5-15% of ozone and 85-95% of oxygen by volume percentage, and the introduction speed of the mixed gas is 5-20L/min.
Optionally, the wavelength of the ultraviolet light is 185-254nm, the power for irradiating the ultraviolet light is 20W, and the time for irradiating the ultraviolet light is 0.5-2h.
Optionally, the mesh number of the flake graphite is 200-1000 meshes.
Optionally, the centrifugation frequency is 4000-8000r/min, and the centrifugation time is 3-15min;
the power of the ultrasonic dispersion is 100-300W, and the time of the ultrasonic dispersion is 2-4h.
Optionally, the ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the flake graphite is (40-60) mL:1g.
Optionally, a volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is (0.5-1): 1, and a volume ratio of the first deionized water to the graphite intercalation mixed solution is (1.5-2): 1.
optionally, the frequency of the first stirring is 100-250r/min, and the time of the first stirring is 1-2h.
Optionally, the frequency of the second stirring is 100-300r/min, the time of the second stirring is 30-60min, and the adding speed of the first deionized water is 15-40mL/min.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the preparation method of the graphene oxide, provided by the embodiment of the invention, the mixed gas and the ultraviolet rays are used as an oxidation means, so that the cost of the oxidant is reduced, the stability of the oxidant is effectively improved, heavy metal ions are not introduced into the oxidant, the oxidation is mild, the damage to the graphene oxide in the oxidation process can be effectively reduced, and the oxidation degree of the graphene oxide product is controllable; by adopting the centrifugal and ultrasonic dispersion method, the sheet diameter size of the graphene oxide product can be effectively controlled, and the operation is simple.
The above description is only an overview of the technical solutions of the present invention, and the present invention can be implemented in accordance with the content of the description so as to make the technical means of the present invention more clearly understood, and the above and other objects, features, and advantages of the present invention will be more clearly understood.
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 are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the invention;
fig. 2 is an X photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention;
fig. 3 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention;
fig. 4 is a raman spectrum of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention;
fig. 5 is an X photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 2 of the present invention;
fig. 6 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in embodiment 2 of the present invention;
fig. 7 is an X photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 3 of the present invention;
fig. 8 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in embodiment 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. For example, room temperature may refer to a temperature in the interval of 10 to 35 ℃.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, a method for preparing graphene oxide is provided, which includes the following steps:
s1, mixing flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquor.
And S2, mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature, and stirring for the second time to obtain a premixed solution.
And S3, introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays at the same time to obtain the treatment liquid.
And S4, mixing the treatment solution with second deionized water, and then precipitating to obtain a supernatant.
S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide.
The mass concentration of the first concentrated sulfuric acid and the mass concentration of the second concentrated sulfuric acid are both 98%.
The preparation method of the graphene oxide can effectively solve the problem that the oxidation degree and the sheet diameter size of a graphene oxide finished product cannot be effectively controlled, reduces the cost of the oxidant by adopting the mixed gas and ultraviolet rays as oxidation means, effectively improves the stability of the oxidant, does not introduce heavy metal ions, is mild in oxidation, can effectively reduce the damage to the graphene oxide in the oxidation process, and thus enables the oxidation degree of the graphene oxide product to be controllable; by adopting a centrifugal and ultrasonic dispersion method, the sheet diameter size of the graphene oxide product can be effectively controlled, and the operation is simple.
Specifically, the mechanism of step S3 is: when ozone is used in conjunction with ultraviolet radiation, the ultraviolet light can decompose the ozone into oxygen and reactive oxygen atoms that first oxidize defective sites, such as hydroxyl groups to carboxyl groups, followed by slow conversion of carbon-carbon bonds to epoxy groups. So that the graphite pre-oxidized by concentrated sulfuric acid is further oxidized, and meanwhile, the sheets are gradually crushed and the size of the sheets is reduced due to the increase of oxygen-containing groups in the sheets.
Specifically, the mechanism of step S5 is: the micro bubbles generated in water by ultrasonic cavitation release huge energy when rapidly collapsing, and can cause peeling and breaking between sheet layers when touching graphene oxide sheets. When the number of the graphene oxide sheets is different from the size of the graphene oxide sheets, the graphene oxide sheets have different specific gravities, and when the number of the graphene oxide sheets is slightly more or the size of the graphene oxide sheets is slightly larger, the graphene oxide sheets are more easily separated out during centrifugation, so that the graphene oxide sheets in different size ranges can be screened by utilizing the characteristic. The combined action of the ultrasonic wave and the centrifugation can better control the size of the graphene oxide sheet layer.
As an alternative embodiment, the predetermined reaction temperature is 60 to 80 ℃.
The reason for controlling the preset temperature range is: when water is mixed with concentrated sulfuric acid, a large amount of heat is released, and equipment for adjusting the temperature is required to keep the reaction environment at a certain temperature. When the temperature is too high, splashing is easily caused, and when the temperature is too low, the reaction speed is slow, so that effective intercalation and weak oxidation effects on the crystalline flake graphite cannot be realized.
As an optional implementation mode, the mixed gas comprises 5-15% of ozone and 85-95% of oxygen by volume percentage, and the introduction speed of the mixed gas is 5-20L/min.
The function of ozone and oxygen in the mixed gas is oxidizing agent, the function of ozone is to carry out deep oxidation on the intercalated graphite, and the function of oxygen is to provide protective atmosphere for ozone and prevent reduction by other substances.
The reason for controlling the ozone volume percentage range is that: when the concentration of ozone is low, the oxidation capacity to graphite is poor, the reaction process is slow, and when the concentration is too high, part of ozone is discharged without reaction, so that waste is caused.
As an optional embodiment, the wavelength of the ultraviolet rays is 185-254nm, the power of irradiating the ultraviolet rays is 20W, and the time of irradiating the ultraviolet rays is 0.5-2h.
The reason for controlling the ultraviolet power is: when the power of the ultraviolet light is too low, the concentration of the active oxygen atoms is low, the oxidizing power is insufficient, and the reaction time is too long.
The reason why the ultraviolet irradiation time is controlled is that: the time of ultraviolet irradiation and the introduction of the mixed gas are synchronous, and the oxidation of the graphite is completed together.
As an alternative embodiment, the mesh number of the crystalline flake graphite is 200-1000 meshes.
The reason for controlling the mesh number of the flake graphite is that: the mesh number of the crystalline flake graphite corresponds to the size of the flake layer, so that the flake size of the final graphene oxide product is also influenced.
As an alternative embodiment, the frequency of the centrifugation is 4000r/min, and the time of the centrifugation is 3-15min; the power of the ultrasonic dispersion is 100-300W, and the time of the ultrasonic dispersion is 2-4h.
The reason for controlling the frequency and time of centrifugation is: when the number of layers and the size of the graphene oxide sheets are different, the graphene oxide sheets have different specific gravities, and the graphene oxide sheets with different sizes and the number of layers can be screened by using the centrifugal frequency and time.
The reason for controlling the power and time of the ultrasonic dispersion is: the micro-bubbles generated in water by ultrasonic cavitation release huge energy when being rapidly collapsed, and can cause the stripping and the breaking between sheet layers when contacting graphene oxide sheets. The time and power of ultrasonic dispersion can be used to further adjust the sheet size of graphene oxide.
As an alternative embodiment, the ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the flake graphite is (40-60) mL:1g.
The reason for controlling the above ratio is that: the concentrated sulfuric acid can perform intercalation and preoxidation functions on flake graphite, and when the proportion is low, the reaction rate is low, the consumed time is long, and when the proportion is high, the waste of the concentrated sulfuric acid can be caused.
In an optional embodiment, the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is (0.5-1): 1, and the volume ratio of the first deionized water to the graphite intercalation mixed liquid is (1.5-2): 1.
the reason for controlling the volume ratio of the first deionized water to the graphite intercalation mixed liquid is as follows: the deionized water reacts with concentrated sulfuric acid to release heat after being added, so that the intercalation effect on the scale graphite can be accelerated, when the volume ratio is smaller than a given value, the intercalation effect is poor, and when the volume ratio is larger than the given value, waste can be caused.
As an alternative embodiment, the frequency of the first stirring is 100-250r/min, and the time of the first stirring is 1-2h.
The reason why the frequency and time of the first stirring are controlled is that: the uniform degree of mixing of the raw materials is controlled by controlling the frequency and time of the first stirring, so that the intercalation effect of concentrated sulfuric acid on the flake graphite is influenced.
As an optional embodiment, the frequency of the second stirring is 100-300r/min, the time of the second stirring is 30-60min, and the adding speed of the first deionized water is 15-40mL/min.
The reason why the frequency and time of the second stirring are controlled is that: the reaction of deionized water and concentrated sulfuric acid gives off heat, and too slow stirring speed or too short stirring time can make the heat release too late, resulting in that the water is boiled and splashed.
The reason why the addition rate of the first deionized water is controlled is that: the splashing of deionized water caused by too high temperature can be caused by too fast addition of the deionized water, the safety is influenced, and the intercalation effect on graphite is influenced by too slow addition of the deionized water.
The present application will be described in detail below with reference to examples, comparative examples, and experimental data.
Example 1
The embodiment provides a preparation method of graphene oxide, which comprises the following steps:
s1, mixing the flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquid.
Wherein:
the mesh number of the crystalline flake graphite is 200 meshes;
the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98%;
the mass ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the scale graphite is 40mL;
the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 1;
the frequency of the first stirring was 150r/min and the time of the first stirring was 0.5h.
And S2, mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature, and stirring for the second time to obtain a premixed solution.
Wherein:
the preset reaction temperature is 60 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed liquid is 1.5:1;
the adding speed of the first deionized water is 20mL/min;
the frequency of the second stirring is 100r/min, and the time of the second stirring is 30min.
And S3, introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays to obtain the treatment liquid.
Wherein:
the mixed gas comprises 5 percent of ozone and 95 percent of oxygen by volume percentage, and the feeding speed of the mixed gas is 5L/min;
the power of ultraviolet irradiation was 20W, and the time of ultraviolet irradiation was 0.5h.
And S4, mixing the treatment solution with second deionized water, and precipitating to obtain a supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide.
Wherein:
centrifuging at 4000-8000r/min for 5min;
the power of ultrasonic dispersion is 150W, and the time of ultrasonic dispersion is 2h.
Example 2
The embodiment provides a preparation method of graphene oxide, which comprises the following steps:
s1, mixing flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquor.
Wherein:
the mesh number of the flake graphite is 500 meshes;
the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98 percent;
the mass ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the scale graphite is 50mL;
the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 2;
the frequency of the first stirring was 200r/min and the time of the first stirring was 1h.
And S2, mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature, and stirring for the second time to obtain a premixed solution.
Wherein:
the preset reaction temperature is 60 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed liquid is 2:1;
the adding speed of the first deionized water is 30mL/min;
the frequency of the second stirring is 200r/min, and the time of the second stirring is 60min.
And S3, introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays at the same time to obtain the treatment liquid.
Wherein:
the mixed gas comprises 10 percent of ozone and 90 percent of oxygen by volume percentage, and the feeding speed of the mixed gas is 10L/min;
the power of the ultraviolet irradiation was 20W, and the time of the ultraviolet irradiation was 75min.
And S4, mixing the treatment solution with second deionized water, and precipitating to obtain a supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide.
Wherein:
centrifuging at 4000-8000r/min for 10min;
the power of ultrasonic dispersion is 200W, and the time of ultrasonic dispersion is 3h.
Example 3
The embodiment provides a preparation method of graphene oxide, which comprises the following steps:
s1, mixing flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquor.
Wherein:
the mesh number of the flake graphite is 1000 meshes;
the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98 percent;
the mass ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the scale graphite is 60mL;
the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 1;
the frequency of the first stirring was 300r/min and the time of the first stirring was 1.5h.
And S2, mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature, and stirring for the second time to obtain a premixed solution.
Wherein:
the preset reaction temperature is 80 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed liquid is 2:1;
the adding speed of the first deionized water is 40mL/min;
the frequency of the second stirring was 250r/min and the time of the second stirring was 90min.
And S3, introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays at the same time to obtain the treatment liquid.
Wherein:
the mixed gas comprises 15 percent of ozone and 85 percent of oxygen by volume percentage, and the feeding speed of the mixed gas is 15L/min;
the power of ultraviolet irradiation was 20W, and the time of ultraviolet irradiation was 2 hours.
And S4, mixing the treatment solution with second deionized water, and then precipitating to obtain a supernatant.
S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide.
Wherein:
centrifuging at 4000-8000r/min for 15min;
the power of ultrasonic dispersion is 250W, and the time of ultrasonic dispersion is 4h.
Comparative example
In the comparative example, a classical improved Hummer method is adopted, crystalline flake graphite with 500 meshes and sodium nitrate are added into concentrated sulfuric acid, and the mixture is obtained after stirring at the speed of 200 r/min. The volume of the concentrated sulfuric acid and the mass ratio of the crystalline flake graphite are respectively 50:1, the volume of concentrated sulfuric acid is mL, the mass of crystalline flake graphite and sodium nitrate is gram, and the mass concentration of concentrated sulfuric acid is 98%. Subsequently, potassium permanganate was added to the mixed solution in a mass ratio of potassium permanganate to sodium nitrate of 6. 960mL of pure water was added, the temperature was raised to 80 ℃ and stirred for 1 hour, followed by addition of 80mL of hydrogen peroxide, and the reaction solution was collected and filtered. And then, filtering and drying the supernatant to obtain graphene oxide powder.
Examples of the experiments
The graphene oxide prepared by the preparation methods provided in examples 1 to 3 and comparative example was subjected to detection of oxygen content and sheet diameter size, each sample was taken in triplicate, and labeled as samples 1 to 1,1 to 2 and 1 to 3, and so on, and measured separately. Specific results are shown in the following table.
Degree of oxidation: performing characterization by adopting X photoelectron spectroscopy;
the size of the sheet diameter is as follows: the measurement was performed on a transmission electron micrograph.
From the above table, the preparation method of the embodiments 1 to 3 of the present application can effectively control the oxidation degree and the sheet diameter size of the graphene oxide product, the oxidation degree can be controlled in three ranges of 15 to 25%, 25 to 35%, and 35 to 45%, and the sheet diameter size can be controlled in three ranges of 1 to 10 μm, 10 to 25 μm, and 25 to 50 μm, which is convenient for application. And the oxidation degree and the sheet diameter size of the graphene oxide prepared by the preparation method provided by the comparative examples 1-N are obviously uncontrollable.
Description of the drawings:
fig. 2 is an X photoelectron energy spectrum of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention, and it can be known that the oxygen content of graphene oxide is 22%;
FIG. 3 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in example 1 of the present invention, from which the graphene oxide has a sheet diameter of 39 μm;
fig. 4 is a raman spectrum of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention, and it can be seen that the material prepared by the preparation method of the present invention is graphene oxide;
fig. 5 is an X photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 2 of the present invention, and it can be known from the X photoelectron spectrum that the oxygen content of graphene oxide is 33%;
FIG. 6 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in example 2 of the present invention, from which the sheet diameter size of graphene oxide is 10 μm;
fig. 7 is an X photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 3 of the present invention, and it can be seen from the graph that the oxygen content of graphene oxide is 39%;
fig. 8 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in embodiment 3 of the present invention, from which the graphene oxide has a sheet diameter size of 4 μm.
Finally, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of graphene oxide is characterized by comprising the following steps:
mixing flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and then filtering the second concentrated sulfuric acid to obtain graphite intercalation mixed liquor;
mixing the graphite intercalation mixed solution with first deionized water at a preset reaction temperature and carrying out second stirring to obtain a premixed solution;
introducing mixed gas into the premixed liquid, and irradiating ultraviolet rays at the same time to obtain a treatment liquid;
mixing the treatment solution with second deionized water and then precipitating to obtain supernatant;
centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide;
wherein:
the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98 percent.
2. The method according to claim 1, wherein the predetermined reaction temperature is 60 to 80 ℃.
3. The preparation method of graphene oxide according to claim 1, wherein the mixed gas comprises 5-15% of ozone and 85-95% of oxygen by volume percentage, and the introduction speed of the mixed gas is 5-20L/min.
4. The method according to claim 1, wherein the wavelength of the ultraviolet light is 185 to 254nm, the power of the ultraviolet light irradiation is 20W, and the time of the ultraviolet light irradiation is 0.5 to 2 hours.
5. The method for preparing graphene oxide according to claim 1, wherein the flake graphite has a mesh size of 200 to 1000 mesh.
6. The method for preparing graphene oxide according to claim 1, wherein the centrifugation frequency is 4000-8000r/min and the centrifugation time is 3-15min;
the power of the ultrasonic dispersion is 100-300W, and the time of the ultrasonic dispersion is 2-4h.
7. The method according to claim 1, wherein a ratio of a total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to a mass of the flake graphite is (40-60) mL:1g.
8. The method for preparing graphene oxide according to claim 1, wherein the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is (0.5-1): 1, and the volume ratio of the first deionized water to the graphite intercalation mixed solution is (1.5-2): 1.
9. the method according to claim 1, wherein the first stirring frequency is 100 to 250r/min, and the first stirring time is 1 to 2 hours.
10. The method for preparing graphene oxide according to claim 1, wherein the frequency of the second stirring is 100 to 300r/min, the time of the second stirring is 30 to 60min, and the adding speed of the first deionized water is 15 to 40mL/min.
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