CN112744811A - Large-sheet-diameter graphene oxide and preparation method thereof - Google Patents
Large-sheet-diameter graphene oxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a large-sheet-diameter graphene oxide and a preparation method thereof, wherein the large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 20-25 parts of crystalline flake graphite, 10-15 parts of sodium nitrate, 150-250 parts of concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% aqueous hydrogen peroxide solution, 5-15 parts of separating agent and the like; adding the crystalline flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid, adding potassium chlorate, stirring for 30min, adding deionized water, heating, adding aqueous hydrogen peroxide, finally adding a separating agent, stirring at a constant speed for 2h, and filtering to obtain separated graphene oxide; the separating agent is added in the separation process, various oxygen-containing functional groups are bonded on a graphite carbon atom layer in the oxidation process, the reaction activity is strong, the graphite oxide can be endowed with strong particle exchange performance, the separating agent is added, and the separating agent is inserted between graphite oxide layers through cation exchange, so that the distance between the graphite oxide layers is enlarged, and the separation is facilitated.
Description
Technical Field
The invention belongs to the technical field of nano carbon materials, and particularly relates to large-sheet-diameter graphene oxide and a preparation method thereof.
Background
The graphene oxide is prepared by adopting a natural graphite raw material, and the graphene oxide can be obtained by firstly preparing the graphite oxide from the natural graphite raw material by adopting an oxidation treatment method and then stripping the graphite oxide. In the process of obtaining graphite oxide by oxidizing natural graphite raw materials, oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy and the like are grafted on an original graphite structure layer. The oxidation treatment method adopted isUsually Hummers method, etc., namely, putting the graphite raw material in a concentrated sulfuric acid and nitrate system and using KMnO4As an oxidant, reacting for 2 hours under the condition of low-temperature ice-water bath, reacting for 0.5-2 hours under the condition of medium temperature of 35-50 ℃, and reacting for 0.5-2 hours under the condition of high temperature of 60-100 ℃ to prepare the graphite oxide. The earliest improvement method is to remove the nitrate in the reaction system, then reduce the low-temperature reaction time to 0.5h, increase the medium-temperature reaction time to 2h and the like.
The Chinese invention patent CN104556021B discloses a method for preparing large-flake-diameter graphene oxide by using natural flaky graphite. The method comprises the following steps: 1) preparing graphite oxide by taking natural flaky graphite with carbon content of 95-99.9% as a raw material, and adding deionized water to obtain a graphite oxide suspension; 2) adding the graphite oxide suspension into deionized water, and stripping by using a high-speed dispersion homogenizer to obtain large-sheet-diameter graphene oxide dispersion mother liquor; the method comprises the following steps of removing impurities in the large-sheet-diameter graphene oxide dispersion mother liquor by adopting a gravity impurity removal method to obtain the large-sheet-diameter graphene oxide, wherein the large-sheet-diameter graphene oxide cannot be stably prepared by the method, and the prepared graphene oxide also contains more structural defects and influences the service performance.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a large-sheet-diameter graphene oxide and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 20-25 parts of crystalline flake graphite, 10-15 parts of sodium nitrate, 150-250 parts of concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% aqueous hydrogen peroxide solution, 5-15 parts of separating agent, 0.2-0.3 part of p-phenylenediamine and 2-5 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60-80 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2-2.5.
In the first step, a separated graphene oxide is prepared by sodium nitrate, concentrated sulfuric acid and other substances to flake graphite, a separating agent is added in the separation process, various oxygen-containing functional groups are bonded on a graphite carbon atom layer in the oxidation process, the reaction activity is strong, the graphite oxide can be endowed with strong particle exchange performance, the separating agent is added, the separating agent is inserted between graphite oxide layers through cation exchange, the distance between the graphite oxide layers is enlarged, the separation is facilitated, the prepared separated graphene oxide is processed to prepare an intermediate product, then aniline is mixed, polyaniline and graphene have a similar pi-pi conjugated structure, and the polyaniline and the graphene can be combined together through pi-pi stacking effect and van der Waals force, and further the excellent corrosion resistance can be endowed.
Further, the mixed solution D is formed by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the weight ratio of 1: 10.
Further, the separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80-90 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering to remove precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine, the 2, 3-epoxypropyltrimethylammonium chloride and the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃, drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50-65 ℃, and drying for 4 hours to obtain the separating agent.
Step S1, melamine and 2, 3-epoxypropyl trimethyl ammonium chloride are mixed, deionized water is added to adjust the pH of the system to be alkaline, 4-pyrrolidinylpyridine is added to serve as a catalyst, the melamine reacts with the 2, 3-epoxypropyl trimethyl ammonium chloride, an epoxy group on the 2, 3-epoxypropyl trimethyl ammonium chloride reacts with an amino group on the melamine, one molecule of the melamine can react with three molecules of the 2, 3-epoxypropyl trimethyl ammonium chloride to generate a concentrate with a symmetrical structure, and then refining and purification are carried out to prepare the separating agent, wherein the separating agent is quaternary ammonium salt.
Further, the mixed solution C is formed by mixing absolute ethyl alcohol and ethyl acetate according to the volume ratio of 1: 1.
A preparation method of large-sheet-diameter graphene oxide comprises the following steps:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60-80 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2-2.5.
The invention has the beneficial effects that:
(1) the invention relates to a large-sheet-diameter graphene oxide which is prepared from scale graphite, sodium nitrate, a separating agent and other raw materials, wherein in the first step in the preparation process, the scale graphite is treated by sodium nitrate, concentrated sulfuric acid and other substances to prepare a separated graphene oxide, the separating agent is added in the separation process, a plurality of oxygen-containing functional groups are bonded on a graphite carbon atomic layer in the oxidation process, the separation agent has stronger reaction activity and can endow the graphite oxide with stronger particle exchange performance, the separating agent is added, and the separating agent is inserted between graphite oxide layers through cation exchange, so that the distance between the graphite oxide layers is enlarged, the separation is more facilitated, in addition, the separation is not carried out in an ultrasonic mode and other modes, the damage of an ultrasonic means to the graphene oxide layers is effectively prevented, then, an intermediate product is prepared after the prepared separated graphene oxide is treated, and then aniline is mixed, polyaniline and graphene have similar pi-pi conjugated structures, and can be combined with van der waals force through pi-pi accumulation, so that excellent corrosion resistance can be endowed.
(2) The invention also prepares a separating agent, in the preparation process, in step S1, melamine and 2, 3-epoxypropyltrimethylammonium chloride are mixed, deionized water is added to adjust the pH of the system to be alkaline, 4-pyrrolidinylpyridine is added as a catalyst, the melamine and the 2, 3-epoxypropyltrimethylammonium chloride react, the epoxy group on the 2, 3-epoxypropyltrimethylammonium chloride reacts with the amino group on the melamine, one molecule of melamine can react with three molecules of 2, 3-epoxypropyltrimethylammonium chloride to generate a concentrate with a symmetrical structure, and then the concentrate is refined and purified to prepare the separating agent, wherein the separating agent is a quaternary ammonium salt.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 20 parts of crystalline flake graphite, 10 parts of sodium nitrate, 150 parts of concentrated sulfuric acid, 2 parts of potassium chlorate, 50 parts of 10% aqueous hydrogen peroxide, 5 parts of separating agent, 0.2 part of p-phenylenediamine and 2 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2.
The mixed liquid D is formed by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the weight ratio of 1: 10.
The separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering, removing precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride to the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃ and drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50 ℃ and drying for 4 hours to obtain the separating agent.
The mixed solution C is formed by mixing absolute ethyl alcohol and ethyl acetate according to the volume ratio of 1: 1.
Example 2
The large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 22 parts of crystalline flake graphite, 12 parts of sodium nitrate, 180 parts of concentrated sulfuric acid, 3 parts of potassium chlorate, 55 parts of 10% aqueous hydrogen peroxide solution, 10 parts of separating agent, 0.2 part of p-phenylenediamine and 2 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2.
The mixed liquid D is formed by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the weight ratio of 1: 10.
The separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering, removing precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride to the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃ and drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50 ℃ and drying for 4 hours to obtain the separating agent.
The mixed solution C is formed by mixing absolute ethyl alcohol and ethyl acetate according to the volume ratio of 1: 1.
Example 3
The large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 24 parts of crystalline flake graphite, 14 parts of sodium nitrate, 230 parts of concentrated sulfuric acid, 3 parts of potassium chlorate, 65 parts of 10% aqueous hydrogen peroxide solution, 10 parts of separating agent, 0.3 part of p-phenylenediamine and 4 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2.
The mixed liquid D is formed by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the weight ratio of 1: 10.
The separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering, removing precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride to the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃ and drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50 ℃ and drying for 4 hours to obtain the separating agent.
The mixed solution C is formed by mixing absolute ethyl alcohol and ethyl acetate according to the volume ratio of 1: 1.
Example 4
The large-sheet-diameter graphene oxide is prepared from the following raw materials in parts by weight: 25 parts of crystalline flake graphite, 15 parts of sodium nitrate, 250 parts of concentrated sulfuric acid, 4 parts of potassium chlorate, 70 parts of 10% aqueous hydrogen peroxide, 15 parts of separating agent, 0.3 part of p-phenylenediamine and 5 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2.
The mixed liquid D is formed by mixing ammonium persulfate and hydrochloric acid with the concentration of 1mol/L according to the weight ratio of 1: 10.
The separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering, removing precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride to the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃ and drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50 ℃ and drying for 4 hours to obtain the separating agent.
The mixed solution C is formed by mixing absolute ethyl alcohol and ethyl acetate according to the volume ratio of 1: 1.
Comparative example 1
In this comparative example, no separating agent was added as compared to example 1.
Comparative example 2
This comparative example is graphene prepared by Hummers method, compared to example 1.
The graphene prepared in examples 1 to 4 and comparative examples 1 to 2 was subjected to performance testing, and the results are shown in the following table;
from the above table, it can be seen that the radial size of the graphene in the examples 1-4 is 180-; the thickness of the graphene in examples 1-4 is 0.5-1.6nm, and the thickness of the graphene in comparative examples 1-2 is 2.5-3.9 nm; the peeling efficiency of examples 1-4 was 85-88%, and that of comparative examples 1-2 was 68-71%; therefore, the separating agent is added in the separation process, various oxygen-containing functional groups are bonded on the graphite carbon atomic layer in the oxidation process, the reaction activity is strong, the graphite oxide can be endowed with strong particle exchange performance, the separating agent is added, and the separating agent is inserted between the graphite oxide layers through cation exchange, so that the distance between the graphite oxide layers is enlarged, and the separation is facilitated.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The large-sheet-diameter graphene oxide is characterized by comprising the following raw materials in parts by weight: 20-25 parts of crystalline flake graphite, 10-15 parts of sodium nitrate, 150-250 parts of concentrated sulfuric acid, 2-4 parts of potassium chlorate, 50-70 parts of 10% aqueous hydrogen peroxide solution, 5-15 parts of separating agent, 0.2-0.3 part of p-phenylenediamine and 2-5 parts of dicyclohexyl carbodiimide;
the large-sheet-diameter graphene oxide is prepared by the following method:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60-80 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2-2.5.
2. The graphene oxide with large flake diameter according to claim 1, wherein the mixed solution D is prepared by mixing ammonium persulfate and hydrochloric acid with a concentration of 1mol/L according to a weight ratio of 1: 10.
3. The large-sheet-diameter graphene oxide according to claim 1, wherein the separating agent is prepared by the following method:
step S1, adding melamine into a three-neck flask, adding 2, 3-epoxypropyltrimethylammonium chloride into the beaker, then sequentially adding deionized water and 4-pyrrolidinylpyridine, adjusting the pH to 9, uniformly stirring at a rotating speed of 150 plus 200r/min for 30min to prepare a mixed solution A, dropwise adding the mixed solution A into the three-neck flask, controlling the dropwise adding time to be 10min, heating in a water bath at 80-90 ℃, uniformly stirring and reacting at the temperature for 10h, then cooling and standing for 5h, filtering to remove precipitated melamine, then concentrating, filtering, removing the melamine dissolved in water to prepare a concentrate, and controlling the weight ratio of the melamine, the 2, 3-epoxypropyltrimethylammonium chloride and the 4-pyrrolidinylpyridine to be 1: 10: 0.1;
and S2, placing the concentrate obtained in the step S1 in a vacuum drying box at 75 ℃, drying for 4 hours under the vacuum condition of-0.10 MPa to obtain mucus, transferring the prepared mucus to a beaker filled with n-butyl alcohol, magnetically stirring for 1 hour to obtain a product B, adding the product B into ethanol, uniformly dispersing, adding ethyl acetate, magnetically stirring for 2 hours to obtain white powder, standing, removing supernatant, adding the mixed solution C, uniformly mixing, standing for layering, removing supernatant, transferring to a vacuum drying box at 50-65 ℃, and drying for 4 hours to obtain the separating agent.
4. The graphene oxide with large flake diameter according to claim 3, wherein the mixed solution C is prepared by mixing absolute ethyl alcohol and ethyl acetate according to a volume ratio of 1: 1.
5. The preparation method of large-sheet-diameter graphene oxide according to claim 1, characterized by comprising the following steps:
adding flake graphite into a beaker, adding sodium nitrate and concentrated sulfuric acid with the mass fraction of 98%, stirring for 15min in an ice-water bath, adding potassium chlorate, continuously stirring for 30min, then heating in a 40 ℃ water bath, reacting for 3h, adding deionized water, heating to 75 ℃, magnetically stirring for 30min, adding aqueous hydrogen peroxide with the mass fraction of 10%, continuously reacting for 10min, finally adding a separating agent, uniformly stirring for 2h, and filtering to obtain separated graphene oxide;
secondly, adding the separated graphene oxide into absolute ethyl alcohol, stirring at a constant speed for 15min, sequentially adding p-phenylenediamine and dicyclohexylcarbodiimide, continuously stirring for 15min, heating to 60-80 ℃, introducing nitrogen to discharge air, stirring at a constant speed, reacting for 10h, washing the reaction product with absolute ethyl alcohol and deionized water for three times after the reaction is finished, and freeze-drying to obtain an intermediate product;
and thirdly, adding the prepared intermediate product into a three-neck flask filled with hydrochloric acid with the concentration of 1mol/L, adding aniline after uniform dispersion, continuously mixing for 15min, transferring to an ice-water bath, dropwise adding the mixed solution D into the three-neck flask, controlling the dropwise adding time to be 10min, stirring at a constant speed and reacting for 10h under the condition after the dropwise adding is finished, washing and drying after the reaction is finished to prepare the large-sheet-diameter graphene oxide, and controlling the weight ratio of the intermediate product to the aniline to be 1: 2 and the weight ratio of the aniline to ammonium persulfate to be 1: 2-2.5.
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