CN110697698B - Graphene oxide and preparation method thereof - Google Patents
Graphene oxide and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of graphene, in particular to graphene oxide and a preparation method thereof. The preparation method of the graphene oxide comprises the following steps: reacting graphite, acid solution and hydrogen peroxide at 75-85 ℃ for 25-45 minutes to obtain acid intercalated graphite; mixing concentrated sulfuric acid and acid intercalated graphite, adding a strong oxidant for reaction, and removing acid to obtain graphene oxide; wherein the acid solution comprises concentrated sulfuric acid and phosphoric acid, or the acid solution comprises concentrated sulfuric acid and phosphorus pentoxide. According to the preparation method of the graphene oxide, intercalation and oxidation are carried out separately, graphite sheets are peeled off in the intercalation step, and the final graphene oxide single sheet can be peeled off under a softer mechanical acting force, so that the graphene oxide with a larger radial size is obtained; maximum is millimeter-sized graphene oxide; the single layer rate is higher. According to the preparation method of the graphene oxide, nitrate ions are not introduced in the whole intercalation and oxidation processes, and the risk of explosion is reduced.
Description
Technical Field
The application relates to the field of graphene, in particular to graphene oxide and a preparation method thereof.
Background
At present, a plurality of methods for preparing graphene oxide exist, such as: mechanical exfoliation, SiC epitaxial growth, Chemical Vapor Deposition (CVD), liquid phase ultrasonic cleavage, chemical redox, electrochemical cleavage, and intercalation expansion.
The mainstream of the existing method for preparing graphene oxide is a Hummers series method, which is mainly used for preparing the graphene oxide by nitric acid or nitrate-containing salt, concentrated sulfuric acid, potassium permanganate and the like according to a certain proportion and through strict temperature control.
Disclosure of Invention
The embodiment of the application aims to provide graphene oxide and a preparation method thereof. The preparation method aims to solve the problem of a preparation method of graphene oxide under mild conditions.
The first aspect of the present application provides a method for preparing graphene oxide, where the method for preparing graphene oxide includes:
reacting graphite, acid solution and hydrogen peroxide at 75-85 ℃ for 25-45 minutes to obtain acid intercalated graphite;
mixing concentrated sulfuric acid and acid intercalated graphite, adding a strong oxidant for reaction, and removing acid to obtain graphene oxide;
wherein the acid solution comprises concentrated sulfuric acid and phosphoric acid, or the acid solution comprises concentrated sulfuric acid and phosphorus pentoxide; the mass ratio of the strong oxidant to the graphite is greater than or equal to 3.
According to the preparation method of the graphene oxide, the acid intercalated graphite is prepared firstly, and then the acid intercalated graphite is oxidized. Intercalation and oxidation are separately carried out, so that multilayer acid is intercalated between graphite sheets, the graphite sheets are peeled off in the intercalation step, and the final graphene oxide can be separated under a softer mechanical action force, so that the graphene oxide with larger radial dimension is obtained; maximum is millimeter-sized graphene oxide; the single layer rate is higher. According to the preparation method of the graphene oxide, nitrate ions are not introduced in the whole intercalation and oxidation processes, and the risk of explosion is reduced.
In some embodiments of the first aspect of the present application, the method of preparing graphene oxide further comprises: and stirring the graphene oxide to strip and delaminate the graphene oxide.
Stirring the graphene oxide to peel and delaminate the graphene oxide to obtain graphene oxide with larger radial size.
In some embodiments of the first aspect of the present application, the step of removing the acid to obtain graphene oxide comprises:
and (3) removing acid by pressure filtration, terminating the oxidation reaction by using hydrogen peroxide, and washing by using water to obtain the graphene oxide.
In some embodiments of the first aspect of the present disclosure, the hydrogen peroxide is present in an amount of 30-65% by weight.
The mass fraction of the hydrogen peroxide is 30-65%, the hydrogen peroxide and the graphite can be fully utilized, and the waste and the transitional consumption of raw materials are avoided.
In some embodiments of the first aspect of the present disclosure, the mass ratio of graphite to concentrated sulfuric acid in the acid solution is from 1:18 to 1: 10.
The mass ratio of the graphite to the concentrated sulfuric acid in the acid solution is 1: 18-1: 10, and more concentrated sulfuric acid can be intercalated between graphite sheets under the action of phosphoric acid.
In some embodiments of the first aspect of the present disclosure, the mass ratio of graphite to phosphoric acid or phosphorous pentoxide in the acid solution is 1:1.2 to 1: 0.8.
Phosphoric acid or phosphorus pentoxide can be fully utilized, and the waste and the transitional consumption of raw materials are avoided.
In some embodiments of the first aspect of the present disclosure, the mass ratio of graphite to strong oxidant is 1:4 to 1:3.
The mass ratio of the graphite to the strong oxidant is 1: 4-1: 3, the using amount of the strong oxidant is only 3-4 times of the mass of the graphite, namely, the oxidation degree is complete, and the utilization rate of the strong oxidant can be increased.
In some embodiments of the first aspect of the present application, the strong oxidizing agent comprises potassium permanganate and/or potassium ferrate.
In some embodiments of the first aspect of the present application, the graphite is flake graphite.
Flake graphite is used as a raw material, so that the finally obtained graphene oxide has larger lamellar size.
Graphene oxide, which is prepared by the preparation method of graphene oxide; the radial dimension of the graphene oxide is greater than 400 μm.
The graphene oxide provided by the application has a large size, the size can reach 400 micrometers or even millimeter level, and the graphene oxide aqueous solution is in an ordered state in a microcosmic manner.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a raman spectrum of graphene oxide prepared in example 1.
Fig. 2 is a scanning electron microscope image of graphene oxide prepared in example 1.
Fig. 3 shows a scanning electron micrograph of graphene oxide prepared in example 3.
Fig. 4 shows a scanning electron micrograph of graphene oxide prepared in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A Hummers series method is mainly characterized in that oxidized graphene is prepared by nitric acid or nitrate-containing salt, concentrated sulfuric acid and potassium permanganate under the condition of strictly controlling the temperature; has the following disadvantages:
the Hummers method consumes a large amount of potassium permanganate, which is 8 to 12 times or even higher than that of graphite;
the Hummers method mainly aims at graphite powder, the worse the graphite crystal structure and the smaller the size, the more thorough the oxidation, and by combining an ultrasonic means, the monolayer graphene oxide with the lamella smaller than 50 micrometers can be obtained;
the Hummers process introduces nitrate and requires strict temperature control, otherwise there is a risk of explosion.
The prior art also describes that the method for bulk graphene oxide comprises the following steps: the intercalation and oxidation are separated, the raw material is made of graphite paper (formed by rolling expanded graphite), the graphite paper is firstly intercalated in concentrated sulfuric acid (98%) by an electrochemical means, then the graphite paper is taken out, partial interlaminar acid is extruded, and then the graphite paper is placed in 50% sulfuric acid solution for electrochemical oxidation.
The method has the advantages that strong oxidant is not needed to be added, but the production efficiency is relatively low, the raw material graphite paper is relatively expensive, more importantly, a large amount of hydrogen can be generated by the negative electrode in the oxidation and intercalation processes, and the method has extremely high potential safety hazard and cannot be used for mass production.
CN201510777025.7 discloses a method for preparing large-size graphene oxide or graphene, which includes intercalating graphite with an intercalation agent, expanding intercalated graphite with an expansion agent, oxidizing the intercalated graphite with an oxidant, reacting graphite and the intercalation agent at 0-130 ℃ for 5 minutes-48 hours while stirring, adding the graphite and the intercalation agent into the expansion agent, and soaking at 0-80 ℃ for 1 hour-7 days to fully release interlayer space, thereby obtaining a graphene aggregate. The process of preparing the large-size graphene oxide by the preparation method is complex in steps and long in time consumption, the intercalation and the expansion are carried out in steps, washing treatment is required after each step is finished, the proportion of waste liquid is greatly increased in the preparation process, and due to the introduction of the expanding agent, the preparation cost is greatly increased, so that the preparation method is not beneficial to subsequent large-scale low-cost preparation of graphene.
According to the preparation method of the graphene oxide, the expanding agent is not introduced, the preparation process is simple, and the problems can be improved to a certain extent.
The following specifically describes graphene oxide and a method for preparing the same in the embodiments of the present application.
The preparation method of the graphene oxide comprises the following steps:
reacting graphite, acid solution and hydrogen peroxide at 75-85 ℃ for 25-45 minutes to obtain acid intercalated graphite;
mixing concentrated sulfuric acid and acid intercalated graphite, adding a strong oxidant for reaction, and removing acid to obtain graphene oxide;
wherein the acid solution comprises concentrated sulfuric acid and phosphoric acid, or concentrated sulfuric acid and phosphorus pentoxide; the mass ratio of the strong oxidant to the graphite is greater than or equal to 3.
According to the preparation method of the graphene oxide, the acid intercalated graphite is prepared firstly, and then the acid intercalated graphite is oxidized. Intercalation and oxidation are separately carried out, so that multilayer acid is intercalated between graphite sheets, the graphite sheets are peeled off in the intercalation step, and the final graphene oxide can be separated under a softer mechanical action force, so that the graphene oxide with larger radial dimension is obtained; maximum is millimeter-sized graphene oxide; the single layer rate is higher.
The flake graphite with very large size can be selected, and the flake graphite with about 10 meshes can be thoroughly oxidized and stripped by the method.
In addition, according to the preparation method of the graphene oxide, nitrate ions are not introduced in the whole intercalation and oxidation process, and the risk of explosion is reduced.
In the examples of the present application, the graphite is flake graphite. More acid can be inserted in the intercalation process, so the oxidation process is relatively thorough, the flake graphite is selected to ensure that the oxidation is still thorough, and in addition, the flake graphite can obtain large-size graphene oxide; the scale graphite can obtain the graphene oxide with the radial size of more than 400 mu m.
In other embodiments of the present application, graphite powder or the like may be used as the graphite.
In the present application, the acid solution includes concentrated sulfuric acid and phosphoric acid, or the acid solution includes concentrated sulfuric acid and phosphorus pentoxide. The mass fraction of the concentrated sulfuric acid is more than or equal to 98 percent.
Phosphoric acid or phosphorus pentoxide can enable concentrated sulfuric acid to enter between the graphite sheet layers, and phosphoric acid or phosphorus pentoxide can enable a large amount of concentrated sulfuric acid to enter between the graphite sheet layers to form acid intercalated graphite.
The mass ratio of the graphite to the concentrated sulfuric acid in the acid solution is (1: 18-1): 10. for example, 1:10, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, or 1:18, etc. In other embodiments of the present application, the mass ratio of graphite to concentrated sulfuric acid in the acid solution may be greater than 1:12, or less than 1: 18.
In the present application, the mass ratio of the concentrated sulfuric acid to the phosphoric acid in the acid solution is 1:18 to 1.5:18, or the mass ratio of the concentrated sulfuric acid to the phosphorus pentoxide in the acid solution is 1:18 to 1.5:18, and may be, for example, 1:18, 1.2:18, 1.3:18, or 1.5: 18.
In some embodiments of the present disclosure, the mass fraction of the hydrogen peroxide is 30-65%, for example, 30%, 35%, 38%, 40%, 45%, 48%, 52%, 58%, 60%, or 65%. In other embodiments of the present application, the concentration of the hydrogen peroxide may also be less than 30% or greater than 65%, for example, 25% or 70%.
In the present application, the mass ratio of the strong oxidant to the graphite is 3 or more; if the mass of the strong oxidant is small compared to the mass of graphite, incomplete oxidation of graphite may result.
In some embodiments of the present application, the mass ratio of graphite to strong oxidant is 1: 4-1: 3. for example, it may be 1:4, 1:3.5, 1:3.7, 1:3.8, or 1:3, the mass ratio of the graphite to the strong oxidant is 1: 4-1: 3, the utilization rate of the strong oxidant is higher; the mass ratio of graphite to strong oxidant can also be less than 1:4 or greater than 1:3 if utilization is not a concern.
In some embodiments of the present application, the strong oxidizing agent comprises potassium permanganate and/or potassium ferrate.
In other words, strong oxidants include potassium permanganate; alternatively, the strong oxidizing agent comprises potassium ferrate; or strong oxidizers include potassium permanganate and potassium ferrate.
In some other embodiments of the present application, the strong oxidizing agent may also be selected from potassium dichromate, chromium trioxide, and the like.
Illustratively, concentrated sulfuric acid is mixed with the acid intercalated graphite and then reacted with a strong oxidizing agent, the amount of concentrated sulfuric acid being 10 to 20 times, for example, 10 times, 12 times, 15 times, 18 times, or 20 times the mass of the graphite.
In some embodiments of the present application, after the step of mixing concentrated sulfuric acid with acid intercalated graphite, adding a strong oxidant to react, and then removing the acid to obtain graphene oxide, the method further includes: stirring the graphene oxide to strip and delaminate the graphene oxide.
For example, the aqueous graphite oxide solution is placed in a high speed stirrer or an emulsifying machine and is peeled off by the energy of the high speed stirring.
In some other embodiments of the present application, a magnetic stirrer, a blending device, an oscillator, or the like may be used to stir the graphene oxide to be exfoliated or layered.
Further, in some embodiments of the present application, the step of removing the acid to obtain the graphene oxide comprises:
and (3) removing acid by pressure filtration, terminating the oxidation reaction by using hydrogen peroxide, and washing by using water to obtain the graphene oxide. In other words, the graphene oxide solution is subjected to filter pressing to remove acid in the graphene oxide, then water is added for dilution, a certain amount of hydrogen peroxide is added to stop the oxidation reaction, and the solution is repeatedly centrifuged and cleaned to be in a deionized state to obtain a pure graphite oxide aqueous solution.
The preparation method of the graphene oxide provided by the embodiment of the application at least has the following advantages:
1) graphite intercalation and graphite oxide are separately carried out, phosphoric acid or phosphorus pentoxide and sulfuric acid are used for co-intercalation, so that multilayer acid is intercalated between graphite flake layers, the graphite flake layers are directly peeled off in the intercalation process, and finally graphene oxide is peeled off conveniently.
2) Nitrate ions are not introduced in the preparation method of the graphene oxide, so that the risk of explosion is reduced; and electrochemical oxidation is not needed in the preparation process, hydrogen is not generated, and the risk of explosion is avoided.
3) In the intercalation step, the graphite sheet layer is opened, the strong oxidant directly acts on the graphite sheet layer, the utilization rate of the strong oxidant is high, the oxidation is thorough, and the oxidation of the large sheet layer can be completed when the mass of the strong oxidant is 3 to 4 times of the graphite amount.
4) The preparation method of the graphene oxide provided by the embodiment of the application is not limited to graphite powder, large-size flake graphite can be adopted, and the flake graphite with the particle size of about 10 meshes can be thoroughly oxidized and stripped by the method provided by the application.
5) The graphene oxide obtained by the preparation method of the graphene oxide provided by the embodiment of the application has high single-layer rate and large radial size, and is maximum millimeter-sized graphene oxide.
6) The graphene oxide aqueous solution obtained by the preparation method of the graphene oxide provided by the embodiment of the application is microscopically ordered and macroscopically disordered, and can be in a liquid crystal state by adding the liquid crystal inducer.
The application also provides graphene oxide, wherein the graphene is prepared by the preparation method of the graphene oxide; the radial dimension of the graphene oxide is greater than 400 μm.
The graphene oxide provided by the application has a large size, the size can reach 400 micrometers or even millimeter level, and the graphene oxide aqueous solution is in an ordered state in a microcosmic manner.
In addition, the graphene oxide provided by the application has a large size, has good heat conduction and electric conduction performance, and can be used for preparing heat conduction materials or electric conduction materials.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides graphene oxide, which is mainly prepared through the following steps:
adding 15 parts of concentrated sulfuric acid into 1 part of flake graphite, fully and uniformly stirring, adding 1 part of phosphorus pentoxide solid powder, fully and uniformly stirring, adding 1 part of hydrogen peroxide, and sealing. Placing the graphite flake in an environment of 80 ℃, fully stirring and reacting for 10 minutes, then standing for 20 minutes to ensure that acid is fully inserted into the graphite flake, and the volume of the graphite flake is fully expanded to be about 100 times of the original volume.
Placing the intercalated graphite in a room temperature environment, adding 15 parts of concentrated sulfuric acid, fully stirring to restore the fluidity, slowly adding 4 parts of potassium permanganate, and fully stirring to react for 2 hours; and removing redundant acid by using a filter pressing device, adding 30 parts of deionized water, then adding a certain amount of hydrogen peroxide until no bubbles are generated in the whole system, enabling the whole liquid to be in a golden yellow state, and then fully centrifugally cleaning to be in a system neutral state to obtain the large graphene oxide sheets which are thoroughly oxidized.
And (3) placing the cleaned graphene oxide water mixed system in a high-speed stirrer, stirring for 5 minutes at the rotating speed of 5000 revolutions, and stripping the graphene oxide sheets into a single-layer graphene oxide water dispersion liquid by utilizing the rapid impact action of water molecules and the graphene oxide sheets.
The raman spectrum of the graphene oxide prepared in this example is shown in fig. 1. Fig. 2 shows a scanning electron micrograph of graphene oxide prepared in example 1. It can be seen that the graphene oxide prepared in example 1 has a size of the order of millimeters.
Example 2
The present embodiment provides a graphene oxide, and the difference between the preparation method of the graphene oxide provided in the present embodiment and the preparation method of embodiment 1 is that:
during the intercalation process, 1 part of concentrated phosphoric acid is added, and the intercalation time is prolonged to 1 hour.
Finally, the oxidized graphene which is thoroughly oxidized is obtained.
Example 3
The present embodiment provides a graphene oxide, and the difference between the preparation method of the graphene oxide provided in the present embodiment and the preparation method of embodiment 1 is that: the strong oxidant adopts potassium ferrate.
Fig. 3 shows a scanning electron micrograph of graphene oxide prepared in example 3.
Example 4
The present embodiment provides a graphene oxide, and the difference between the preparation method of the graphene oxide provided in the present embodiment and the preparation method of embodiment 1 is that: the strong oxidant adopts potassium ferrate.
The adding amount of potassium permanganate is 3 parts, and the oxidation time is prolonged to 4 hours. Finally, the oxidized graphene which is thoroughly oxidized is obtained.
Fig. 4 shows a scanning electron micrograph of graphene oxide prepared in example 4. As can be seen from fig. 4, the radial size of the graphene oxide prepared in example 4 is greater than 400 μm.
Comparative example 1
The present comparative example provides a graphene oxide, and the preparation method of the graphene oxide provided by the present comparative example is different from the preparation method of example 1 in that:
as in example 1, potassium permanganate was added only 2 times as much as graphite and the oxidation time was 10 hours.
Finally, the graphite is incompletely oxidized, the edge of the graphite sheet is yellow, and the inner wall of the graphite sheet is in a black state; when the amount of the strong oxidizing agent is too small, the oxidation may not be completed even if the oxidation time is prolonged.
Comparative example 2
The method comprises the following steps of oxidizing flake graphite by adopting a traditional hummers method: adding 0.5 part of sodium nitrate solid into 1 part of crystalline flake graphite, adding 15 parts of concentrated sulfuric acid, placing the mixture into an ice water bath, fully stirring, slowly adding 8 parts of potassium permanganate for multiple times, controlling the reaction temperature to be below 20 ℃, stirring and reacting for about 5 hours, finding that the graphite still presents a black state, removing temperature control, continuously oxidizing for more than 24 hours, controlling the temperature by using the ice water bath, adding 30 parts of deionized water and a certain amount of hydrogen peroxide, finally finding that the solution cannot become a golden yellow state, and failing to oxidize.
In summary, the preparation method of graphene oxide provided by the embodiment of the present application can obtain large-sized graphene oxide, and nitric acid is not used in the preparation process, so that the safety performance is good.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A preparation method of graphene oxide is characterized by comprising the following steps:
reacting graphite, acid solution and hydrogen peroxide at 75-85 ℃ for 25-45 minutes to obtain acid intercalated graphite;
mixing concentrated sulfuric acid with the acid intercalated graphite, adding a strong oxidant for reaction, and then removing acid to obtain graphene oxide;
stirring the graphene oxide to strip and delaminate the graphene oxide;
wherein the acid solution comprises concentrated sulfuric acid and phosphoric acid, or the acid solution comprises concentrated sulfuric acid and phosphorus pentoxide;
the mass ratio of the strong oxidant to the graphite is greater than or equal to 3.
2. The method according to claim 1, wherein the step of removing the acid to obtain graphene oxide comprises:
and (3) removing acid by pressure filtration, terminating the oxidation reaction by using hydrogen peroxide, and washing by using water to obtain the graphene oxide.
3. The method for producing graphene oxide according to any one of claims 1 to 2,
the mass fraction of the hydrogen peroxide is 30-65%.
4. The method for producing graphene oxide according to any one of claims 1 to 2,
the mass ratio of the graphite to the concentrated sulfuric acid in the acid solution is (1: 18-1): 10.
5. the method for producing graphene oxide according to any one of claims 1 to 2,
the mass ratio of the graphite to the phosphoric acid or the phosphorus pentoxide in the acid solution is 1: 1.2-1: 0.8.
6. the method for producing graphene oxide according to any one of claims 1 to 2,
the mass ratio of the graphite to the strong oxidant is 1: 4-1: 3.
7. the method for producing graphene oxide according to any one of claims 1 to 2, wherein the strong oxidizing agent includes potassium permanganate and/or potassium ferrate.
8. The method for producing graphene oxide according to any one of claims 1 to 2, wherein the graphite is flake graphite.
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