CN109336094B - Nitrogen-doped graphene and preparation method thereof - Google Patents
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Abstract
The invention discloses nitrogen-doped graphene and a preparation method thereof, and the preparation method comprises the following steps: preparing graphene oxide; adding deionized water into graphene oxide, performing ultrasonic treatment and centrifugation to obtain a graphene oxide dispersion solution, adding urea I into the graphene oxide dispersion solution, performing ultrasonic treatment, and placing the mixture into a reaction kettle, wherein the reaction temperature is 160 ℃, and the reaction time is 3 hours to obtain nitrogen-doped graphene I; adding anhydrous ethanol into melamine, mixing with the graphene oxide dispersion liquid, and putting into a high-pressure reaction kettle, wherein the reaction temperature is 180 ℃, and the reaction time is 8 hours, so as to obtain nitrogen-doped graphene II; ultrasonically mixing the graphene oxide dispersion liquid, calcium chloride and oxalic acid powder, ultrasonically mixing thioacetamide dissolved in deionized water, mixing the two, ultrasonically vibrating for 1h, and heating on an induction cooker at the reaction temperature of 80 ℃ for 6h to obtain the nitrogen-doped graphene III. The nitrogen-doped graphene prepared by the preparation method provided by the invention has high quality, reduces defects and improves the comprehensive performance of the nitrogen-doped graphite.
Description
Technical Field
The invention relates to the technical field of inorganic non-metallic materials, in particular to nitrogen-doped graphene and a preparation method thereof.
Background
Due to the excellent properties of high specific surface area, high strength, high thermal conductivity, good electrical conductivity and the like of graphene, the graphene is widely applied to various fields, such as new energy, catalysts, biomedicine and the like. The surface of the graphene with a complete structure is inert, and the graphene is compounded with other elements or materials by a common method to obtain good comprehensive performance.
Chemical element doping is one of the more effective methods to improve the performance of graphene. The existing method for preparing nitrogen-doped graphene mainly comprises the following steps: (1) a chemical vapor deposition method, in which a gaseous precursor is reacted on a substrate to form a thin film, requires a metal catalyst, and is difficult to separate the metal catalyst from nitrogen-doped graphene and complicated in process; (2) a nitrogen-containing precursor conversion method, wherein a nitrogen-containing substance is mixed with a transition metal compound catalyst, and then the mixture is reacted at a high temperature, and a nitrogen-doped graphene is obtained after a metal compound is removed; (3) a nitrogen-doped graphene oxide method is disclosed in the patent with the publication number of CN104465113, wherein the nitrogen-doped graphene oxide is prepared by taking graphene oxide as a raw material, taking a nitrogen-containing substance as a nitrogen source and carrying out nitrogen doping under a high-temperature or hydrothermal condition, the method is characterized in that the graphene oxide is taken as the raw material, mixed with urea and sulfuric acid and then subjected to hydrothermal reaction for 2 hours at 180 ℃ to obtain the nitrogen-doped graphene, and the graphene oxide is difficult to obtain and has high cost, so the method is limited.
Due to the problems of the method, such as low nitrogen doping amount, low graphene reduction rate, more doped graphene defects and the like. Therefore, the preparation method which has the advantages of simple process, easily available raw materials, low cost and no need of using a metal catalyst is very important.
Disclosure of Invention
The present invention is directed to solving the above problems and providing a method for preparing high-quality nitrogen-doped graphene.
In order to achieve the above object, the present disclosure provides a nitrogen-doped graphene and a preparation method thereof, including the following steps:
s1: preparing graphene oxide;
s2: adding deionized water into graphene oxide, and performing ultrasonic treatment and centrifugation to obtain a graphene oxide dispersion liquid;
s3: adding urea into the graphene oxide dispersion liquid to obtain a mixture I, carrying out ultrasonic treatment on the mixture I for 30min, and then putting the mixture I into a reaction kettle, wherein the reaction temperature is 160 ℃, and the reaction time is 3h to obtain nitrogen-doped graphene I;
s4: adding anhydrous ethanol into melamine, performing ultrasonic treatment for 10min, mixing with the graphene oxide dispersion liquid to obtain a mixture II, performing ultrasonic treatment on the mixture II for 30min, and placing the mixture II into a high-pressure reaction kettle, wherein the reaction temperature is 180 ℃, and the reaction time is 8h to obtain nitrogen-doped graphene II;
s5: and carrying out ultrasonic treatment on the graphene oxide dispersion liquid, calcium chloride and oxalic acid powder for 30min to obtain a mixture III, dissolving thioacetamide in deionized water, carrying out ultrasonic treatment for 30min to obtain a mixture IV, mixing the mixture III and the mixture IV, carrying out ultrasonic vibration for 1h, placing the mixture IV on an induction cooker, heating, and carrying out reaction at the temperature of 80 ℃ for 6h to obtain the nitrogen-doped graphene III.
Optionally, the step S1 specifically includes: taking graphite powder, sodium nitrate and concentrated sulfuric acid under an ice bath condition, stirring and reacting, adding a strong oxidant, stirring at room temperature until the color is changed, then dropwise adding deionized water, stirring, simultaneously adding hydrogen peroxide for reaction, washing with dilute hydrochloric acid and deionized water after the reaction until the solution is neutral, and drying to obtain graphene oxide.
Optionally, the strong oxidant is at least one of sulfuric acid, potassium permanganate and sodium nitrate.
Alternatively, in S3, the graphene oxide dispersion and urea are mixed at a ratio of 1 mL: 20mg in a ratio.
Optionally, in S3, after the mixture I is heated in the reaction kettle, it is naturally cooled, and then washed with a dilute hydrochloric acid solution and deionized water until the solution is neutral, and dried to obtain the nitrogen-doped graphene I.
Alternatively, in S4, the graphene oxide dispersion, the absolute ethanol, and the melamine are mixed in a ratio of 1 mL: 1mL of: 4mg in a ratio.
Optionally, in S4, the mixture II is naturally cooled after reacting in a high-pressure reactor for 8 hours, and then washed with a dilute hydrochloric acid solution and deionized water until the solution becomes neutral, and dried to obtain the nitrogen-doped graphene II.
Alternatively, in S5, the graphene oxide dispersion, calcium chloride, and oxalic acid powder were mixed at a ratio of 10 mL: 50 mg: 41mg of the mixture III, thioacetamide and deionized water in a proportion of 50 mg: 5mL of the mixture was mixed to obtain a mixture IV.
Alternatively, in S5, when the temperature of the mixed solution of mixture III and mixture IV in a 1300W induction cooker is raised to 80 ℃, 0.1 mol. L is dropwise added-1The pH of the mixed solution was adjusted to 10, and the heating was continued.
Alternatively, in S5, after 6 hours of reaction, the supernatant in the vessel was poured off, the precipitate was taken out, washed with deionized water several times, dried at 70 ℃ for 24 hours, and the dried complex was dissolved in 5 mol. L-1Stirring and carrying out ultrasonic treatment for 1h in a hydrochloric acid solution, washing with deionized water to be neutral, filtering, and drying at 60 ℃ for 24h to obtain the nitrogen-doped graphene III.
The invention has the beneficial effects that:
according to the invention, the graphene oxide is prepared by an improved Hummers method, the nitrogen-doped graphene is prepared by a hydrothermal method, and compared with the nitrogen-doped graphene prepared by other methods such as chemical vapor deposition and arc discharge, the hydrothermal method has the advantages of simple required equipment, low requirement on conditions and suitability for laboratory preparation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is an XRD pattern of nitrogen-doped graphene I, nitrogen-doped graphene II, nitrogen-doped graphene III and graphene according to the present invention;
fig. 2 is a raman spectrum of the nitrogen-doped graphene I, the nitrogen-doped graphene II, and the nitrogen-doped graphene III according to the present invention;
FIG. 3 is a cyclic voltammogram of nitrogen-doped graphene II according to the present invention at different scanning rates in a potassium hydroxide solution;
FIG. 4 is a charge-discharge curve of the nitrogen-doped graphene II according to the present invention at a current density of 1A/g.
Description of the reference numerals
NG-1-nitrogen-doped graphene I, NG-2-nitrogen-doped graphene II, NG-3-nitrogen-doped graphene III and GR-graphene.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The invention relates to nitrogen-doped graphene and a preparation method thereof, wherein the preparation method comprises the following steps:
s1: preparing graphene oxide;
s2: preparing a graphene oxide dispersion liquid;
s3: weighing graphene oxide dispersion liquid, and taking urea as a nitrogen source to prepare nitrogen-doped graphene I by a hydrothermal method;
s4: weighing a graphene oxide dispersion liquid, and preparing nitrogen-doped graphene II by using melamine as a nitrogen source through a hydrothermal method;
s5: weighing the graphene oxide dispersion liquid, and taking thioacetamide as a nitrogen source to prepare the nitrogen-doped graphene III by a hydrothermal method.
The specific content of S1 is:
firstly, 2.5g of graphite powder and 1.25g of sodium nitrate are added into a 500mL beaker, and secondly, 58mL of concentrated sulfuric acid is added, the mass fraction of which is 98%. Stirring the obtained mixed solution for 2 hours at the temperature of about 0 ℃; secondly, under the condition of stirring, slowly adding 15g of potassium permanganate into the obtained mixture for reaction, keeping the reaction temperature below 20 ℃, removing an ice bath device after the addition of the potassium permanganate is completed, stirring the obtained reaction product at room temperature, and changing the solution from black to dark green paste; then, 300mL of deionized water was added dropwise to the beaker with stirring, the reaction temperature rapidly increased to 95 ℃ and a large amount of bubbles were generated, and the color of the solution in the beaker instantaneously changed to a bright yellow color. Stirring the obtained product at 95 ℃ for 2h, and then adding 50mL of 30% hydrogen peroxide to obtain a crude product of graphene oxide; and finally, centrifugally washing the obtained crude product of the graphene oxide with 5% diluted hydrochloric acid for three times, washing with deionized water for several times, stopping washing until the washing liquid is neutral, and drying the obtained solid to obtain the graphene oxide.
The specific content of S2 is:
weighing 100mg of graphene oxide solid, adding 100mL of deionized water, carrying out ultrasonic treatment on the solution for 30min, centrifuging the solution for 10min at 3500r/min, repeating the centrifugation for multiple times to remove obvious large-particle solid, taking the upper-layer solution, centrifuging the upper-layer solution for 10min at 5000r/min, and dispersing the solid on the wall and the bottom of the centrifugal tube into water to obtain 1mg/mL of graphene oxide dispersion liquid with good quality.
The specific content of S3 is:
and adding 400mg of urea into 20mL of graphene oxide dispersion liquid, and performing ultrasonic dispersion for 30 min. And (3) putting the dispersion into a reaction kettle, heating to 160 ℃, reacting for 3 hours, and naturally cooling after heating. Washing the cooling liquid with 5% dilute hydrochloric acid to remove alkaline ions, washing the cooling liquid with deionized water for multiple times until the solution is neutral, and drying the solution at 70 ℃ to obtain the nitrogen-doped graphene I.
The specific content of S4 is:
20mL of graphene oxide dispersion liquid, 20mL of absolute ethyl alcohol and 80mg of melamine are measured. Firstly, adding melamine into absolute ethyl alcohol, performing ultrasonic treatment for 10min, then mixing with the graphene oxide dispersion liquid, and performing ultrasonic treatment for 30 min. And (3) putting the mixed solution into a high-pressure reaction kettle, reacting at 180 ℃ for 8 hours, and naturally cooling. The resulting black solid was washed three times with 5% dilute hydrochloric acid, then washed several times with deionized water to remove the dilute hydrochloric acid, and the washing was stopped when the test solution was neutral. And drying the solid at 70 ℃ to obtain the nitrogen-doped graphene II.
The specific content of S5 is:
and (3) taking 100ml of graphene oxide dispersion liquid, adding 0.5g of calcium chloride and 0.41g of oxalic acid powder, and carrying out ultrasonic treatment for 30 min. Meanwhile, 0.5g thioacetamide was dissolved in 50mL deionized water and sonicated for 30 min. Stirring and mixing the two solutions uniformly, ultrasonically vibrating for 1h, then placing the mixed solution on a 1300W induction cooker for heating, and dropwise adding 0.1 mol.L when the temperature is raised to 80 DEG C-1And (3) adjusting the pH value of the solution to 10, continuously heating, reacting for 6 hours, pouring out supernatant, taking out precipitate, washing with deionized water for multiple times, and drying at 70 ℃ for 24 hours to obtain the nitrogen-doped graphene/calcium oxalate compound. Dissolving the prepared nitrogen-doped graphene/calcium oxalate compound in 5 mol.L-1And stirring and carrying out ultrasonic treatment for 1h in a hydrochloric acid solution, repeatedly washing for three times, then washing for several times by using deionized water until the solution is neutral, filtering, and then drying for 24h at 60 ℃ to obtain the nitrogen-doped graphene III.
According to the method, the graphene oxide is prepared by an improved Hummers method, the nitrogen-doped graphene is prepared by a hydrothermal method, urea, melamine and thioacetamide are respectively adopted as nitrogen sources to reduce the graphene oxide and carry out nitrogen doping, the preparation time of the nitrogen-doped graphene I is shortest, the preparation process of the nitrogen-doped graphene II is simpler, and the heating temperature is higher than that of the nitrogen-doped graphene III. The preparation time of the nitrogen-doped graphene III is longest, the preparation procedures are multiple, and the problems of hydrogen sulfide release in the preparation process and the like exist.
And respectively carrying out X-ray diffraction analysis, Raman spectrum analysis and cyclic voltammetry analysis on the prepared graphene oxide, nitrogen-doped graphene I, nitrogen-doped graphene II and nitrogen-doped graphene III.
X-ray diffraction analysis:
as shown in fig. 1, the nitrogen-doped graphene II has the smallest interlayer spacing and the obvious peak position relative to the nitrogen-doped graphene I and the nitrogen-doped graphene III, so that the melamine reduces the graphene oxide more thoroughly, and the recovery degree of the graphite lattice structure is also the highest.
And (3) Raman spectrum analysis:
as shown in fig. 2, the nitrogen-doped graphene II has the smallest ID/IG value and the narrowest peak, indicating that the defect is the least and the degree of order is higher, and the nitrogen-doped graphene II has the largest I2D/IG value, indicating that the number of layers is the thinnest and the quality is the highest among the three.
Cyclic voltammetry analysis:
as shown in fig. 3, under the same current density condition, the cyclic voltammetry area of the nitrogen-doped graphene II is the largest, the nitrogen-doped graphene I is the smallest, and the nitrogen-doped graphene III is located between the two, so that compared with the nitrogen-doped graphene I and the nitrogen-doped graphene III, the nitrogen-doped graphene II has a larger specific capacitance, the cyclic life is the best, the charge-discharge structure is stable, and the performance of the supercapacitor is more excellent.
Constant current charge and discharge analysis:
as shown in fig. 4, the charge and discharge curves of the nitrogen-doped graphene II all show good symmetry at different current densities, so that the nitrogen-doped graphene II has a good structure and stable charge and discharge performance, and has good capacitance retention rate and good electric double layer capacitance characteristics as a modified electrode material.
The comprehensive comparison of the analysis results shows that under the hydrothermal condition, the nitrogen-doped graphene obtained by reacting melamine serving as a nitrogen source with high-quality graphene oxide dispersion liquid and ethanol for 8 hours has the best quality, the method ensures that the graphene oxide is reduced more thoroughly, and the electrical property of the graphene oxide is the most excellent.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (9)
1. The nitrogen-doped graphene and the preparation method are characterized by comprising the following steps:
s1: preparing graphene oxide; the method specifically comprises the following steps: taking graphite powder, sodium nitrate and concentrated sulfuric acid under an ice bath condition, stirring and reacting, adding a strong oxidant, stirring at room temperature until the color is changed, then dropwise adding deionized water, stirring, simultaneously adding hydrogen peroxide for reaction, washing with dilute hydrochloric acid and deionized water after the reaction until the solution is neutral, and drying to obtain graphene oxide;
s2: adding deionized water into graphene oxide, and performing ultrasonic treatment and centrifugation to obtain a graphene oxide dispersion liquid;
s3: adding urea into the graphene oxide dispersion liquid to obtain a mixture I, carrying out ultrasonic treatment on the mixture I for 30min, and then putting the mixture I into a reaction kettle, wherein the reaction temperature is 160 ℃, and the reaction time is 3h to obtain nitrogen-doped graphene I;
s4: adding anhydrous ethanol into melamine, performing ultrasonic treatment for 10min, mixing with the graphene oxide dispersion liquid to obtain a mixture II, performing ultrasonic treatment on the mixture II for 30min, and placing the mixture II into a high-pressure reaction kettle, wherein the reaction temperature is 180 ℃, and the reaction time is 8h to obtain nitrogen-doped graphene II;
s5: and carrying out ultrasonic treatment on the graphene oxide dispersion liquid, calcium chloride and oxalic acid powder for 30min to obtain a mixture III, dissolving thioacetamide in deionized water, carrying out ultrasonic treatment for 30min to obtain a mixture IV, mixing the mixture III and the mixture IV, carrying out ultrasonic vibration for 1h, placing the mixture IV on an induction cooker, heating, and carrying out reaction at the temperature of 80 ℃ for 6h to obtain the nitrogen-doped graphene III.
2. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: the strong oxidant is at least one of sulfuric acid, potassium permanganate and sodium nitrate.
3. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: in S3, the graphene oxide dispersion and urea were mixed at a ratio of 1 mL: 20mg in a ratio.
4. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: and S3, after the mixture I is heated in the reaction kettle, naturally cooling, washing with a dilute hydrochloric acid solution and deionized water until the solution is neutral, and drying to obtain the nitrogen-doped graphene I.
5. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: in S4, the graphene oxide dispersion, absolute ethanol, and melamine were mixed in a ratio of 1 mL: 1mL of: 4mg in a ratio.
6. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: and in S4, reacting the mixture II in a high-pressure reaction kettle for 8 hours, naturally cooling, washing with a dilute hydrochloric acid solution and deionized water until the solution is neutral, and drying to obtain the nitrogen-doped graphene II.
7. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: in S5, the graphene oxide dispersion, calcium chloride, and oxalic acid powder were mixed in a 10 mL: 50 mg: 41mg of the mixture III, thioacetamide and deionized water in a proportion of 50 mg: 5mL of the mixture was mixed to obtain a mixture IV.
8. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: in S5, 0.1 mol. L is dropwise added to the mixed solution of mixture III and mixture IV when the temperature of the mixed solution rises to 80 ℃ in a 1300W induction cooker-1The pH of the mixed solution was adjusted to 10, and the heating was continued.
9. The nitrogen-doped graphene and the preparation method thereof according to claim 1, wherein the preparation method comprises the following steps: s5, after 6h of reaction, pouring out supernatant in a container, taking out precipitate, washing the precipitate with deionized water for multiple times, drying the precipitate at 70 ℃ for 24h, and dissolving the dried compound in 5 mol/L-1Stirring and carrying out ultrasonic treatment for 1h in a hydrochloric acid solution, washing with deionized water to be neutral, filtering, and drying at 60 ℃ for 24h to obtain the nitrogen-doped graphene III.
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| CN115318268A (en) * | 2021-09-30 | 2022-11-11 | 湘潭大学 | Preparation method and application of nonmetallic catalyst for liquid-phase hydrogenation of nitroarene |
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| CN114892451A (en) * | 2022-06-02 | 2022-08-12 | 山东东宇鸿翔装饰材料有限公司 | Copper-nitrogen doped TiO 2 Antibacterial paper, antibacterial board and preparation method thereof |
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