CN110980716A - Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole - Google Patents
Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole Download PDFInfo
- Publication number
- CN110980716A CN110980716A CN201911361873.4A CN201911361873A CN110980716A CN 110980716 A CN110980716 A CN 110980716A CN 201911361873 A CN201911361873 A CN 201911361873A CN 110980716 A CN110980716 A CN 110980716A
- Authority
- CN
- China
- Prior art keywords
- amino
- triazole
- graphene
- nitrogen
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a 4-amino-1, 2, 4-triazole-based nitrogen-doped graphene material, which comprises the steps of dispersing graphene in deionized water, adding an aqueous solution of 4-amino-1, 2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to room temperature, and drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole eutectic compound; grinding the graphene oxide into powder, and placing the powder in a tube furnace to be heated for 3-5 hours at 500-800 ℃ to obtain the nitrogen-doped graphene material. Graphene in the material obtained by the invention is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 4-amino-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 4-amino-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 4-amino-1, 2, 4-triazole, and aims to solve the problem that the application is limited because the graphene material is not easily compounded with other materials.
The invention provides a preparation method of a nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole, which comprises the following steps: dispersing graphene in deionized water, adding an aqueous solution of 4-amino-1, 2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to room temperature, drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole eutectic compound, grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain a nitrogen-doped graphene material; the mass ratio of the graphene to the 4-amino-1, 2, 4-triazole in the 4-amino-1, 2, 4-triazole aqueous solution 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 4-amino-1, 2, 4-triazole is 1: 4-8.
Preferably, the concentration of 4-amino-1, 2, 4-triazole in the aqueous solution of 4-amino-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 graphene aqueous dispersion is prepared by the following method: adding graphene into deionized water, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the deionized water is 1: 20-30.
According to the preparation method of the nitrogen-doped graphene material, provided by the invention, 4-amino-1, 2, 4-triazole is used for reacting with graphene to obtain the graphene material with high nitrogen-doped content. In the material, graphene is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 4-amino-1, 2, 4-triazole crystal is completely maintained. By the heat evolved during the thermal cracking of 4-amino-1, 2, 4-triazole and the liberation of N2The free radicals further open the energy band gap and C-C bond of the graphene, adjust the conductivity type and change the electronic structure; 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
Adding 0.1g of graphene with the sheet diameter of 0.2 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 60 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.4 g of 4-amino-1, 2, 4-triazole into 25ml of deionized water, adding the graphene solution, heating at 100 ℃ for 30min, cooling to 0 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound.
Grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic crystal 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 10.76%.
Example 2
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.2g of 4-amino-1, 2, 4-triazole into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound.
Grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic crystal 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 7.86%.
Example 3
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.1g of 4-amino-1, 2, 4-triazole into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound.
Grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic crystal 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 5.29%.
Example 4
Adding 0.1g of graphene with the sheet diameter of 100 mu m into 25ml of deionized water, magnetically stirring for 60 minutes at the rotating speed of 600r/min, and then placing the graphene in an ultrasonic dispersion instrument for ultrasonic treatment for 30 minutes to obtain a graphene solution with the concentration of 4 mg/ml.
And (2) melting 0.8g of 4-amino-1, 2, 4-triazole into 25ml of deionized water, adding the graphene solution, heating at 70 ℃ for 60min, cooling to 4 ℃, and drying for 48h to obtain the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound.
Grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic mixture 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 8.56%.
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 shown in figure 1, graphene in the material is uniformly coated on the surface of the 4-amino-1, 2, 4-triazole eutectic crystal, and auxiliaries such as an adhesive are not needed, so that the surface performance of the 4-amino-1, 2, 4-triazole eutectic 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. 2, 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, 401.7, and 402.8eV, respectively.
Further, by performing X-ray photoelectron spectroscopy analysis on C1s of nitrogen-doped graphene, as shown in fig. 4, C-C, C-N, C-O and C = O/C = N bonds appear at 284.4, 285.4, 286.6 and 289.2eV, which indicates that 4-amino-1, 2, 4-triazole eutectic compound as a nitrogen source is used for preparing nitrogen-doped graphene to play a role in the mechanism of graphene.
The above tests are combined to show that the 4-amino-1, 2, 4-triazole eutectic is feasible to be used as a nitrogen source for doping graphene.
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 4-amino-1, 2, 4-triazole is characterized by comprising the following steps: dispersing graphene in deionized water, adding an aqueous solution of 4-amino-1, 2, 4-triazole, heating at 50-100 ℃ for 30-60 min, cooling to room temperature, drying to obtain a graphene-coated 4-amino-1, 2, 4-triazole eutectic compound, grinding the graphene-coated 4-amino-1, 2, 4-triazole eutectic compound into powder, and heating in a tubular furnace at 500-800 ℃ for 3-5 h to obtain a nitrogen-doped graphene material; the mass ratio of the graphene to the 4-amino-1, 2, 4-triazole in the 4-amino-1, 2, 4-triazole aqueous solution is 1: 1-10.
2. The preparation method of the nitrogen-doped graphene material based on the 4-amino-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 4-amino-1, 2, 4-triazole according to claim 1, wherein the mass ratio of the graphene to the 4-amino-1, 2, 4-triazole is 1: 4-8.
4. The preparation method of the nitrogen-doped graphene material based on the 4-amino-1, 2, 4-triazole according to claim 1, wherein the concentration of the 4-amino-1, 2, 4-triazole in the 4-amino-1, 2, 4-triazole solution is 1-5 mg/mL.
5. The preparation method of the nitrogen-doped graphene material based on the 4-amino-1, 2, 4-triazole according to claim 1, wherein 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 4-amino-1, 2, 4-triazole according to claim 1, wherein the aqueous graphene dispersion is prepared by the following method: dispersing graphene into deionized water, stirring for 30-90 min, and ultrasonically shaking for 30-60 min, wherein the mass ratio of the graphene to the deionized water is 1: 20-30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911361873.4A CN110980716A (en) | 2019-12-26 | 2019-12-26 | Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911361873.4A CN110980716A (en) | 2019-12-26 | 2019-12-26 | Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110980716A true CN110980716A (en) | 2020-04-10 |
Family
ID=70076935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911361873.4A Withdrawn CN110980716A (en) | 2019-12-26 | 2019-12-26 | Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110980716A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2019
- 2019-12-26 CN CN201911361873.4A patent/CN110980716A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| B. GRZYB ET AL.: "Guanidine, amitrole and imidazole as nitrogen dopants for the synthesis of N-graphenes", 《RSC ADV.》 * |
| JINGSHUAI YANG ET AL.: "Novel composite membranes of triazole modified graphene oxide and polybenzimidazole for high temperature polymer electrolyte membrane fuel cell applications", 《RSC ADV.》 * |
| YONGFENG LI ET AL.: "Advanced oxygen reduction reaction catalyst based on nitrogen and sulfur co-doped graphene in alkaline medium", 《PHYS.CHEM.CHEM.PHYS.》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108101037B (en) | Preparation method of nitrogen-doped graphene material based on diamino azo furazan | |
| CN108101038B (en) | Preparation method of nitrogen-doped graphene with furazan derivatives as nitrogen source | |
| KR20130084120A (en) | Thermoelectric nano-composite, and thermoelectric module and thermoelectric apparatus comprising same | |
| US7150911B2 (en) | Electrical insulating vapor grown carbon fiber and method for producing the same, and use thereof | |
| CN104103821B (en) | The preparation method of silicon-carbon cathode material | |
| CN111747385B (en) | In-situ synthesis boron nitride nanosheet-nanotube composite material and preparation method thereof | |
| CN111154994B (en) | Graphene-aluminum composite material and preparation method thereof | |
| CN110331405B (en) | Liquid metal and graphite composite heat dissipation film and preparation method thereof | |
| CN111072021A (en) | Preparation method of nitrogen-doped graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole | |
| CN110937597A (en) | Preparation method of nitrogen-doped graphene material based on 3, 5-diamino-1-hydro-1, 2, 4-triazole | |
| CN111017917A (en) | Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole-5-one | |
| CN112321990B (en) | Preparation method of molybdenum diselenide and carbon nano tube composite wave-absorbing material | |
| CN102249652B (en) | Fiber composite material with microwave absorbing function and preparation method thereof | |
| CN110980716A (en) | Preparation method of nitrogen-doped graphene material based on 4-amino-1, 2, 4-triazole | |
| CN110980714A (en) | Preparation method of nitrogen-doped graphene material based on 4, 4' -azo-1, 2, 4-triazole | |
| CN111003707A (en) | Preparation method of nitrogen-doped graphene material based on 4, 4' -azo-1, 2, 4-triazole-5-ketone | |
| CN110980713A (en) | Preparation method of graphene material based on 5,5 '-diamino-3, 3' -1,2, 4-triazole cobalt salt | |
| CN110980715A (en) | Preparation method of nitrogen-cobalt co-doped graphene material based on 4-amino-1, 2, 4-triazole-5-keto cobalt salt | |
| CN109950113B (en) | Preparation method and application of silver-rich silver selenide flexible field emission cathode material grown on carbon cloth | |
| CN114031074B (en) | Three-dimensional heat-conducting wave-absorbing reinforced composite film and preparation method thereof | |
| WO2019119460A1 (en) | Method for preparing nitrogen-doped graphene from furazan derivatives as nitrogen source | |
| CN114804886A (en) | Preparation method of carbon modified nano silicon carbide composite material and application of carbon modified nano silicon carbide composite material as radiation detector material | |
| KR102172600B1 (en) | Manufacturing method of silicon nitride having excellent heat dissipation properties | |
| TW559910B (en) | Heat treatment apparatus and wafer support ring | |
| CN112592667A (en) | Heat-conductive electric appliance insulation foam adhesive tape for high temperature and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200410 |