CN115403038B - Preparation method of graphene oxide - Google Patents
Preparation method of graphene oxide Download PDFInfo
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- CN115403038B CN115403038B CN202211104584.8A CN202211104584A CN115403038B CN 115403038 B CN115403038 B CN 115403038B CN 202211104584 A CN202211104584 A CN 202211104584A CN 115403038 B CN115403038 B CN 115403038B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 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 61
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 230000002687 intercalation Effects 0.000 claims abstract description 27
- 238000009830 intercalation Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005119 centrifugation Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 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 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 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 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000007800 oxidant agent Substances 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012286 potassium permanganate 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
- 238000013019 agitation Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 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
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000354 decomposition reaction 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
- 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
- 239000003973 paint Substances 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
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (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 flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and filtering the second concentrated sulfuric acid to obtain a graphite intercalation mixed solution; mixing the graphite intercalation mixed solution with first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix; introducing mixed gas into the premix liquid, and simultaneously irradiating ultraviolet rays 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 graphene oxide. The mixed gas and ultraviolet rays are adopted as the oxidation means, so that the cost of the oxidant is reduced, the stability of the oxidant is effectively improved, and the oxidation degree of the graphene oxide product is controllable; by adopting the methods of centrifugation and ultrasonic dispersion, 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 physical and chemical characteristics, and can be applied to various fields such as pollutant adsorption, composite material preparation, corrosion prevention, energy sources and the like. 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, so that the method has certain danger. Meanwhile, the reaction process is not easy to control, and finally the graphene oxide obtained by separation shows a mixed state of high oxidation degree and small sheet diameter size. However, in practical application, different requirements on properties of graphene oxide are eliminated in different use scenes, for example, when the graphene oxide is used for forming polymers with chitosan and the like, the graphene oxide is required to have oxygen-containing groups as much as possible, and when the graphene oxide is used alone for adsorbing heavy metal ions in water, the graphene oxide is required to have fewer oxygen-containing functional groups; when the modified carbon fiber is used in the field of anticorrosive paint, the size of the sheet diameter is required to be larger, and when the modified carbon fiber is used for roughening modification, the size of the sheet diameter is required to be smaller; therefore, the existing production mode is difficult to meet the actual demands.
Disclosure of Invention
The application aims to provide a preparation method of graphene oxide, which aims to solve the technical problem that the preparation method in the prior art cannot effectively control the oxidation degree and the sheet diameter size of a graphene oxide finished product.
The embodiment of the invention provides a preparation method of graphene oxide, which comprises the following steps:
mixing flake graphite with first concentrated sulfur and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution;
Mixing the graphite intercalation mixed solution with first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix;
introducing mixed gas into the premix liquid, and irradiating ultraviolet rays to obtain a treatment liquid;
Mixing the treatment liquid with second deionized water, and 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%.
Optionally, the preset reaction temperature is 60-80 ℃.
Optionally, the mixed gas comprises 5-15% of ozone and 85-95% of oxygen by volume percent, and the introducing speed of the mixed gas is 5-20L/min.
Optionally, the wavelength of the ultraviolet rays is 185-254nm, the power of the irradiated ultraviolet rays is 20W, and the time of the irradiated ultraviolet rays is 0.5-2h.
Optionally, the mesh number of the crystalline flake graphite is 200-1000 mesh.
Optionally, the frequency of the centrifugation is 4000-8000r/min, and the centrifugation time is 3-15min;
The power of ultrasonic dispersion is 100-300W, and the time of 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 crystalline flake graphite is (40-60) mL/1 g.
Optionally, 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.
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 at least have 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 ultraviolet rays are adopted as the 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 a graphene oxide product is controllable; by adopting the methods of centrifugation and ultrasonic dispersion, the sheet diameter size of the graphene oxide product can be effectively controlled, and the operation is simple.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of graphene oxide prepared by the preparation method provided in example 1 of the present invention;
FIG. 4 is a Raman spectrum of graphene oxide prepared by the preparation method provided in example 1 of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided by example 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-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided in example 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 advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning 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. In case of conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. For example, room temperature may refer to a temperature in the range of 10 to 35 ℃.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for preparing graphene oxide, including the steps of:
s1, mixing the flake graphite with first concentrated sulfuric acid and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution.
S2, mixing the graphite intercalation mixed solution with the first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix.
And S3, introducing mixed gas into the premix liquid, and irradiating ultraviolet rays simultaneously to obtain the treatment liquid.
S4, mixing the treatment liquid with second deionized water, and precipitating to obtain a supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide.
The mass concentrations of the first concentrated sulfuric acid and the second concentrated sulfuric acid are 98%.
According to the preparation method of the graphene oxide, the problem that the oxidation degree and the sheet diameter size of a graphene oxide finished product cannot be effectively controlled can be effectively solved, the mixed gas and the ultraviolet rays are adopted as an oxidation means, the cost of the oxidant is reduced, the stability of the oxidant is effectively improved, heavy metal ions cannot be introduced into the oxidant, the oxidation is mild, the damage to the graphene oxide in the oxidation process can be effectively reduced, and therefore the oxidation degree of the graphene oxide product is controllable; by adopting the methods of centrifugation and ultrasonic dispersion, 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 combined 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, and then slowly convert carbon-carbon bonds to epoxy groups. Therefore, the graphite pre-oxidized by the concentrated sulfuric acid is oxidized in a deeper level, and meanwhile, the increase of oxygen-containing groups in the sheets gradually breaks the sheets, so that the size of the sheets is reduced.
Specifically, the mechanism of step S5 is: the micro bubbles generated in the water by the ultrasonic cavitation can release huge energy when rapidly collapsing, and can cause stripping and fragmentation among sheets when touching the graphene oxide sheets. The graphene oxide sheets have different specific gravities when the number of layers and the size of the graphene oxide sheets are different, and are more easily separated out during centrifugation when the number of layers is slightly more or the size is slightly larger, so that the characteristics can be utilized to screen the graphene oxide sheets in different size ranges. The ultrasonic and centrifugal combined action can better control the lamellar size of the graphene oxide.
As an alternative embodiment, the preset reaction temperature is 60-80 ℃.
The reason for controlling the preset temperature range is that: when water is mixed with concentrated sulfuric acid, a large amount of heat is released, and a temperature-adjusting device is required to keep the reaction environment at a certain temperature. When the temperature is too high, splashing is easy to occur, and when the temperature is too low, the reaction speed is slower, and the effective intercalation and weak oxidation effects on the crystalline flake graphite cannot be realized.
As an alternative implementation mode, the mixed gas comprises 5-15% of ozone and 85-95% of oxygen in percentage by volume, and the introducing speed of the mixed gas is 5-20L/min.
The effect of ozone and oxygen in the mixed gas is an oxidant, the effect of the ozone is to deeply oxidize the intercalated graphite, and the effect of the oxygen is to provide a protective atmosphere for the ozone to 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 capability 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 alternative embodiment, the wavelength of the ultraviolet rays is 185-254nm, the power of the ultraviolet rays is 20W, and the time of the ultraviolet rays is 0.5-2h.
The reason for controlling the ultraviolet power is that: the ultraviolet rays can decompose ozone into oxygen and active oxygen atoms, when the ultraviolet power is too high, the decomposition rate is too high, most active oxygen atoms are discharged without reaction, so that waste is caused, and when the power is too low, the concentration of the active oxygen atoms is low, the oxidation capability is insufficient, and the reaction time is too long.
The reason for controlling the ultraviolet irradiation time is that: the time of ultraviolet irradiation is synchronous with the gas mixture, and the oxidation of graphite is completed together.
As an alternative embodiment, the mesh number of the flake graphite is 200-1000 mesh.
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 flakes, so that the size of the flakes of the final finished graphene oxide is also affected.
As an alternative embodiment, the frequency of the centrifugation is 4000r/min, and the centrifugation time is 3-15min; the power of ultrasonic dispersion is 100-300W, and the time of ultrasonic dispersion is 2-4h.
The reason for controlling the frequency and time of centrifugation is that: 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 frequency and time of centrifugation can be utilized to screen the graphene oxide sheets with the size and the number of layers.
The reason for controlling the power and time of ultrasonic dispersion is that: the micro bubbles generated in the water by the ultrasonic cavitation can release huge energy when rapidly collapsing, and can cause stripping and fragmentation among sheets when touching the graphene oxide sheets. The time and power of ultrasonic dispersion can be utilized to further adjust the platelet 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 crystalline flake graphite is (40-60) mL:1g.
The reason for controlling the above ratio is that: the concentrated sulfuric acid can play a role in intercalation and pre-oxidation of the crystalline flake graphite, and when the proportion is low, the reaction rate is slow, the consumed time is long, and when the proportion is high, the waste of the concentrated sulfuric acid can be caused.
As an alternative 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 mixture is (1.5-2): 1.
The reason for controlling the volume ratio of the first deionized water to the graphite intercalation mixed solution is as follows: the deionized water reacts with the concentrated sulfuric acid to release heat, so that intercalation of the crystalline flake graphite can be accelerated, when the volume is smaller than a given value, the intercalation effect is poor, and when the volume is larger than the given value, waste is 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 for controlling the frequency and time of the first agitation is that: the uniform degree of the mixing of the raw materials is controlled by controlling the frequency and time of the first stirring, so that the intercalation effect of the concentrated sulfuric acid on the crystalline flake graphite is influenced.
As an alternative 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 for controlling the frequency and time of the second agitation is that: the reaction of deionized water and concentrated sulfuric acid is exothermic, and too slow or too short stirring speed can make the heat not be released, resulting in boiling and splashing of water.
The reason for controlling the addition rate of the first deionized water is that: too fast deionized water addition may cause splashing due to too high temperature, which affects safety, and too slow addition may affect intercalation effect on graphite.
The present application will be described in detail 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 sulfuric acid and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution.
Wherein:
The mesh number of the flake graphite is 200 meshes;
The mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98%;
the ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the crystalline flake graphite is 40 mL/1 g;
The volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 1:1;
the frequency of the first stirring is 150r/min, and the time of the first stirring is 0.5h.
S2, mixing the graphite intercalation mixed solution with the first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix.
Wherein:
the preset reaction temperature is 60 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed solution is 1.5:1, a step of;
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 premix liquid, and simultaneously irradiating ultraviolet rays to obtain the treatment liquid.
Wherein:
the mixed gas comprises 5% of ozone and 95% of oxygen by volume percent, and the introducing speed of the mixed gas is 5L/min;
the power of the irradiation of ultraviolet light was 20W, and the irradiation time of ultraviolet light was 0.5h.
S4, mixing the treatment solution with second deionized water, and precipitating to obtain supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain graphene oxide.
Wherein:
the frequency of centrifugation is 4000-8000r/min, and the time of centrifugation is 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 the flake graphite with first concentrated sulfuric acid and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution.
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%;
the ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the crystalline flake graphite is 50mL:1g;
the volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 2:3;
the frequency of the first stirring is 200r/min, and the time of the first stirring is 1h.
S2, mixing the graphite intercalation mixed solution with the first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix.
Wherein:
the preset reaction temperature is 60 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed solution is 2:1, a step of;
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 premix liquid, and simultaneously irradiating ultraviolet rays to obtain the treatment liquid.
Wherein:
The mixed gas comprises 10% of ozone and 90% of oxygen by volume percent, and the introducing speed of the mixed gas is 10L/min;
The power of the irradiation of ultraviolet light was 20W, and the irradiation time of ultraviolet light was 75min.
S4, mixing the treatment solution with second deionized water, and precipitating to obtain supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain graphene oxide.
Wherein:
the frequency of centrifugation is 4000-8000r/min, and the time of centrifugation is 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 the flake graphite with first concentrated sulfuric acid and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution.
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%;
The ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the crystalline flake graphite is 60 mL/1 g;
The volume ratio of the first concentrated sulfuric acid to the second concentrated sulfuric acid is 1:1;
The frequency of the first stirring is 300r/min, and the time of the first stirring is 1.5h.
S2, mixing the graphite intercalation mixed solution with the first deionized water under the condition of a preset reaction temperature, and stirring for the second time to obtain a premix.
Wherein:
the preset reaction temperature is 80 ℃;
the volume ratio of the first deionized water to the graphite intercalation mixed solution is 2:1, a step of;
the adding speed of the first deionized water is 40mL/min;
the frequency of the second stirring is 250r/min, and the time of the second stirring is 90min.
And S3, introducing mixed gas into the premix liquid, and simultaneously irradiating ultraviolet rays to obtain the treatment liquid.
Wherein:
the mixed gas comprises 15% of ozone and 85% of oxygen in percentage by volume, and the introducing speed of the mixed gas is 15L/min;
the power of the irradiation of ultraviolet light was 20W, and the irradiation time of ultraviolet light was 2 hours.
S4, mixing the treatment solution with second deionized water, and precipitating to obtain supernatant.
And S5, centrifuging, ultrasonically dispersing and drying the supernatant to obtain graphene oxide.
Wherein:
The frequency of centrifugation is 4000-8000r/min, and the time of centrifugation is 15min;
the power of ultrasonic dispersion is 250W, and the time of ultrasonic dispersion is 4h.
Comparative example
The comparative example adopts a classical improved Hummer method, and 500-mesh crystalline flake graphite and sodium nitrate are added into concentrated sulfuric acid and stirred at the speed of 200r/min to obtain a mixed solution. The mass ratio of the concentrated sulfuric acid to the crystalline flake graphite is 50:1, and the mass ratio of the crystalline flake graphite to the sodium nitrate is 1:1, the unit of the volume of the concentrated sulfuric acid is mL, the unit of the mass of the crystalline flake graphite and the sodium nitrate is gram, and the mass concentration of the concentrated sulfuric acid is 98%. Then adding potassium permanganate into the mixed solution, stirring for 90 minutes at0 ℃ with the mass ratio of potassium permanganate to sodium nitrate being 6:1, then raising the temperature to 35 ℃ and stirring for 2 hours. 960mL of pure water was added, the temperature was raised to 80℃and stirred for 1 hour, followed by 80mL of hydrogen peroxide, and the reaction solution was collected and filtered. And then carrying out suction filtration and drying on the supernatant to obtain graphene oxide powder.
Experimental example
The graphene oxide prepared by the preparation methods provided in examples 1-3 and comparative examples was subjected to detection of oxygen content and sheet diameter size, three samples were taken for each sample, labeled as samples 1-1,1-2 and 1-3, and so on, and measured separately. The specific results are shown in the following table.
Degree of oxidation: characterizing by adopting X-ray photoelectron spectroscopy;
sheet diameter size: the measurement was performed on a transmission electron microscope image.
From the above table, the preparation method of the embodiment 1-3 of the 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 sections of 15-25%, 25-35% and 35-45%, and the sheet diameter size can be controlled in three sections of 1-10 μm, 10-25 μm and 25-50 μm, so that the preparation method is convenient to apply. And the oxidation degree and the sheet diameter size of the graphene oxide prepared by the preparation method provided by comparative examples 1-N are obviously uncontrollable.
Description of the drawings:
Fig. 2 is an X-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided in embodiment 1 of the present invention, where it can be seen 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 by the embodiment 1 of the present invention, where the size of the graphene oxide is 39 μm;
FIG. 4 is a Raman spectrum of graphene oxide prepared by the preparation method provided by the embodiment 1 of the present invention, and as can be seen from the graph, the graphene oxide is a material prepared by the preparation method of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided by example 2 of the present invention, wherein 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 by the embodiment 2 of the present invention, where the size of the graphene oxide is 10 μm;
FIG. 7 is an X-ray photoelectron spectrum of graphene oxide prepared by the preparation method provided by the embodiment 3 of the present invention, wherein the oxygen content of the 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, where the size of the graphene oxide is 4 μm.
Finally, it is also 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. It is therefore intended that the following claims be interpreted as including the 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 modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. The preparation method of the graphene oxide is characterized by comprising the following steps of:
Mixing flake graphite with first concentrated sulfuric acid and second concentrated sulfuric acid, stirring for the first time, and filtering to obtain a graphite intercalation mixed solution;
Mixing the graphite intercalation mixed solution with first deionized water at the temperature of 60-80 ℃ and stirring for the second time to obtain a premix;
introducing mixed gas into the premix liquid, and irradiating ultraviolet rays to obtain a treatment liquid;
Mixing the treatment liquid with second deionized water, and precipitating to obtain supernatant;
Centrifuging, ultrasonically dispersing and drying the supernatant to obtain the graphene oxide;
Wherein:
The mesh number of the crystalline flake graphite is 200-1000 meshes, the mass concentration of the first concentrated sulfuric acid and the second concentrated sulfuric acid is 98%, the mixed gas comprises 5-15% of ozone and 85-95% of oxygen by volume percent, the introducing speed of the mixed gas is 5-20L/min, the wavelength of ultraviolet rays is 185-254nm, the power of irradiating ultraviolet rays is 20W, the time of irradiating ultraviolet rays is 0.5-2h,
The frequency of the centrifugation is 4000-8000r/min, and the time of the centrifugation is 3-15min;
The power of ultrasonic dispersion is 100-300W, and the time of ultrasonic dispersion is 2-4h;
The ratio of the total volume of the first concentrated sulfuric acid and the second concentrated sulfuric acid to the mass of the crystalline flake graphite is (40-60) mL 1g.
2. 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 mixture is (1.5-2): 1.
3. The method for preparing graphene oxide according to claim 1, wherein the frequency of the first stirring is 100-250r/min, and the time of the first stirring is 1-2h.
4. The method for preparing graphene oxide according to claim 1, wherein 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.
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