A method for preparing amino-graphene

Abstract

The application discloses a preparation method of amino-graphene. The traditional preparation method has high production cost, low yield, complicated steps and causes serious pollution to the environment. The method comprises the following steps: firstly, under water bath cooling, graphene oxide is added into concentrated hydrochloric acid, and after ultrasonic dispersion, the graphene oxide is extracted and filtered, and the precipitate is washed to neutral, and then dried to obtain purified graphene oxide; then, the purified graphene oxide is added into hydrogen peroxide solution, and an amino acid aqueous solution is added into the mixed solution, and after ultrasonic, the mixture is stirred and reacted, and after the reaction product is filtered, washed and dried, amino-graphene is obtained. The method can realize the amino-graphene of graphene by effectively controlling the reaction conditions and adding appropriate reagents, and high-purity amino-graphene is prepared. The method simplifies the technological process, reduces the use of harmful solvents and chemical reagents, and reduces the adverse effects on the environment.

Description

Technical Field

[0001] This invention belongs to the field of graphene technology and relates to a method for preparing amino-based graphene. Background Technology

[0002] Aminated graphene is a carbon material with unique properties and potential applications. Compared to traditional graphene, aminated graphene has a higher specific surface area, better electrical conductivity and chemical activity, as well as greater stress and mechanical properties. Due to its outstanding performance, aminated graphene shows great application potential in fields such as energy storage, catalysts, sensors, biomedicine, and optoelectronic devices.

[0003] Traditional methods for preparing aminated graphene often employ chemical vapor deposition (CVD), chemical vapor deposition (CVD), and foam template methods. These methods suffer from high production costs, low yields, and cumbersome procedures. Furthermore, traditional methods frequently use harmful solvents and chemical reagents, causing serious environmental pollution. Therefore, there is a need for an efficient, economical, environmentally friendly, and controllable method for preparing aminated graphene to meet the demands of various fields. Summary of the Invention

[0004] The purpose of this invention is to provide an efficient, economical, environmentally friendly and controllable method for preparing aminated graphene, so as to solve the technical problems of low yield, complex process, high cost and environmental pollution of traditional methods.

[0005] The method of this invention first purifies graphene oxide, and then amination is performed on the purified graphene oxide, as follows:

[0006] Step (1) Under water bath cooling, add graphene oxide to concentrated hydrochloric acid with a mass fraction of 30-40%, adding 100-200g of graphene oxide per liter of concentrated hydrochloric acid; disperse by ultrasonication at 20-50kHz for 10-50min; then stir at 20-50℃ for 2-5h, filter and wash the precipitate with water until neutral; vacuum dry at 60-80℃ for 5-10h to obtain purified graphene oxide.

[0007] Step (2) Add purified graphene oxide to a 10-30% hydrogen peroxide aqueous solution, stir and mix to obtain a mixed solution; add 100-200 grams of purified graphene oxide per liter of hydrogen peroxide aqueous solution;

[0008] In step (3), add an amino acid aqueous solution with a concentration of 5-10 mg / ml to the mixed solution, sonicate at 20-50 kHz for 5-20 min in a water bath, and continue stirring for 20-60 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 1:0.5-1.

[0009] Step (4) Vacuum filtration: The filter cake is repeatedly washed and filtered with anhydrous ethanol and distilled water. The filter residue is vacuum dried at 60-80℃ for 2-5 hours, ground, and then vacuum dried at 60-80℃ for 1-2 hours to obtain amino-based graphene.

[0010] This invention utilizes a method that effectively controls reaction conditions and adds appropriate amounts of reagents to achieve the amination of graphene, producing high-purity ammoniated graphene. This method significantly increases the yield of ammoniated graphene and simplifies the process. The resulting ammoniated graphene has potential applications in materials science, electronic devices, and other fields. Furthermore, this invention introduces an environmentally friendly preparation method, reducing the use of harmful solvents and chemical reagents, thus minimizing adverse environmental impacts.

[0011] This invention enables controlled growth of aminated graphene by rationally designing preparation conditions and parameters, thereby regulating the morphology, structure, and properties of aminated graphene and meeting the specific performance requirements of aminated graphene in different application fields. Attached Figure Description

[0012] Figure 1 The infrared spectrum of an amino-based graphene is shown in one embodiment of the present invention. Detailed Implementation

[0013] The present invention will be further illustrated by specific embodiments below. The graphene oxide used in all the following embodiments is from Huzhou Huasi New Material Technology Co., Ltd. Example 1

[0014] Step (1) Under water bath cooling, 100g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 30% and ultrasonically dispersed at 30kHz for 30min; then stirred at 20℃ for 5h, filtered and the precipitate was washed with water until neutral; vacuum dried at 60℃ for 10h to obtain purified graphene oxide.

[0015] Step (2) Take 80g of purified graphene oxide and add it to 0.5L of 20% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0016] In step (3), add an amino acid aqueous solution with a concentration of 6 mg / ml to the mixed solution, sonicate at 30 kHz for 16 min in a water bath, and continue stirring for 20 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 3:2.

[0017] Step (4) Vacuum filtration: The filter cake is first washed and filtered with anhydrous ethanol, then washed and filtered with distilled water. The filter residue is vacuum dried at 60°C for 5 hours, ground, and then vacuum dried at 65°C for 2 hours to obtain amino-based graphene. Example 2

[0018] Step (1) Under water bath cooling, 200g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 40% and ultrasonically dispersed at 20kHz for 50min; then stirred at 30℃ for 3h, filtered and the precipitate was washed with water until neutral; vacuum dried at 70℃ for 7h to obtain purified graphene oxide.

[0019] Step (2) Take 150g of purified graphene oxide and add it to 1.5L of 10% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0020] In step (3), add an amino acid aqueous solution with a concentration of 5 mg / ml to the mixed solution, sonicate at 50 kHz for 5 min in a water bath, and continue stirring for 60 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 1:1.

[0021] Step (4) Vacuum filtration: The filter cake is first washed with distilled water, then washed with anhydrous ethanol, and then washed with distilled water. The filter residue is vacuum dried at 70°C for 3.5 hours, ground, and then vacuum dried at 75°C for 1 hour and 20 minutes to obtain amino-based graphene. Example 3

[0022] Step (1) Under water bath cooling, 150g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 35% and ultrasonically dispersed at 50kHz for 10min; then stirred at 50℃ for 2h, filtered and the precipitate was washed with water until neutral; vacuum dried at 80℃ for 5h to obtain purified graphene oxide.

[0023] Step (2) Take 120g of purified graphene oxide and add it to 1 liter of 15% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0024] In step (3), add an amino acid aqueous solution with a concentration of 10 mg / ml to the mixed solution, sonicate at 20 kHz for 20 min in a water bath, and continue stirring for 30 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 2:1.

[0025] Step (4) Vacuum filtration: The filter cake is washed twice each with anhydrous ethanol and distilled water. The filter residue is vacuum dried at 80°C for 2 hours, ground, and then vacuum dried at 65°C for 1 hour and 45 minutes to obtain amino-based graphene. Example 4

[0026] Step (1) Under water bath cooling, 120g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 36% and dispersed by ultrasonication at 40kHz for 35min; then stirred at 40℃ for 3h, filtered and the precipitate was washed with water until neutral; and dried under vacuum at 65℃ for 8h to obtain purified graphene oxide.

[0027] Step (2) Take 100g of purified graphene oxide and add it to 0.5L of 30% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0028] In step (3), add an amino acid aqueous solution with a concentration of 9 mg / ml to the mixed solution, sonicate at 40 kHz for 10 min in a water bath, and continue stirring for 50 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 2:3.

[0029] Step (4) Vacuum filtration: The filter cake is first washed and filtered with anhydrous ethanol, then washed and filtered with distilled water. The filter residue is vacuum dried at 65°C for 4 hours, ground, and then vacuum dried at 60°C for 2 hours to obtain amino-based graphene. Example 5

[0030] Step (1) Under water bath cooling, 180g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 32% and ultrasonically dispersed at 35kHz for 25min; then stirred at 25℃ for 4h, filtered and the precipitate was washed with water until neutral; vacuum dried at 75℃ for 6h to obtain purified graphene oxide.

[0031] Step (2) Take 140g of purified graphene oxide and add it to 1 liter of 21% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0032] In step (3), add an amino acid aqueous solution with a concentration of 8 mg / ml to the mixed solution, sonicate at 45 kHz for 8 min in a water bath, and continue stirring for 40 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 5:3.

[0033] Step (4) Vacuum filtration: The filter cake is washed twice each with anhydrous ethanol and distilled water in turn. The filter residue is vacuum dried at 75°C for 3 hours, ground, and then vacuum dried at 80°C for 1 hour to obtain amino-based graphene. Example 6

[0034] Step (1) Under water bath cooling, 135g of graphene oxide was added to 1 liter of concentrated hydrochloric acid with a mass fraction of 38% and ultrasonically dispersed at 45kHz for 15min; then stirred at 35℃ for 3.5h, filtered and the precipitate was washed with water until neutral; vacuum dried at 72℃ for 8h to obtain purified graphene oxide.

[0035] Step (2) Take 100g of purified graphene oxide and add it to 0.6L of 25% hydrogen peroxide aqueous solution. Stir and mix well to obtain a mixed solution.

[0036] In step (3), add an amino acid aqueous solution with a concentration of 7 mg / ml to the mixed solution, sonicate at 35 kHz for 15 min in a water bath, and continue stirring for 45 min. The volume ratio of the mixed solution to the amino acid aqueous solution is 4:3.

[0037] Step (4) Vacuum filtration: The filter cake is first washed with distilled water, then washed with anhydrous ethanol, and then washed with distilled water. The filter residue is vacuum dried at 70°C for 4 hours, ground, and then vacuum dried at 70°C for 1.5 hours to obtain amino-based graphene.

[0038] After testing, the infrared spectrum of amino-based graphene is as follows: Figure 1 As shown:

[0039] 1. The appearance of CN-bond stretching vibration bands: The original C-C bond vibration bands in graphene will be replaced by CN-bond stretching vibration bands. This indicates that carbon atoms on the graphene surface are replaced by amino groups.

[0040] 2. The appearance of new NH bond stretching vibration bands: The amino groups on the graphene surface lead to the appearance of new NH bond stretching vibration bands, indicating that the amino groups have successfully reacted chemically with the graphene.

[0041] 3. Reduced or lost original graphene features: During the amination process of graphene, some original graphene features are reduced or lost. This includes the vibrational bands of the C-C bonds in graphene. By analyzing these features in the infrared spectrum, it can be concluded that the graphene has been amination.

Claims

1. A method for preparing amino-graphene, which comprises purifying graphene oxide and then subjecting the purified graphene oxide to amination; characterized in that, Specific as follows: Step (1) under the water bath cooling, graphene oxide is added into 30-40% mass fraction of concentrated hydrochloric acid, 100-200g graphene oxide is added into each liter of concentrated hydrochloric acid; ultrasonic dispersion is carried out for 10-50min at 20-50kHz; then stirring is carried out for 2-5h at 20-50℃, the precipitate is washed to neutral with water after suction filtration; vacuum drying is carried out for 5-10h at 60-80℃, and the purified graphene oxide is obtained; Step (2) the purified graphene oxide is added into 10-30% mass fraction of hydrogen peroxide aqueous solution, and stirring is carried out to obtain a mixed solution; 100-200g purified graphene oxide is added into each liter of hydrogen peroxide aqueous solution; Step (3) the mixed solution is added into 5-10mg / ml amino acid aqueous solution, ultrasonic dispersion is carried out for 5-20min at 20-50kHz under water bath, and stirring reaction is continuously carried out for 20-60min, the volume ratio of the mixed solution to the amino acid aqueous solution is 1:0.5-1; Step (4) vacuum filtration is carried out, the filter cake is repeatedly cleaned and filtered with anhydrous ethanol and distilled water, the filter residue is vacuum dried for 2-5h at 60-80℃, and after grinding, vacuum drying is continuously carried out for 1-2h at 60-80℃, and the amino-functionalized graphene is obtained.

Images