CN110950325A - Porous multi-element doped graphene prepared by chemical method and preparation method thereof - Google Patents
Porous multi-element doped graphene prepared by chemical method and preparation method thereof Download PDFInfo
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- CN110950325A CN110950325A CN201911131146.9A CN201911131146A CN110950325A CN 110950325 A CN110950325 A CN 110950325A CN 201911131146 A CN201911131146 A CN 201911131146A CN 110950325 A CN110950325 A CN 110950325A
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Abstract
The invention belongs to the technical field of new materials, and particularly relates to porous multi-element doped graphene prepared by a chemical method and a preparation method thereof. The graphene sheet has a two-dimensional sheet structure, and the surface of the graphene sheet is provided with abundant in-plane holes; has one or more doped elements, wherein the doped elements are as follows: nitrogen, sulfur, oxygen; the preparation method comprises the following steps: mixing the organic micromolecule precursor with the oxidizing inorganic metal salt, and then realizing chemical polymerization under the condition of a hot solvent; and removing the metal by high-temperature calcination and strong acid to obtain the graphene product. The graphene prepared by the invention has excellent conductivity and hydrophilicity; the preparation method has the advantages of high yield, low production cost, simple process and convenient operation, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to porous multi-element doped graphene and a preparation method thereof.
Background
Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, and thus has many applications including use in transparent electrodes, lithium batteries, effect transistors, and the like. However, at present, graphene still faces three problems which are difficult to solve, namely, inter-lamellar stacking caused by van der waals acting force and pi-pi bond action, difficult modification of the graphene surface due to an inert surface formed by carbon atom arrangement, and low material transfer efficiency in the c-axis direction. How to better regulate and modify the structure of the graphene, expand the application of the graphene material in various fields, solve the defects of the graphene material at present, are key points and difficulties in the research of the nano-science, and also realize the direction and the target from basic research to application of the graphene material. With the deep research of graphene, graphene is entering the industrial mass production stage from the laboratory research stage, and the conventional oxidation method has many defects in the synthesized graphene, so that the yield is always low, and the industrial production requirements are difficult to meet. Therefore, a process and a system capable of realizing large-scale industrial production of graphene are needed.
Disclosure of Invention
The invention aims to provide graphene with excellent surface performance, high yield and low cost and a preparation method thereof.
The preparation method of the graphene provided by the invention is to prepare porous multi-element doped graphene by a chemical method, and comprises the following specific steps:
(1) mixing an organic micromolecule precursor and an oxidizing inorganic metal salt according to a certain proportion, and uniformly dissolving the organic micromolecule precursor and the oxidizing inorganic metal salt in an aqueous solution to form a mixed solution;
(2) heating the mixed solution to a reaction temperature, carrying out reflux reaction for a period of time, and directly and rapidly cooling the mixed solution to form ice block solid by using liquid nitrogen after the mixed solution is completely polymerized;
(3) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(4) placing the dried powder into a tube furnace, and calcining for a period of time under the inert gas atmosphere;
(5) and putting the calcined solid into a hot strong acid solution, removing metals, filtering, washing and drying to obtain the product.
Preferably, the organic small molecule in step (1) may be one or more of pyrrole, aniline, dopamine, 2-thio-4-thiazolidone.
Preferably, the inorganic nonmetallic salt in the step (1) can be one of ferric chloride and potassium permanganate.
Preferably, the mass ratio between the organic small molecule and the inorganic metal salt is controlled to be between 1:8 and 1:3 (namely 1 (3-8)).
Preferably, the reaction temperature in the step (2) is controlled to be between 80 and 100 ℃, and the reflux polymerization reaction time is controlled to be between 12 and 72 hours.
Preferably, the calcination temperature in the step (4) is 800-1100 ℃, the calcination time is 1-4 hours, and the temperature rise rate is 2-5 ℃ per minute.
Preferably, in the metal removing process by using the strong acid in the step (5), the strong acid solution can be one of sulfuric acid or hydrochloric acid solution with the concentration of 1-3 mol/L, the heating temperature is kept between 40-60 ℃, and the reaction time is 24-72 hours.
The graphene prepared by the method is of a two-dimensional sheet structure, and the surface of the graphene is provided with abundant in-plane holes; has one or more kinds of impurity elements, including nitrogen element (4-10 wt%), sulfur element (2-6 wt%) and oxygen element (5-12 wt%).
The graphene prepared by the method contains various doping elements, so that the inert surface of the graphene can be obviously improved, and the modifiability and the hydrophilicity of the graphene are greatly improved; the surface of the graphene material is provided with abundant in-plane holes, so that the problem of mass transfer limitation of the graphene material can be solved; the chemical preparation method disclosed by the invention is high in yield, low in production cost, simple in process, convenient to operate, suitable for large-scale industrial production, capable of overcoming the defects of the traditional graphene preparation method, and suitable for the fields of catalysis, energy and the like.
Drawings
Fig. 1 shows relevant elements contained in graphene.
Fig. 2 is a transmission electron micrograph of graphene.
Detailed Description
The invention is further illustrated by the following examples and figures. It should be noted that these examples are provided to help understanding of the present invention, but are not to be construed as limiting the present invention. Further, the technical elements involved in the respective embodiments described below may be combined with each other as long as they do not conflict with each other.
Example 1:
the preparation method of the porous multi-element doped graphene by a chemical method comprises the following specific steps:
(a) mixing the organic micromolecule dopamine and ferric chloride according to the mass ratio of 1:8, and uniformly dissolving the mixture in an aqueous solution to form a mixed solution;
(b) heating the mixed solution to 80 ℃, carrying out reflux reaction for 12 hours, and directly and rapidly cooling the mixed solution to be ice-cube solid by using liquid nitrogen after the mixed solution is completely polymerized;
(c) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(d) placing the dried powder into a tube furnace, calcining for 2 hours at 800 ℃ under the atmosphere of argon gas, and raising the temperature at a rate of 5 ℃ per minute;
(e) and putting the calcined solid into 1 mol/L hydrochloric acid solution, heating to 60 ℃, keeping the temperature for 24 hours to remove metals, filtering, washing and drying to obtain the porous multi-element doped graphene. The test shows that the content of nitrogen element is 4 percent, and the content of oxygen element is 12 percent. The surface of the graphene presents a porous structure.
Example 2:
the preparation method of the porous multi-element doped graphene by a chemical method comprises the following specific steps:
(a) mixing organic micromolecule 2-sulfo-4-thiazolidone and ferric chloride according to the mass ratio of 1:6, and uniformly dissolving the mixture in an aqueous solution to form a mixed solution;
(b) heating the mixed solution to 90 ℃, carrying out reflux reaction for 24 hours, and directly and rapidly cooling the mixed solution to be ice-cube solid by using liquid nitrogen after the mixed solution is completely polymerized;
(c) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(d) placing the dried powder into a tubular furnace, calcining for 1 hour at 1000 ℃ under the atmosphere of argon gas, and raising the temperature at a rate of 5 ℃ per minute;
(e) and putting the calcined solid into a 3 mol/L sulfuric acid solution, heating to 50 ℃, keeping the temperature for 48 hours to remove metals, filtering, cleaning and drying to obtain the porous multi-element doped graphene. The test shows that the content of nitrogen element is 10%, the content of oxygen element is 5% and the content of sulfur element is 6%, as shown in figure 1. The graphene surface has a rich pore structure, as shown in the transmission electron microscope picture of fig. 2.
Example 3:
the preparation method of the porous multi-element doped graphene by a chemical method comprises the following specific steps:
(a) mixing organic micromolecular pyrrole with ferric chloride according to the mass ratio of 1:3, and uniformly dissolving the organic micromolecular pyrrole and the ferric chloride in an aqueous solution to form a mixed solution;
(b) heating the mixed solution to 100 ℃, carrying out reflux reaction for 72 hours, and directly and rapidly cooling the mixed solution to be ice-cube solid by using liquid nitrogen after the mixed solution is completely polymerized;
(c) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(d) placing the dried powder into a tube furnace, calcining for 1 hour at 1100 ℃ under the atmosphere of argon gas, and raising the temperature at the rate of 2 ℃ per minute;
(e) and putting the calcined solid into a hydrochloric acid solution of 3 mol/L, heating to 60 ℃, keeping the temperature for 48 hours to remove metals, filtering, washing and drying to obtain the porous multi-element doped graphene. The content of nitrogen element is 6% by test. The surface of the graphene presents a porous structure.
Example 4:
the preparation method of the porous multi-element doped graphene by a chemical method comprises the following specific steps:
(a) mixing organic micromolecular aniline and potassium permanganate according to the mass ratio of 1:4, and uniformly dissolving the mixture in an aqueous solution to form a mixed solution;
(b) heating the mixed solution to 80 ℃, carrying out reflux reaction for 12 hours, and directly and rapidly cooling the mixed solution to be ice-cube solid by using liquid nitrogen after the mixed solution is completely polymerized;
(c) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(d) placing the dried powder into a tube furnace, calcining for 4 hours at 800 ℃ under the atmosphere of argon gas, and raising the temperature at a rate of 5 ℃ per minute;
(e) and putting the calcined solid into a hydrochloric acid solution of 2 mol/L, heating to 40 ℃, keeping the temperature for 72 hours to remove metals, filtering, cleaning and drying to obtain the porous multi-element doped graphene. The test shows that the content of nitrogen element is 7 percent, and the content of oxygen element is 5 percent. The surface of the graphene presents a porous structure.
The foregoing has outlined, rather broadly, the more preferred embodiment of the present invention in order that those skilled in the art may better understand and utilize the present invention. It will be apparent to those skilled in the art that numerous, simple inferences and substitutions can be made without departing from the spirit of the invention without undue experimentation. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention.
Claims (7)
1. A porous multi-element doped graphene prepared by a chemical method is characterized in that a graphene sheet is of a two-dimensional sheet structure, and the surface of the graphene sheet is provided with abundant in-plane holes; has one or more kinds of doped elements, wherein the doped elements are: nitrogen element: 4-10% of mass fraction, sulfur element: 2-6% of mass fraction, oxygen element: the mass fraction is 5-12%.
2. A preparation method of porous multi-element doped graphene adopts a chemical method and is characterized by comprising the following specific steps:
(1) mixing an organic micromolecule precursor with an oxidizing inorganic metal salt to be uniformly dissolved in an aqueous solution to form a mixed solution;
(2) heating the mixed solution to a reaction temperature, carrying out reflux reaction, and directly and rapidly cooling the mixed solution to form ice block solid by using liquid nitrogen after the mixed solution is completely polymerized;
(3) removing water from the ice cake solid in a freeze drying mode to obtain dry powder;
(4) placing the dried powder into a tube furnace and calcining in an inert gas atmosphere;
(5) and placing the calcined solid into a hot strong acid solution, removing metal, filtering, cleaning and drying to obtain the porous multi-element doped graphene product.
3. The preparation method according to claim 2, wherein the organic small molecule in step (1) is one or more of pyrrole, aniline, dopamine, 2-thio-4-thiazolidinone; the inorganic non-metallic salt is one of ferric chloride and potassium permanganate.
4. The preparation method according to claim 3, wherein the mass ratio of the organic small molecules to the inorganic metal salt in step (1) is controlled to 1 (3-8).
5. The method according to claim 2 or 3, wherein the reaction temperature in the step (2) is controlled to be 80 to 100 ℃ and the reflux polymerization reaction time is controlled to be 12 to 72 hours.
6. The preparation method as claimed in claim 5, wherein the calcination temperature in step (4) is 800-1100 ℃, the calcination time is 1-4 hours, and the temperature rise rate is 2-5 ℃ per minute.
7. The method of claim 6, wherein in the step (5), the strong acid solution is 1-3 mol/l sulfuric acid or hydrochloric acid solution, the temperature is maintained between 40-60 ℃, and the reaction time is 24-72 hours.
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| CN111659444A (en) * | 2020-06-20 | 2020-09-15 | 珠海复旦创新研究院 | Carbon-based limited-area interface supported palladium single-atom catalyst and preparation method thereof |
| CN112028063A (en) * | 2020-07-31 | 2020-12-04 | 珠海复旦创新研究院 | Porous graphene material |
| CN112680056A (en) * | 2020-12-10 | 2021-04-20 | 珠海复旦创新研究院 | Anticorrosive paint and preparation method and application thereof |
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