CN111137875A - In-situ doped graphite monoalkyne, preparation method and application - Google Patents
In-situ doped graphite monoalkyne, preparation method and application Download PDFInfo
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Abstract
The invention discloses an in-situ doped graphite monoalkyne, a preparation method and application thereof, wherein calcium carbide and polyhalogenated hydrocarbon containing heteroatoms are mixed, then the mixture is added into a ball mill once or for many times, and ball milling reaction is carried out under the protection of vacuum or normal pressure inert gas to obtain a reaction product; washing the reaction product with dilute nitric acid, and then washing with ethanol or benzene to obtain a washing product; and (3) drying the washing product in vacuum, and then grinding the washing product into powder to obtain the powdery in-situ doped graphite mono-alkyne material. The invention has the advantages of cheap and easily obtained reaction raw materials, mild reaction conditions, simple reaction equipment and simple and convenient reaction process. The synthesized doped graphite monoalkyne has various types, and the type and the heteroatom content of the synthesized in-situ doped graphite monoalkyne can be regulated and controlled according to the selection of different polyhalogenated hydrocarbons containing heteroatoms. The generated alkyne carbon material has uniform texture, excellent physical and chemical properties, good pore structure and important and wide application prospect in the fields of energy, catalysis, environmental protection and the like.
Description
Technical Field
The invention relates to preparation of a carbon nano material, in particular to in-situ doped graphite monoalkyne, a preparation method and application thereof.
Background
The discovery and application exploration of novel carbon materials is one of the leading edges and research hotspots of material science. In recent years, carbon nanotubes and fullerene C60Novel carbon materials such as graphene and graphdiyne are discovered or synthesized in succession, have great influence on scientific research and human life by virtue of unique structures and properties, and provide great assistance for the fields of energy, environment, catalysis and the like. Wherein the graphatidyne (including graphatidyne and graphatidyne) is sp and sp2The alkynyl-rich carbon material with a wide-area two-dimensional planar network structure, which is formed by combining hybridized carbon atoms, has general attention to the unique physicochemical property, electrical property and structure adjustability.
At present, graphite diyne is successfully synthesized through Glaser-Hay cross coupling reaction, and has been deeply researched in the application of the graphite diyne in the fields of supercapacitors, lithium ion batteries, solar batteries, photocatalysis, electrocatalysis, photodetectors and the like. Meanwhile, breakthrough research progress is made on the mechanochemical synthesis technology of the graphite monoalkyne, and huge application potential is shown in the fields of energy storage, environment and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to realize the doping preparation of the graphite monoalkyne, and provides an in-situ doped graphite monoalkyne, a preparation method and application thereof.
The invention solves the technical problems through the following technical scheme, and the preparation method of the in-situ doped graphite monoalkyne comprises the following steps:
(1) mixing calcium carbide and polyhalogenated hydrocarbon containing heteroatoms according to a molar ratio of 4-12: 1, mixing, adding the mixture into a ball mill once or for multiple times, and carrying out ball milling reaction for 0.5-10 h under the protection of vacuum or normal pressure inert gas to obtain a reaction product;
(2) washing the reaction product with dilute nitric acid, and then washing with ethanol or benzene to obtain a washing product;
(3) and (3) drying the washing product at 120 ℃ in vacuum, and then grinding the washing product into powder to obtain the powdery in-situ doped graphite monoalkyne material.
In a preferred embodiment of the present invention, the ball milling reaction temperature is normal temperature, and the ball milling rate is 400 to 700 r/min.
As one of the preferred modes of the invention, the heteroatom-containing polyhalogenated hydrocarbon is selected from pentachloropyridine C5Cl5N, tetrabromothiophene C4Br4S, tetrabromophthalic anhydride C8Br4O3Endosulfan C9H6Cl6O3S, pentachloronitrobenzene C6Cl5NO2Decabromodiphenyl ether C12Br10O or a combination of several O.
In a preferred embodiment of the present invention, the ball mill is selected from any one of a vibration ball mill, an agitator ball mill, a tumbling ball mill and a planetary ball mill.
An in-situ doped graphitic monoalkyne prepared using the method.
In the preparation process of the in-situ doped graphite single alkyne, the mechanical ball milling is used for exciting the reaction activity of the calcium carbide, so that the alkynyl in the calcium carbide is free, the property of a strong nucleophilic group is embodied, the nucleophilic substitution of halogen on the polyhalogenated hydrocarbon containing the heteroatom is completed, and the alkyne carbon nano-net containing the heteroatom is finally constructed.
The in-situ doped graphite single alkyne is a heteroatom-containing carbon skeleton with an ultra-wide conjugated structure connected by alkynyl. By selecting different precursors, the change of doping elements or structures can be realized.
The in-situ doped graphite monoalkyne is applied to the preparation of electricity storage materials, semiconductors and catalytic materials.
Compared with the prior art, the invention has the following advantages: the invention provides a novel method for synthesizing in-situ doped graphite monoalkyne by taking calcium carbide and polyhalogenated hydrocarbon containing heteroatoms as raw materials and utilizing a mechanochemical principle, wherein the reaction raw materials are cheap and easy to obtain, the reaction conditions are mild, the reaction equipment is simple, the reaction process is simple and convenient, and complex post-treatment is not required. The synthesized doped graphite monoalkyne has various types, and the type and the heteroatom content of the synthesized in-situ doped graphite monoalkyne can be regulated and controlled according to the selection of different polyhalogenated hydrocarbons containing heteroatoms. The generated alkyne carbon material has uniform texture, excellent physical and chemical properties, good pore structure and important and wide application prospect in the fields of energy, catalysis, environmental protection and the like.
Drawings
FIG. 1 is a schematic structural diagram of in-situ doped graphite monoalkyne prepared in examples 1-5;
FIG. 2 is an X-ray photoelectron spectrum C of the in-situ doped graphite monoalkyne prepared in examples 1-2;
FIG. 3 is a Scanning Electron Microscope (SEM) of in-situ doped graphite monoalkyne prepared in examples 1-5;
FIG. 4 is a Transmission Electron Micrograph (TEM) of the in-situ doped graphitic monoalkyne prepared in examples 1-5;
FIG. 5 is an X-ray diffraction pattern (XRD) of the in-situ doped graphite monoalkyne prepared in examples 1-5;
FIG. 6 is a Raman spectrum (Raman) of the in-situ doped graphite monoalkyne prepared in examples 1-5;
FIG. 7 is an electrochemical CV curve of in-situ doped graphite monoalkyne prepared in examples 1-2.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
This example follows calcium carbide (CaC)2) And pentachloropyridine (C)5Cl5N) molar ratio 7.5: 1, respectively weighing calcium carbide and pentachloropyridine, placing the calcium carbide and the pentachloropyridine in a vacuum ball milling tank, and controlling the mass ratio of a grinding ball to total materials to be 20: 1. then replacing air in the ball milling tank with high-purity nitrogen, sealing, and then placing the ball milling tank on an all-directional planetary ball mill. Ball milling was carried out at a ball milling rate of 600 revolutions per minute for 2 hours. To prevent overheating of the machine during operation, the machine was stopped for 5 minutes every 45 minutes of operation. After the reaction is finished, the ball milling tank is opened, the original gray powder is changed into paint black, and the generation of the carbon material is proved. Subsequently, part of the reaction product was taken out and placed in a beaker, treated with dilute nitric acid and the chloride ion content of the filtrate was measured, thereby determining pentachloropyridineThe dechlorination rate of the product was 96.6%. The reaction product was washed with acid and alcohol, and then vacuum dried at 120 ℃ for 5 hours to obtain the in-situ N-doped graphite monoalkyne of the present example, which was weighed and the apparent carbon yield was calculated to be 98%.
The chemical structural formula of the obtained in-situ N-doped graphite monoalkyne is shown in figure 1 a. Elemental analysis showed that the N content of the obtained in-situ N-doped graphitic monoalkyne was 8.5%. The carbon spectrum of the X-ray photoelectron spectrum of the sample (FIG. 2a) shows the presence of sp between the carbon elements in the sample2And sp hybridization, demonstrating the built-in alkynyl structure. The scanning electron microscope test results (fig. 3a-b) show that the in-situ N-doped graphite monoalkyne prepared by the method has a good pore structure. The transmission electron microscope test results (fig. 4a-b) of the in-situ N-doped graphite monoalkyne show that the alkyne carbon material has a typical graphene-like layered structure. X-ray diffraction analysis (fig. 5a) of the resulting in situ N-doped graphitic mono-acetylene shows that the carbon material has a certain crystalline structure. The Raman spectrum (figure 6a) of the obtained in-situ N-doped graphite monoalkyne shows that the carbon material has good order degree.
And placing the obtained in-situ N-doped graphite monoalkyne on foamed nickel to prepare the electrode material of the super capacitor, and carrying out super-capacitance performance test on the electrode material. The CV diagram (figure 7) of the in-situ N-doped graphite monoalkyne obtained by the experiment proves that the in-situ N-doped graphite monoalkyne has excellent super-capacitance performance and the specific volume of the in-situ N-doped graphite monoalkyne can reach 179F/g.
Example 2
According to calcium carbide (CaC)2) And tetrabromothiophene (C)4Br4S) molar ratio of 4: 1, respectively weighing calcium carbide and tetrabromothiophene, placing the calcium carbide and the tetrabromothiophene in a vacuum ball-milling tank, and controlling the mass ratio of grinding balls to total materials to be 30: 1. then replacing the air in the ball milling tank with high-purity argon, sealing, and then placing the ball milling tank on an all-directional planetary ball mill. Ball milling was carried out at a ball milling rate of 550 revolutions per minute for 4 hours. To prevent overheating of the machine during operation, the machine was stopped for 5 minutes every 45 minutes of operation. After the reaction is finished, the ball milling tank is opened, the original gray powder is changed into paint black, and the generation of the carbon material is proved. Subsequently, a part of the reaction product was taken out and placed in a beaker, treated with dilute nitric acid and the chloride ion content in the filtrate was measured, whereby it was determined that the debromination rate of tetrabromothiophene was 956 percent. The reaction product was washed with acid and alcohol, and then vacuum dried at 120 ℃ for 5 hours to obtain the in-situ S-doped graphite monoalkyne of the present example, which was weighed and calculated to have an apparent carbon yield of 102%.
The chemical structural formula of the obtained in-situ S-doped graphite monoalkyne is shown in figure 1 b. Elemental analysis showed that the S content of the obtained in-situ N-doped graphitic monoalkyne was 12.2%. The carbon spectrum of the X-ray photoelectron spectrum of the sample (FIG. 2b) shows the presence of sp between the carbon elements in the sample2And sp hybridization, demonstrating the built-in alkynyl structure. The scanning electron microscope test result (figure 3c) shows that the in-situ S-doped graphite monoalkyne prepared by the method has a good pore structure. The transmission electron microscope test result (fig. 4c) of the in-situ S-doped graphite monoalkyne shows that the alkyne carbon material has a typical graphene-like layered structure. X-ray diffraction analysis (fig. 5b) of the resulting in situ S-doped graphitic mono-acetylene shows that the carbon material has a certain crystalline structure. The Raman spectrum (figure 6b) of the obtained in-situ S-doped graphite monoalkyne shows that the carbon material has good order degree.
And placing the obtained in-situ S-doped graphite monoalkyne on foamed nickel to prepare the electrode material of the super capacitor, and carrying out super-capacitance performance test on the electrode material. The CV diagram (figure 7) of the in-situ S-doped graphite monoalkyne obtained by the experiment proves that the in-situ S-doped graphite monoalkyne has excellent super-capacitance performance and the specific volume of the in-situ S-doped graphite monoalkyne can reach 101F/g.
Example 3
According to calcium carbide (CaC)2) And tetrabromophthalic anhydride (C)8Br4O3) The molar ratio is 6: 1, respectively weighing calcium carbide and tetrabromophthalic anhydride, placing the calcium carbide and the tetrabromophthalic anhydride in a vacuum ball-milling tank, and controlling the mass ratio of a grinding ball to total materials to be 40: 1. then replacing the air in the ball milling tank with high-purity argon, sealing, and then placing the ball milling tank on an all-directional planetary ball mill. Ball milling was carried out at a ball milling rate of 500 revolutions per minute for 6 hours. To prevent overheating of the machine during operation, the machine was stopped for 5 minutes every 45 minutes of operation. After the reaction is finished, the ball milling tank is opened, the original gray powder is changed into paint black, and the generation of the carbon material is proved. Subsequently, a part of the reaction product was taken out and placed in a beaker, treated with dilute nitric acid and the chloride ion content in the filtrate was measured, whereby the debromination rate of tetrabromophthalic anhydride was determined to be 97.8%.The reaction product was washed with acid and alcohol, and then vacuum dried at 120 ℃ for 5 hours to obtain the in-situ O-doped graphite monoalkyne of the present example, which was weighed and the apparent carbon yield was calculated to be 99.5%.
The chemical structural formula of the obtained in-situ O-doped graphite monoalkyne is shown in figure 1 c. Elemental analysis showed that the O content of the obtained in-situ N-doped graphite monoalkyne was 10.3%. The scanning electron microscope test result (figure 3d) shows that the in-situ O-doped graphite monoalkyne prepared by the method has a good pore structure. The transmission electron microscope test result (fig. 4d) of the in-situ S-doped graphite monoalkyne shows that the alkyne carbon material has a typical graphene-like layered structure. X-ray diffraction analysis (fig. 5c) of the resulting in situ O-doped graphitic mono-acetylene showed that the carbon material had a certain crystalline structure. The Raman spectrum (figure 6c) of the obtained in-situ O-doped graphite monoalkyne shows that the carbon material has good order degree.
And pressing the obtained in-situ O-doped graphite monoacyne into a sheet, and testing the conductivity of the sheet by a four-probe method. The conductivity of the obtained in-situ O-doped graphite monoalkyne is 16.1S/cm, and the in-situ O-doped graphite monoalkyne has excellent conductivity and has the potential of becoming a semiconductor material.
Example 4
According to calcium carbide (CaC)2) And endosulfan (C)9H6Cl6O3S) molar ratio of 9: 1, respectively weighing calcium carbide and endosulfan, placing the calcium carbide and endosulfan in a vacuum ball milling tank, and controlling the mass ratio of grinding balls to total materials to be 50: 1. then replacing the air in the ball milling tank with high-purity argon, sealing, and then placing the ball milling tank on an all-directional planetary ball mill. Ball milling was carried out at a ball milling rate of 400 revolutions per minute for 10 hours. To prevent overheating of the machine during operation, the machine was stopped for 5 minutes every 45 minutes of operation. After the reaction is finished, the ball milling tank is opened, the original gray powder is changed into paint black, and the generation of the carbon material is proved. Subsequently, a part of the reaction product was taken out and placed in a beaker, treated with dilute nitric acid and the chloride ion content of the filtrate was measured, whereby it was confirmed that the dechlorination rate of endosulfan was 99.1%. The reaction product is washed by acid and alcohol, and then dried in vacuum for 5 hours at 120 ℃ to obtain the in-situ S, O doped graphite monoalkyne of the embodiment, and the product is weighed and the apparent carbon yield is calculatedThe content was 102.6%.
The chemical structural formula of the obtained in-situ S, O doped graphite monoalkyne is shown in figure 1 d. Elemental analysis showed that the S, O contents of the obtained in-situ N-doped graphitic monoalkyne were 4.1% and 9.3%, respectively. The scanning electron microscope test result (fig. 3e) shows that the in-situ S, O doped graphite monoalkyne prepared by the method has a good pore structure. The transmission electron microscope test result (fig. 4e) of the in-situ S, O doped graphite monoalkyne shows that the alkyne carbon material has a typical graphene-like laminated structure. X-ray diffraction analysis of the resulting in situ S, O doped graphitic mono-acetylene (fig. 5d) showed that the carbon material had a crystalline structure. The Raman spectrum (fig. 6d) of the obtained in-situ S, O doped graphite monoalkyne shows that the carbon material has good order degree.
And pressing the obtained in-situ S, O doped graphite monoacyne into a sheet, and testing the conductivity of the sheet by a four-probe method. The conductivity of the obtained graphite is 17.8S/cm, and the in-situ S, O doped graphite monoalkyne is proved to have excellent conductivity and potential to become a semiconductor material.
Example 5
According to calcium carbide (CaC)2) And pentachloronitrobenzene (C)6Cl5NO2) The molar ratio is 5: 1, respectively weighing calcium carbide and quintozene, placing the calcium carbide and the quintozene in a vacuum ball milling tank, and controlling the mass ratio of grinding balls to total materials to be 50: 1. then replacing the air in the ball milling tank with high-purity argon, sealing, and then placing the ball milling tank on an all-directional planetary ball mill. Ball milling was carried out at a ball milling rate of 700 revolutions per minute for 0.5 hour. After the reaction is finished, the ball milling tank is opened, the original gray powder is changed into paint black, and the generation of the carbon material is proved. Subsequently, a part of the reaction product was taken out and placed in a beaker, treated with dilute nitric acid and the chloride ion content of the filtrate was measured, whereby the dechlorination rate of pentachloronitrobenzene was determined to be 99.8%. The reaction product was washed with acid and alcohol, and then vacuum dried at 120 ℃ for 5 hours to obtain the in-situ N, O doped graphite monoalkyne of the present example, which was weighed and the apparent carbon yield was calculated to be 106.7%.
The chemical structural formula of the obtained in-situ N, O doped graphite monoalkyne is shown in figure 1 e. Elemental analysis showed that the N, O content of the obtained in-situ N-doped graphitic monoalkyne was 5.5% and 10.3%, respectively. The scanning electron microscope test result (fig. 3f) shows that the in-situ N, O doped graphite monoalkyne prepared by the method has a good pore structure. The transmission electron microscope test result (fig. 4f) of the in-situ N, O doped graphite monoalkyne shows that the alkyne carbon material has a typical graphene-like laminated structure. X-ray diffraction analysis (fig. 5e) of the resulting in situ N, O doped graphitic mono-acetylene showed that the carbon material had a crystalline structure. The Raman spectrum (fig. 6e) of the obtained in-situ N, O doped graphite monoalkyne shows that the carbon material has good order degree.
And pressing the obtained in-situ N, O doped graphite monoacyne into a sheet, and testing the conductivity of the sheet by a four-probe method. The conductivity of the obtained graphite is 14.9S/cm, and the in-situ N, O doped graphite monoalkyne is proved to have excellent conductivity and potential to become a semiconductor material.
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 (7)
1. The preparation method of the in-situ doped graphite monoalkyne is characterized by comprising the following steps:
(1) mixing calcium carbide and polyhalogenated hydrocarbon containing heteroatoms according to a molar ratio of 4-12: 1, mixing, adding the mixture into a ball mill once or for multiple times, and carrying out ball milling reaction for 0.5-10 h under the protection of vacuum or normal pressure inert gas to obtain a reaction product;
(2) washing the reaction product with dilute nitric acid, and then washing with ethanol or benzene to obtain a washing product;
(3) and (3) drying the washing product at 120 ℃ in vacuum, and then grinding the washing product into powder to obtain the powdery in-situ doped graphite monoalkyne material.
2. The preparation method of in-situ doped graphite monoalkyne according to claim 1, wherein the ball milling reaction temperature is normal temperature, and the ball milling speed is 400-700 r/min.
3. The method for preparing in-situ doped graphite monoalkyne according to claim 1, wherein the polyhalogenated hydrocarbon containing hetero atoms is selected from pentachloropyridine C5Cl5N, tetrabromothiophene C4Br4S, tetrabromophthalic anhydride C8Br4O3Endosulfan C9H6Cl6O3S, pentachloronitrobenzene C6Cl5NO2Decabromodiphenyl ether C12Br10O or a combination of several O.
4. The method of claim 1, wherein the ball mill is selected from any one of a vibration ball mill, an agitator ball mill, a roller ball mill and a planetary ball mill.
5. An in-situ doped graphitic monoalkyne prepared using the method of any one of claims 1-4.
6. The in-situ doped graphitic monoalkyne according to claim 5, wherein the in-situ doped graphitic monoalkyne is a heteroatom-containing carbon skeleton of an alkynyl-linked ultra-broad conjugated structure.
7. The use of the in-situ doped graphitic monoalkyne according to claim 5 in the preparation of electricity storage, semiconductors and catalytic materials.
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| CN111689486A (en) * | 2020-06-15 | 2020-09-22 | 上海工程技术大学 | Preparation method of N-containing graphdiyne material |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN112777584A (en) * | 2021-01-27 | 2021-05-11 | 安徽工业大学 | Graphene alkyne, preparation method and application thereof |
| CN114308026A (en) * | 2021-12-07 | 2022-04-12 | 天津理工大学 | Graphite alkynyl diatomic catalyst and preparation method and application thereof |
| CN114789995A (en) * | 2022-04-16 | 2022-07-26 | 复旦大学 | Specific site sulfur/nitrogen co-doped graphite monoalkyne and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689486A (en) * | 2020-06-15 | 2020-09-22 | 上海工程技术大学 | Preparation method of N-containing graphdiyne material |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN112777584A (en) * | 2021-01-27 | 2021-05-11 | 安徽工业大学 | Graphene alkyne, preparation method and application thereof |
| CN112777584B (en) * | 2021-01-27 | 2022-08-09 | 安徽工业大学 | Graphene alkyne, preparation method and application thereof |
| CN114308026A (en) * | 2021-12-07 | 2022-04-12 | 天津理工大学 | Graphite alkynyl diatomic catalyst and preparation method and application thereof |
| CN114308026B (en) * | 2021-12-07 | 2023-07-25 | 天津理工大学 | Graphite alkynyl diatomic catalyst and preparation method and application thereof |
| CN114789995A (en) * | 2022-04-16 | 2022-07-26 | 复旦大学 | Specific site sulfur/nitrogen co-doped graphite monoalkyne and preparation method and application thereof |
| CN114789995B (en) * | 2022-04-16 | 2023-11-07 | 复旦大学 | Specific site sulfur/nitrogen co-doped graphite monoacetylene and preparation method and application thereof |
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