CN111689486A - Preparation method of N-containing graphdiyne material - Google Patents
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Abstract
The invention discloses a preparation method of an N-containing graphite alkyne material, which comprises the steps of taking an N-containing hexatomic heterocyclic compound and a metal acetylide as raw materials, taking ethanol as a solvent, carrying out ultrasonic reaction under the condition that the ultrasonic frequency is 50-55 KHZ, separating after the reaction is finished, washing and drying collected solids, and thus obtaining the N-containing graphite alkyne material. According to the invention, an ultrasonic method is adopted, the N-containing graphite alkyne material is prepared by taking the N-containing hexatomic heterocyclic compound and the metal acetylide as raw materials and ethanol as a solvent, nitrogen elements in the prepared N-containing graphite alkyne material are distributed orderly, and the whole preparation method is simple to operate, mild in condition, green and environment-friendly, and has low requirements on equipment; in addition, experiments show that the N-containing graphdiyne material prepared by the method has excellent hydrogen evolution performance and energy storage performance, effectively promotes the application of the graphdiyne material in multiple fields of hydrogen evolution materials, supercapacitors, lithium ion battery cathode materials and the like, and has wide industrial application prospects.
Description
Technical Field
The invention relates to a preparation method of an N-containing graphdiyne material, belonging to the technical field of carbon materials.
Background
Graphyne (Graphyne) is a novel carbon material following fullerenes, carbon nanotubes, graphene. The graphyne is a stable two-dimensional layered structure carbon material and is formed by sp hybridized carbon atoms and sp2The hybridized carbon atom is formed by conjugation, has a unique delocalized big pi-bond structure, shows unique photoelectrochemistry and energy storage properties, and has wide application in the fields of energy, catalysis, electrons and the likeAnd 4, application prospect.
Researches find that the nitrogen element doping can effectively improve the performances of the graphite alkyne in the aspects of electrochemical performance, redox activity and the like. At present, few reports about the preparation of the N-containing graphyne material are reported, and the preparation of the N-containing graphyne material is not beneficial to the popularization and application of the N-containing graphyne material because the distribution of nitrogen elements in the prepared graphyne is disordered or the requirements on equipment and conditions are high in the preparation process.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing an N-containing graphdiyne material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an N-containing graphite alkyne material comprises the steps of taking an N-containing hexatomic heterocyclic compound and a metal acetylide as raw materials, taking ethanol as a solvent, carrying out ultrasonic reaction under the condition that the ultrasonic frequency is 50-55 KHZ, separating after the reaction is finished, washing and drying collected solids, and obtaining the N-containing graphite alkyne material.
In one embodiment, the preparation of the N-containing graphdiyne material comprises the steps of:
a) adding a N-containing hexatomic heterocyclic compound, a metal acetylide and ethanol into a reaction container, and then carrying out ultrasonic reaction under the conditions of inert gas protection, normal temperature and ultrasonic frequency of 50-55 KHZ;
b) and separating after the reaction is finished, and carrying out acid washing, drying, ethanol washing and drying on the collected solid in sequence to obtain the N-containing graphite alkyne material.
In one embodiment, step a), the N-containing six-membered heterocyclic compound is selected from any one of substituted or unsubstituted pyridine, substituted or unsubstituted pyrazine, substituted or unsubstituted triazine, substituted or unsubstituted pyrimidine, and substituted or unsubstituted pyridazine.
In a preferred embodiment, in step a), the N-containing six-membered heterocyclic compound is selected from any one of pyridine, pyrazine, triazine, pyrimidine, pyridazine and trichlorotriazine, preferably pyrazine.
In one embodiment, step a), the metal acetylide is an alkali metal or alkaline earth metal acetylide, preferably calcium acetylide (aka calcium acetylide, calcium carbide).
In one embodiment, in step a), the molar ratio of the N-containing six-membered heterocyclic compound to the metal acetylide is 1:4 to 1: 20.
In one embodiment, in the step b), dilute nitric acid with the concentration of 0.1-2.5 mol/L is used for washing during acid washing.
In one embodiment, in the step b), the drying temperature is 60-80 ℃.
Compared with the prior art, the invention has the following remarkable beneficial effects:
according to the invention, an ultrasonic method is adopted, the N-containing graphite alkyne material is prepared by taking the N-containing hexatomic heterocyclic compound and the metal acetylide as raw materials and ethanol as a solvent, nitrogen elements in the prepared N-containing graphite alkyne material are distributed orderly, and the whole preparation method is simple to operate, mild in condition, green and environment-friendly, and has low requirements on equipment; in addition, experiments show that the N-containing graphdiyne material prepared by the method has excellent hydrogen evolution performance and energy storage performance, effectively promotes the application of the graphdiyne material in multiple fields of hydrogen evolution materials, supercapacitors, lithium ion battery cathode materials and the like, and has wide industrial application prospects.
Drawings
FIG. 1 is a block diagram of the N-containing graphdine of example 1;
FIG. 2 is an X-ray diffraction energy spectrum of N-containing graphdine of example 1;
FIG. 3 is a Raman plot of the N-containing graphdine of example 1;
FIG. 4 is an infrared image of N-containing graphdine of example 1;
FIG. 5 is a Tafel plot of N-containing graphdine of example 2;
FIG. 6 is a linear voltammogram scan of the N-containing graphdine of example 2;
FIG. 7 is a plot of the cyclic voltammetry measurements for N-containing graphdine of example 3;
FIG. 8 is a constant current charge and discharge curve for N-containing graphdiyne in example 3;
fig. 9 is a graph of the capacitive stability of the N-containing graphdiyne of example 3.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining specific embodiments.
Example 1
Adding pyrazine and calcium carbide in a molar ratio of 1:5 into a reaction container, adding absolute ethyl alcohol (the addition amount of the ethyl alcohol is larger than that of a sample), carrying out ultrasonic reaction for 12 hours under the conditions of argon protection, normal temperature and ultrasonic frequency of 53KHz, finishing the reaction, separating, washing the collected solid with 1mol/L dilute nitric acid to remove unreacted calcium carbide, drying the obtained solid at 60 ℃, grinding, washing the obtained solid with ethyl alcohol to remove unreacted pyrazine, drying the obtained solid at 60 ℃, and grinding to obtain powdery N-containing grapyne.
FIG. 1 is a structural diagram of N-containing graphdiyne prepared in this example, in which the nitrogen elements are arranged in order in a two-dimensional structure;
FIG. 2 is an X-ray diffraction energy spectrum of the N-containing graphyne prepared in this example, from which it can be seen that there are substantially no impurities other than the characteristic peaks of the N-containing graphyne;
fig. 3 is a raman chart of the N-containing graphyne prepared in the present example, and fig. 4 is an infrared chart of the N-containing graphyne prepared in the present example, and as can be seen from fig. 3 and 4, characteristic peaks of C — N bonds exist in the spectra, which proves that the prepared product is the N-containing graphyne.
Example 2
Adding pyrazine and calcium carbide in a molar ratio of 1:10 into a reaction container, adding absolute ethyl alcohol (the addition amount of the ethyl alcohol is larger than that of a sample), carrying out ultrasonic reaction for 12 hours under the conditions of argon protection, normal temperature and ultrasonic frequency of 53KHz, finishing the reaction, separating, washing collected solids with dilute nitric acid with the concentration of 1mol/L to remove unreacted calcium carbide, drying the obtained solids at 70 ℃, grinding, washing the obtained solids with ethyl alcohol to remove unreacted pyrazine, drying the obtained solids at 70 ℃, and grinding to obtain powdery N-containing grapyne.
The N-containing graphdiyne prepared in this example was tested for hydrogen evolution performance:
20mg of the N-containing graphdine obtained in the example was added to a hydrothermal reaction kettle, 5 pieces of cleaned nickel foam were added, and the hydrothermal reaction was carried out at 160 ℃ for 12 hours, that is, the N-containing graphdine was supported on the nickel foam, which was then subjected to an electrochemical test, and the test results are shown in fig. 5 and 6.
Fig. 5 is a tafel test curve of the N-containing graphyne prepared in this example, and fig. 6 is a linear voltammetry scan curve of the N-containing graphyne prepared in this example, and as can be seen from fig. 5 and 6, the N-containing graphyne prepared in this example has smaller resistance compared to the common pure graphyne, and the overpotential is increased with the increase of the scan rate, which indicates that the N-containing graphyne prepared by the method of the present invention has more excellent hydrogen evolution performance and is expected to be developed into a hydrogen evolution material.
Example 3
Adding pyrazine and calcium carbide in a molar ratio of 1:15 into a reaction container, adding absolute ethyl alcohol (the addition amount of the ethyl alcohol is larger than that of a sample), carrying out ultrasonic reaction for 12 hours under the conditions of argon protection, normal temperature and ultrasonic frequency of 53KHz, finishing the reaction, separating, washing the collected solid with 1mol/L dilute nitric acid to remove unreacted calcium carbide, drying the obtained solid at 80 ℃, grinding, washing the obtained solid with ethyl alcohol to remove unreacted pyrazine, drying the obtained solid at 80 ℃, and grinding to obtain powdery N-containing grapyne.
The energy storage performance of the N-containing graphdiyne prepared in this example was tested:
adding the N-containing graphdiyne prepared in the embodiment, a conductive agent (acetylene black) and a binder (polytetrafluoroethylene dispersion liquid) into absolute ethyl alcohol according to a mass ratio of 8:1:1, stirring and mixing the materials into a slurry under a dry atmosphere, then uniformly coating the slurry on foamed nickel, tabletting and drying the slurry, then placing the obtained material on a Chenghua CHI660E instrument, and measuring at different scanning rates and current densities to obtain a linear voltammetry curve and a constant current charge-discharge curve, which are respectively shown in FIG. 7 and FIG. 8; the resulting material was then measured for its cycling stability at 3A/g, with the results shown in FIG. 9.
FIG. 7 is a plot of cyclic voltammetry measurements for N-containing graphdiynes prepared in this example; FIG. 8 is a constant current charge and discharge curve of N-containing graphdiyne prepared in this example; as can be seen from fig. 7 and 8, the N-containing graphdiyne prepared in this example has excellent electrochemical properties.
Fig. 9 is a graph of capacitance stability of the N-containing graphdiyne prepared in this example, and as can be seen from fig. 9, the N-containing graphdiyne prepared in this example has high capacitance retention rate and good capacitance stability, which indicates that it has good energy storage performance and is expected to be developed into an energy storage material.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (6)
1. A preparation method of an N-containing graphdiyne material is characterized by comprising the following steps: the method comprises the steps of taking an N-containing hexatomic heterocyclic compound and a metal acetylide as raw materials, taking ethanol as a solvent, carrying out ultrasonic reaction under the condition that the ultrasonic frequency is 50-55 KHZ, separating after the reaction is finished, washing and drying collected solids, and obtaining the N-containing graphite alkyne material.
2. The method of claim 1, wherein the preparation of the N-containing graphdiyne material comprises the steps of:
a) adding a N-containing hexatomic heterocyclic compound, a metal acetylide and ethanol into a reaction container, and then carrying out ultrasonic reaction under the conditions of inert gas protection, normal temperature and ultrasonic frequency of 50-55 KHZ;
b) and separating after the reaction is finished, and carrying out acid washing, drying, ethanol washing and drying on the collected solid in sequence to obtain the N-containing graphite alkyne material.
3. The method of claim 2, wherein: in the step a), the N-containing six-membered heterocyclic compound is selected from any one of substituted or unsubstituted pyridine, substituted or unsubstituted pyrazine, substituted or unsubstituted triazine, substituted or unsubstituted pyrimidine and substituted or unsubstituted pyridazine.
4. The production method according to claim 3, characterized in that: the N-containing six-membered heterocyclic compound is selected from any one of pyridine, pyrazine, triazine, pyrimidine, pyridazine and trichlorotriazine.
5. The method of claim 2, wherein: in step a), the metal acetylide is an alkali metal or alkaline earth metal acetylide.
6. The method of claim 2, wherein: in the step a), the molar ratio of the N-containing hexatomic heterocyclic compound to the metal acetylide is 1: 4-1: 20.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112138691A (en) * | 2020-10-13 | 2020-12-29 | 青岛科技大学 | Preparation method of graphite alkyne enhanced CoP nanoparticle electrocatalyst wrapped by N, C and P containing layers |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
| CN113075279A (en) * | 2021-04-30 | 2021-07-06 | 南京师范大学 | Application of nitrogen-doped graphite alkyne quantum dots in chloramphenicol detection |
| CN113214829A (en) * | 2021-04-30 | 2021-08-06 | 南京师范大学 | Preparation method of graphite alkyne quantum dot, quantum dot prepared by preparation method and application of quantum dot |
| CN113224322A (en) * | 2021-04-30 | 2021-08-06 | 南京师范大学 | Nitrogen-doped electrocatalyst and preparation method and application thereof |
| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114229828A (en) * | 2021-11-24 | 2022-03-25 | 上海工程技术大学 | Preparation method of gamma-graphite monoalkyne |
| CN114604848A (en) * | 2022-03-17 | 2022-06-10 | 武汉工程大学 | Nitrogen-rich graphdiyne and preparation method thereof |
| CN115159507A (en) * | 2022-08-12 | 2022-10-11 | 郑州大学 | Preparation method of ferromagnetic graphdiyne |
| CN115448290A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院化学研究所 | Method for synthesizing graphdiyne and introducing two different structural units into graphdiyne |
Citations (1)
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| CN111137875A (en) * | 2020-01-14 | 2020-05-12 | 安徽工业大学 | In-situ doped graphite monoalkyne, preparation method and application |
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- 2020-06-15 CN CN202010543049.7A patent/CN111689486A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111137875A (en) * | 2020-01-14 | 2020-05-12 | 安徽工业大学 | In-situ doped graphite monoalkyne, preparation method and application |
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| CN112138691A (en) * | 2020-10-13 | 2020-12-29 | 青岛科技大学 | Preparation method of graphite alkyne enhanced CoP nanoparticle electrocatalyst wrapped by N, C and P containing layers |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
| CN113224322B (en) * | 2021-04-30 | 2022-05-03 | 南京师范大学 | Nitrogen-doped electrocatalyst and preparation method and application thereof |
| CN113214829A (en) * | 2021-04-30 | 2021-08-06 | 南京师范大学 | Preparation method of graphite alkyne quantum dot, quantum dot prepared by preparation method and application of quantum dot |
| CN113224322A (en) * | 2021-04-30 | 2021-08-06 | 南京师范大学 | Nitrogen-doped electrocatalyst and preparation method and application thereof |
| CN113075279A (en) * | 2021-04-30 | 2021-07-06 | 南京师范大学 | Application of nitrogen-doped graphite alkyne quantum dots in chloramphenicol detection |
| CN113075279B (en) * | 2021-04-30 | 2023-07-21 | 南京师范大学 | Application of nitrogen doped graphite alkyne quantum dot in chloramphenicol detection |
| CN115448290A (en) * | 2021-06-08 | 2022-12-09 | 中国科学院化学研究所 | Method for synthesizing graphdiyne and introducing two different structural units into graphdiyne |
| CN115448290B (en) * | 2021-06-08 | 2023-05-16 | 中国科学院化学研究所 | Method for synthesizing graphite alkyne and introducing two different structural units into graphite alkyne |
| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN113578362B (en) * | 2021-07-23 | 2023-09-08 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114229828A (en) * | 2021-11-24 | 2022-03-25 | 上海工程技术大学 | Preparation method of gamma-graphite monoalkyne |
| CN114604848A (en) * | 2022-03-17 | 2022-06-10 | 武汉工程大学 | Nitrogen-rich graphdiyne and preparation method thereof |
| CN114604848B (en) * | 2022-03-17 | 2023-03-21 | 武汉工程大学 | Nitrogen-rich graphdiyne and preparation method thereof |
| CN115159507A (en) * | 2022-08-12 | 2022-10-11 | 郑州大学 | Preparation method of ferromagnetic graphdiyne |
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Application publication date: 20200922 |