CN111072021A - Preparation method of nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole - Google Patents
Preparation method of nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole, which comprises the steps of dispersing graphene in N, N '-dimethylformamide, adding an N, N' -dimethylformamide solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, and drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic compound; grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic compound into powder, and heating at 500-800 ℃ for 3-5 h to obtain a nitrogen-doped graphene material; according to the invention, the graphene is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 5,5 '-diamino-3, 3' -1,2, 4-triazole crystal is completely maintained.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole.
Background
Graphene (G) is a two-dimensional honeycomb lattice material formed by closely bonding planar single-layer carbon atoms, has a thickness of about 0.35nm, and is the thinnest two-dimensional material in the world.
The electrons of the graphene pass through the graphene without any resistance, the generated heat is less, the conductive efficiency is high, the graphene is the material with the best known conductive performance, and the graphene has unique performance, for example, the tensile strength can reach 130 GPa; the carrier mobility can reach 15000-2Vs (square centimeter per volt-second), which can be more than 10 times that of a silicon wafer; the thermal conductivity can reach 5000W/mK (watt per milli heat conductivity coefficient), which is 3 times of that of diamond; it also has the special properties of room-temperature quantum Hall effect and room-temperature ferromagnetism.
However, graphene has no band gap, its conductivity cannot be controlled as in a conventional semiconductor, and its surface is smooth and inert, which is not conducive to compounding with other materials. The above disadvantages limit the applications of graphene.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole, and aims to solve the problem that the application of the graphene material is limited due to the fact that the graphene material is not easy to be compounded with other materials.
The invention provides a preparation method of a nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole, which is characterized by comprising the following steps: dispersing graphene in N, N '-dimethylformamide, adding an N, N' -dimethylformamide solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, and drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic compound; grinding the graphene oxide powder into powder, and placing the powder in a tubular furnace to be heated for 3-5 hours at 500-800 ℃ to obtain a nitrogen-doped graphene material; the mass ratio of the graphene to the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole in the N, N ' -dimethylformamide solution of the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole is 1: 1-10.
Preferably, the number of graphene layers is 1 to 2, and the sheet diameter is 0.2 to 100 μm.
Preferably, the mass ratio of the graphene to the 5,5 '-diamino-3, 3' -1,2, 4-triazole is 1: 4-8.
Preferably, the concentration of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole in the N, N ' -dimethylformamide solution of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole is 1 to 5 mg/mL.
Preferably, the heating temperature of the tube furnace is set to 600 ℃ and the heating time is 4 h.
In the above, the following method was used for the N, N' -dimethylformamide dispersion of graphene: adding graphene into N, N '-dimethylformamide, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the N, N' -dimethylformamide is 1: 20-30.
According to the preparation method of the nitrogen-doped graphene material, provided by the invention, 5 '-diamino-3, 3' -1,2, 4-triazole is used for reacting with graphene to obtain the graphene material with high nitrogen doping content. In the material, graphene is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the diamino-bis-triazole crystal is completely maintained. Through the heat released during thermal cracking of the 5,5 '-diamino-3, 3' -1,2, 4-triazole and the release of N2 free radicals, the energy band gap and the C-C bond of the graphene are further opened, the conductivity type is adjusted, and the electronic structure is changed; the density of free carriers is improved, and the conductivity and stability are improved; the introduction of the functional group containing nitrogen increases the active sites of the metal particles adsorbed on the surface, enhances the interaction between the metal particles and the graphene, and expands the application of the graphene.
Drawings
Fig. 1 is a scanning electron microscope test chart of the nitrogen-doped graphene material prepared in embodiment 1 of the present invention.
Fig. 2 is an X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene material prepared in example 1 of the present invention.
Fig. 3 is an X-ray photoelectron spectroscopy test chart of the nitrogen-doped graphene material N1s prepared in example 1 of the present invention.
Fig. 4 is an X-ray photoelectron spectroscopy test chart of C1s of the nitrogen-doped graphene material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the embodiments of the present invention will be described in detail and fully with reference to the accompanying drawings. 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
0.1g of graphene with the sheet diameter of 0.2 mu m is added into 25ml of N, N' -dimethylformamide, magnetic stirring is carried out for 60 minutes at the rotating speed of 600r/min, and then the graphene is placed into an ultrasonic dispersion instrument and subjected to ultrasonic treatment for 60 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.8 g of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole into 25ml of N, N ' -dimethylformamide, adding the graphene solution, heating at 100 ℃ for 30min, cooling to 0 ℃, and drying for 48h to obtain the graphene-coated 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole eutectic compound.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic substance into powder, placing the powder in a tube furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the nitrogen-doped graphene material with the nitrogen content of 18.3%.
Example 2
0.1g of graphene with the sheet diameter of 100 mu m is added into 25ml of N, N' -dimethylformamide, magnetic stirring is carried out for 60 minutes at the rotating speed of 600r/min, and then the graphene is placed in an ultrasonic dispersion instrument and is subjected to ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.2g of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole into 25ml of N, N ' -dimethylformamide, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole eutectic compound.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic substance coated by the graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the nitrogen-doped graphene material with the nitrogen content of 15.4%.
Example 3
0.1g of graphene with the sheet diameter of 100 mu m is added into 25ml of N, N' -dimethylformamide, magnetic stirring is carried out for 60 minutes at the rotating speed of 600r/min, and then the graphene is placed in an ultrasonic dispersion instrument and is subjected to ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.1g of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole into 25ml of N, N ' -dimethylformamide, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole eutectic compound.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic substance coated by the graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the nitrogen-doped graphene material with the nitrogen content of 8.19%.
Example 4
0.1g of graphene with the sheet diameter of 100 mu m is added into 25ml of N, N' -dimethylformamide, magnetic stirring is carried out for 60 minutes at the rotating speed of 600r/min, and then the graphene is placed in an ultrasonic dispersion instrument and is subjected to ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.4g of 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole into 25ml of N, N ' -dimethylformamide, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole eutectic compound.
Grinding the 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic substance coated by the graphene into powder, placing the powder in a tubular furnace, heating to 600 ℃, and preserving heat for 4 hours to obtain the nitrogen-doped graphene material with the nitrogen content of 17.5%.
Scanning electron microscope tests are performed on the nitrogen-doped graphene material prepared in example 1, and as shown in fig. 1, fig. 1 shows a scanning electron microscope test chart of the nitrogen-doped graphene material prepared in example 1. As can be seen from fig. 1, in the material, graphene is uniformly coated on the surface of the 5,5 '-diamino-3, 3' -1,2, 4-triazole crystal, and additives such as an adhesive are not required, so that the surface performance of the 5,5 '-diamino-3, 3' -1,2, 4-triazole crystal is completely maintained.
The nitrogen-doped graphene material and the non-nitrogen-doped graphene material prepared in example 1 were subjected to X-ray photoelectron spectroscopy. As shown in fig. 3, it can be seen from fig. 2 that a peak appears in the binding energy at 398-.
Further, X-ray photoelectron spectroscopy analysis was performed on N1s of nitrogen-doped graphene, and as shown in fig. 3, pyridine type N, pyrrole type N, graphite type N, and pyridine N oxide appeared at 398.4, 400.1, 401.2, and 402.4eV, respectively.
Further, X-ray photoelectron spectroscopy analysis was performed on C1s of nitrogen-doped graphene, and as shown in fig. 4, C-C, C-N and C ═ O (C ═ N) bonds appeared at 284.5, 285.5, and 287.8eV, respectively, indicating that 5,5 '-diamino-3, 3' -1,2, 4-triazole was used as a nitrogen source to prepare nitrogen-doped graphene, which acted on the mechanism of graphene.
Combining the above tests, it was demonstrated that 5,5 '-diamino-3, 3' -1,2, 4-triazole is feasible to dope graphene as a nitrogen source.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of a nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole, is characterized by comprising the following steps: dispersing graphene in N, N '-dimethylformamide, adding an N, N' -dimethylformamide solution of 5,5 '-diamino-3, 3' -1,2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to 0-4 ℃, and drying to obtain a graphene-coated 5,5 '-diamino-3, 3' -1,2, 4-triazole eutectic compound; grinding the graphene oxide powder into powder, and placing the powder in a tubular furnace to be heated for 3-5 hours at 500-800 ℃ to obtain a nitrogen-doped graphene material; the mass ratio of the graphene to the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole in the N, N ' -dimethylformamide solution of the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole is 1: 1-10.
2. The preparation method of the nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole according to claim 1, wherein the number of graphene layers is 1-2, and the sheet diameter is 0.2-100 μm.
3. The preparation method of the nitrogen-doped graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole according to claim 1, wherein the mass ratio of the graphene to the 5,5 '-diamino-3, 3' -1,2, 4-triazole is 1: 4-8.
4. The preparation method of the nitrogen-doped graphene material based on the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole according to claim 1, wherein the concentration of the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole in the N, N ' -dimethylformamide solution of the 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole is 1-5 mg/mL.
5. The preparation method of the nitrogen-doped graphene material based on the 5,5 '-diamino-3, 3' -1,2, 4-triazole according to the claim 1, characterized in that the heating temperature of the tube furnace is set to 600 ℃ and the heating time is 4 h.
6. The preparation method of the nitrogen-doped graphene material based on 5,5 ' -diamino-3, 3 ' -1,2, 4-triazole according to claim 1, characterized in that the following method is adopted for the N, N ' -dimethylformamide dispersion liquid of graphene: adding graphene into N, N '-dimethylformamide, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the N, N' -dimethylformamide is 1: 20-30.
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| CN111508726A (en) * | 2020-06-10 | 2020-08-07 | 广东石油化工学院 | Preparation method of dendritic fiber-shaped hollow nitrogen-doped carbon nanocage for supercapacitor |
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| CN108101037A (en) * | 2017-12-23 | 2018-06-01 | 深圳大学 | A kind of preparation method of the nitrogen-doped graphene material based on diamino azo furazan |
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| CN108101037A (en) * | 2017-12-23 | 2018-06-01 | 深圳大学 | A kind of preparation method of the nitrogen-doped graphene material based on diamino azo furazan |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111508726A (en) * | 2020-06-10 | 2020-08-07 | 广东石油化工学院 | Preparation method of dendritic fiber-shaped hollow nitrogen-doped carbon nanocage for supercapacitor |
| CN111508726B (en) * | 2020-06-10 | 2021-10-08 | 广东石油化工学院 | Preparation method of dendritic fiber-shaped hollow nitrogen-doped carbon nanocage for supercapacitor |
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