CN111017907B - Large-scale production method of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nanocomposite powder - Google Patents
Large-scale production method of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nanocomposite powder Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 title claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 29
- 239000010439 graphite Substances 0.000 title claims abstract description 29
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 22
- 238000011031 large scale production Methods 0.000 title claims abstract description 12
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229950002499 Fytic acid Drugs 0.000 claims abstract description 13
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 13
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- 235000002949 phytic acid Nutrition 0.000 claims abstract description 13
- 239000000467 phytic acid Substances 0.000 claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
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- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 nitrogen-and phosphorus Chemical compound 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 150000001722 carbon compounds Chemical class 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 125000005842 heteroatoms Chemical group 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000011858 nanopowder Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 2
- 229920000767 polyaniline Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 22
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- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
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- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
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- 230000001105 regulatory Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
Abstract
A large-scale production method of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nano composite powder belongs to the technical field of nano powder production. In order to realize the large-scale production of the method, aniline, ammonium persulfate, phytic acid, graphite carbon and other raw materials widely used in industry are utilized, a simple wet chemical in-situ polymerization method is combined with a common heat treatment method, various parameters are adjusted, polyaniline which is a conductive high polymer material is polymerized and carbonized, the doping amount of nitrogen and phosphorus of the amorphous carbon/graphite carbon composite nano powder is increased, and the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon composite nano powder with different nano microstructures is formed by controlling the proportion of aniline monomers and graphite carbon. The invention has the beneficial effects that: the production efficiency is greatly improved, the cost is reduced, the method is suitable for large-scale production, the doping content of the hetero atoms is high, and the purity of the prepared powder is high.
Description
Technical Field
The invention relates to the technical field of nano powder production, in particular to a large-scale production method of a nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon nano composite.
Background
Wet chemical and thermal processes are the two most common processes in industrial production. Among them, the wet chemical method is a method for preparing a material by a chemical reaction with participation of a liquid phase, and the heat treatment method is a method for treating a material only by heating at an elevated temperature, but parameter settings and processes thereof are very important. The method can be used for preparing the amorphous carbon material by combining a wet chemical method and a subsequent heat treatment process. For preparing amorphous carbon material doped with heterogeneous elements (such as nitrogen element and phosphorus element, N, P), in order to meet the practical application, a proper nano structure needs to be designed and prepared, and the amorphous carbon material is suitable for large-scale industrial production, and a specific process is needed to realize the preparation.
In order to realize large-scale preparation of nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon composites, a number of technical problems need to be solved, mainly in the past production methods: low efficiency, high cost, low purity, pollution in the production process, and difficulty in preparing the heteroatom doped amorphous carbon with special structure and the composite thereof with the graphite carbon on a large scale and keeping the higher doping content of the heteroatom N, P. We summarize the existing wet chemistry and heat treatment combined process for preparing hetero-atom doped amorphous carbon and its composite material with graphitic carbon as follows:
1) low production efficiency and high cost
In order to complete the doping of heterogeneous atoms to the amorphous carbon material, in the current production process, in order to make the heterogeneous atom doped amorphous carbon/graphite carbon composite material have a high doping content, it is often necessary to add other surfactant materials (generally having hydrophobicity), such as polyoxyethylene polyoxypropylene ether block copolymer (F127), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), sodium dodecylbenzenesulfonate, imidazole ionic liquid, etc., which are helpful to improve the solubility of the carbon source material in water, and can introduce more solvent molecules during the reaction process, but also increase the production cost. In addition, in order to dissolve the substances and enable the substances to interact with the carbon source material, the actual dissolution time of the substances is long, and generally accounts for 20-80% of the total production time, so that the overall production efficiency is reduced. Meanwhile, the reaction is carried out by processing methods such as ultrasonic treatment and the like, so that a large amount of energy is consumed, and the production cost is increased; the difficulty of removing these materials during subsequent cleaning processes will further increase the production costs.
2) Low purity
After other surfactants or other solvent molecules except water are added into a reaction system, the substances are difficult to remove in the subsequent cleaning process due to the interaction of hydrogen bonds, covalent bonds, van der waals force and the like, so that the purification of the heterogeneous atom doped amorphous carbon and the composite nano powder thereof is more difficult.
3) Is difficult to produce on a large scale
At present, in the production process for preparing the amorphous carbon doped with the hetero atoms (such as nitrogen, phosphorus, sulfur, boron and the like) and the composite thereof, although a plurality of carbon sources are selected, the problems of less carbon source materials, complex production process, low production efficiency, high preparation equipment cost, long production time, low product purity and the like in composite production are solved, and the problems of high production cost and low production efficiency are caused, so that the large-scale, high-efficiency and high-quality production of the amorphous carbon doped with the hetero atoms and the composite material thereof cannot be realized in a real sense.
Disclosure of Invention
The invention aims to solve the technical problems of low hetero atom doping content of amorphous carbon, difficult large-scale preparation on the premise of ensuring high nitrogen element doping content, low preparation purity and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a large-scale production method of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nanocomposite powder comprises the following steps:
(1) selecting raw materials: graphite carbon (comprising multi-wall carbon nanotubes with different diameters and graphene oxide with different stacking layers), aniline monomer, water, ammonium persulfate and phytic acid are selected as raw materials for large-scale production of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon composite powder through wet chemistry and heat treatment, the raw materials are all common materials in industry, the price is low, and the selection is favorable for reducing the production cost of the powder.
The purity of the multi-wall carbon nano tube is more than or equal to 95 percent, and the diameter of the multi-wall carbon nano tube is adjustable; the purity of the graphene oxide is more than or equal to 95%, and the number of stacked layers is adjustable; the purity of the aniline monomer is more than or equal to 99 percent, and the water content is less than 0.1 percent; the purity of the ammonium sulfate is more than or equal to 95 percent; the mass fraction of the phytic acid is 35-40%.
(2) Aniline pretreatment: carrying out reduced pressure distillation treatment on a purchased industrial aniline monomer, continuously introducing pure nitrogen in the process to prevent the aniline monomer from generating oxidation reaction, heating the aniline monomer to 100-130 ℃ by using an oil bath after reduced pressure distillation for 0.2-0.5 h in the reduced pressure process to prevent the influence of moisture on the aniline purity, and then sealing and shading the aniline monomer after treatment, and putting the aniline monomer into a refrigerator for cooling and storage.
The oil bath is filled with glycerol (glycerin).
(3) Pretreatment of graphite carbon: (a) the mixed solution of concentrated sulfuric acid and concentrated nitric acid with a certain volume ratio is used as the acid solution for pretreatment of graphite carbon, and the graphite carbon is treated for 1.5-2.5 hours at 130-160 ℃. In the process, the high-temperature solution needs to be subjected to condensation reflux and magnetic stirring continuously, and the step is suitable for large-scale acidification of industrial original multi-walled carbon nanotubes and increase of oxygen-containing functional groups on the surfaces of the multi-walled carbon nanotubes. The modified acidified carbon nanotubes (CNTs-COOH) have more active chemical properties and are more prone to complex reaction; and (b) the industrial-grade graphene oxide does not need to be pretreated.
The stirring speed of the continuous stirring is more than or equal to 500 revolutions per minute.
The volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4: 1; the mass fraction of the concentrated sulfuric acid is more than or equal to 70 percent; the mass fraction of the concentrated nitric acid is about 68 percent.
(4) Graphite carbon dispersion: dissolving pretreated multi-walled carbon nanotube/graphene oxide with a certain mass in a certain amount of water according to a certain proportion, and ultrasonically dispersing until suspension or solution is formed: the acidified carbon nano tube still can not be dissolved in water, and finally uniform turbid liquid is formed; graphene oxide can be dissolved in water to form a homogeneous solution.
The mass ratio of the carbon nano tube/graphene oxide to water is adjustable, wherein the mass fraction of the carbon material is not higher than 0.04%.
(5) Aniline dispersion: dropwise adding the aniline monomer purified in the step (2) into the obtained suspension/solution of the step (4) under the condition of high-speed magnetic stirring, and stirring for at least 1 hour to form uniform suspension/solution.
The stirring speed is more than or equal to 500 r/min, the mass ratio of the purified aniline monomer to water is adjustable, and the mass fraction of the aniline is not higher than 0.4%.
(6) Controlling the environment of the reaction solution: adding a certain amount of phytic acid into the suspension/solution in the step (5), and controlling the pH of the reaction solution to be 0-3. Wherein the volume ratio of the added phytic acid to the water is 0.1-0.3.
(7) Aniline in-situ polymerization: and (4) adding ammonium persulfate into the suspension/solution obtained in the step (6), and continuously stirring for 24 hours under the ice-water bath condition.
In the step (7), the mole number of the ammonium persulfate is controlled to be the same as that of the aniline, and the stirring speed of continuous stirring is more than or equal to 500 r/min; controlling the temperature of the ice water bath at 0-5 ℃;
(8) cleaning and collecting the nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon compound: and (3) carrying out vacuum filtration cleaning on the solution in the step (7), wherein the cleaning step is simple, the cleaning solvents are water and absolute ethyl alcohol, the cleaning times of each solvent are not less than three times, and finally, the powder is dried at 60 ℃ overnight, and the powder is collected to be the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nano composite material (PANi-CNTs), at the moment, the pore structure in the powder is determined, the subsequent heat treatment process can controllably regulate and control the porous structure according to the needs of people, namely, the subsequent heat treatment process can be regulated and controlled to form an amorphous pore structure meeting the needs of people.
In the step (8), the stirring and cleaning time of the water and the absolute ethyl alcohol is respectively 2-4 hours and 2-3 hours, and the stirring speed is 400-600 r/min.
(9) And (3) at room temperature, placing the powder dried and collected in the step (8) in an environment filled with nitrogen, raising the temperature in the nitrogen environment to 600-1300 ℃ at a certain temperature raising rate, preserving the temperature for 1.5-3 hours, then naturally cooling, introducing pure nitrogen and isolating air in the process until the reaction temperature is slowly reduced to room temperature, and finally collecting the prepared powder, thus obtaining the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon composite nano powder product (N, P-C @ CNTs).
The temperature rise speed is 1-8 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
1) is suitable for large-scale production and has low cost
The raw materials selected by the production process are all the raw materials which are commonly used in industry and have lower cost, the large-scale production of the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon composite nano powder can be realized by the raw materials with low cost, and the amorphous property, the ultrahigh nitrogen and phosphorus content, the formation of a one-dimensional/two-dimensional nano structure and other properties of the prepared material are ensured; the process steps are simple, the operation is simple and convenient, the cost of required production equipment is low, the energy consumption is low, and the method is suitable for large-scale production, so that the production cost can be well controlled.
2) High efficiency of production
In the invention, all production processes except raw material pretreatment are creatively integrated into two production environments, namely room temperature, low temperature solution and high temperature nitrogen atmosphere, so that the problem of unavoidable environmental conversion in the production process of the amorphous carbon and the composite thereof is avoided to the maximum extent, and the high-efficiency production of the amorphous carbon/carbon nanotube nano composite powder is realized.
3) High content of nitrogen and phosphorus doping
It is very difficult to increase the hetero atom doping content of amorphous carbon materials. For graphite carbon sources, the stable carbon atom ring means that hetero atoms are difficult to combine with the carbon ring through covalent bonds, hydrogen bonds and the like, for example, high temperature or plasma treatment is required to improve hetero atom doping in graphene or carbon nanotubes. For a non-graphite carbon source, the heterogeneous element doping is ensured to have two modes, namely external doping and internal retention, and the high-nitrogen-content nitrogen and phosphorus doping of the amorphous carbon material is realized by preparing a high-nitrogen-content conductive polymer compound, namely polyaniline, and simultaneously controlling the heating rate, the final temperature and the heat preservation time in the heat treatment carbonization process by ensuring the aniline purity and the modification of the graphite carbon material, so that the nitrogen element content in the amorphous carbon material and the nitrogen element content in the amorphous carbon material are maximized. The phytic acid containing phosphorus with proper concentration is added, so that high-content phosphorus doping can be obtained to the maximum extent, and finally nitrogen-rich and phosphorus doping of the amorphous carbon/graphite carbon nano composite powder is realized.
4) Nano structure construction for realizing one-dimensional/two-dimensional amorphous carbon material
The method for realizing the nano structure construction of the amorphous carbon material is extremely difficult for most amorphous carbon materials, and can be realized mostly under extremely complex and harsh experimental conditions.
5) The amorphous carbon/carbon nano tube nano composite powder has high purity
The method avoids adding other surfactants or other solvent molecules except water, reduces the difficulty degree of the subsequent cleaning process, and ensures that the purity of the heterogeneous atom doped amorphous carbon and the composite nano powder thereof can reach 99.9 percent.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nitrogen-rich, phosphorus-doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1.
Figure 2 is a SEM photograph of nitrogen-rich, phosphorus-doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1.
Figure 3 is a TEM micrograph of a nitrogen-rich, phosphorus-doped amorphous carbon/graphitic carbon nanocomposite prepared according to example 1.
FIG. 4 is a photograph of a BET (Brunauer-Emmett-Teller, obtained by nitrogen adsorption testing) of nitrogen-rich, phosphorus-doped amorphous carbon/graphitic carbon nanocomposites prepared in example 1.
FIG. 5 is an abstract figure illustrating the preparation process of nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon nanocomposite.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1
1. Distilling aniline monomer (purity is more than or equal to 99% and water content is less than 0.1%) under reduced pressure, introducing nitrogen gas continuously in the process to protect aniline from oxidation, heating to 100 ℃ by using oil bath (glycerol and glycerol) after reducing pressure, treating for 0.5 h, sealing and shading after distilling, and putting into a refrigerator for cooling and storing;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1(40ml, the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is about 68%), heating to 130 ℃, heating at the speed of 0.5 ℃/min, carrying out oil bath heating for 2.5 hours, and carrying out condensation reflux and continuous stirring on the high-temperature solution in the process (the stirring speed for continuous stirring is 500 r/min);
adding 3.40 mg of acidified CNTs/graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.4ml aniline into the constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. dropping 20ml of phytic acid (35-40% by mass), adding 1.36g of ammonium persulfate, and continuously stirring at the stirring speed of 500 revolutions per minute;
7. stirring for 24 hours at a stirring speed of 500 revolutions per minute, washing with deionized water and absolute ethyl alcohol for three times respectively, wherein the stirring and cleaning time of the water and the absolute ethyl alcohol is respectively 2 hours and 2 hours, the stirring speed is 600 revolutions per minute, and finally drying at 60 ℃ for 12 hours to finally obtain a powder sample;
8. and (2) placing the dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a certain temperature raising rate (the initial temperature is room temperature, the temperature raising speed is 1 ℃/min) until the temperature reaches 600 ℃, then preserving the temperature for 3 hours, then naturally cooling, introducing pure nitrogen and isolating the air in the process until the reaction temperature is reduced to the room temperature, and finally collecting the prepared powder, thereby obtaining the powder product of the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nano composite. As shown in the attached figure 1 of the specification, a characteristic peak at 26.2 degrees of 2 theta corresponds to a (002) crystal face of the composite; FIGS. 2 and 3 show a carbon nanotube and a one-dimensional structure thereof; figure 4 illustrates that the composite is a typical type IV pore structure (microporous and mesoporous together predominate).
Example 2
1. Distilling aniline monomer (purity is more than or equal to 99% and water content is less than 0.1%) under reduced pressure, introducing nitrogen gas continuously in the process to protect aniline from oxidation, heating to 130 deg.C with oil bath (glycerol and glycerol) after reduced pressure, treating for 0.2 hr, sealing and shading after distillation, and cooling and storing in refrigerator;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1(40ml, the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is about 68%), heating to 160 ℃, heating at the speed of 1 ℃/min, carrying out oil bath heating for 1.5 hours, and carrying out condensation reflux and continuous stirring on the high-temperature solution in the process (the stirring speed for continuous stirring is 500 r/min);
adding 3.20 mg of acidified CNTs/graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.2ml aniline into a constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. 60ml of phytic acid (35-40 percent by mass) is added in, 0.68g of ammonium persulfate is added in, and the stirring is continuously carried out at the stirring speed of 500 r/min;
7. stirring for 24 hours at a stirring speed of 500 revolutions per minute, washing with deionized water and absolute ethyl alcohol for three times respectively, wherein the stirring and cleaning time of the water and the absolute ethyl alcohol is respectively 4 hours and 3 hours, the stirring speed is 400 revolutions per minute, and finally drying at 60 ℃ for 12 hours to finally obtain a powder sample;
8. and (2) placing the dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a certain temperature raising rate (the initial temperature is room temperature, the temperature raising speed is 8 ℃/min) until the temperature reaches 1300 ℃, then preserving the temperature for 1.5 hours, then naturally cooling, continuously introducing pure nitrogen and isolating air in the process until the reaction temperature is reduced to the room temperature, and finally collecting the prepared powder, thereby obtaining the powder product of the nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon nano composite.
Example 3
1. Distilling aniline monomer (purity is more than or equal to 99% and water content is less than 0.1%) under reduced pressure, introducing nitrogen gas continuously in the process to protect aniline from oxidation, heating to 110 deg.C with oil bath (glycerol and glycerol) after reduced pressure, treating for 0.3 hr, sealing and shading after distillation, and cooling and storing in refrigerator;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1(40ml, the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is about 68%), heating to 140 ℃, heating at the speed of 0.8 ℃/min, carrying out oil bath heating for 2 hours, and carrying out condensation reflux and continuous stirring on the high-temperature solution in the process (the stirring speed for continuous stirring is 500 r/min);
adding 3.30 mg of acidified CNTs/graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h at the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.3ml aniline into a constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. 40ml of phytic acid (35-40 percent by mass) is dropped, 1.02g of ammonium persulfate is added, and the stirring is continuously carried out at the stirring speed of 500 r/min;
7. stirring for 24 hours at a stirring speed of 500 revolutions per minute, washing with deionized water and absolute ethyl alcohol for three times respectively, wherein the stirring and washing time of the water and the absolute ethyl alcohol is respectively 3 hours and 2.5 hours, the stirring speed is 500 revolutions per minute, and finally drying at 60 ℃ for 12 hours to finally obtain a powder sample;
8. and (2) placing the dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a certain temperature raising rate (the initial temperature is room temperature, the temperature raising speed is 5 ℃/min) until reaching 800 ℃, then preserving the temperature for 2 hours, then naturally cooling, introducing pure nitrogen and isolating air in the process until the reaction temperature is reduced to room temperature, and finally collecting the prepared powder, thus obtaining the nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nano composite powder product.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (5)
1. A large-scale production method of nitrogen-rich and phosphorus-doped amorphous carbon/graphite carbon nano composite powder is characterized by comprising the following steps:
(1) selecting raw materials: selecting graphite carbon, aniline monomers, water, ammonium persulfate and phytic acid as raw materials, wherein the graphite carbon is a multi-walled carbon nanotube with different diameters;
(2) aniline pretreatment: under the protection of nitrogen, carrying out reduced pressure distillation treatment on an industrial aniline monomer at the temperature of 100-130 ℃ for 0.2-0.5 hour, sealing and shading after distillation, and cooling and storing;
(3) pretreatment of graphite carbon: adding the multi-walled carbon nano-tube into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for pretreatment, wherein the pretreatment temperature is 130-160 ℃, and the pretreatment time is 1.5-2.5 hours;
(4) graphite carbon dispersion: dissolving the multi-walled carbon nanotubes pretreated in the step (3) in water, and performing ultrasonic dispersion until a suspension is formed: the pretreated multi-walled carbon nano-tube can not be dissolved in water to form uniform turbid liquid; the mass ratio of the multi-wall carbon nano-tube to water is adjustable, wherein the mass fraction of the carbon material is not higher than 0.04%;
(5) aniline dispersion: dropwise adding the aniline monomer purified in the step (2) into the suspension obtained in the step (4) under the condition of high-speed magnetic stirring, and stirring for at least 1 hour to form uniform suspension; the mass ratio of the purified aniline monomer to water is adjustable, wherein the mass fraction of aniline is not higher than 0.4%;
(6) controlling the environment of the reaction solution: adding phytic acid into the suspension obtained in the step (5), and controlling the pH of the reaction solution to be 0-3; wherein the volume ratio of the added phytic acid to the water in the step (4) is 0.1-0.3;
(7) aniline in-situ polymerization: adding ammonium persulfate into the suspension obtained in the step (6), and continuously stirring for 24 hours under the condition of an ice water bath; in the step (7), the mole number of the ammonium persulfate is the same as that of the aniline;
(8) cleaning and collecting the nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon compound: vacuum pumping, filtering and washing the reaction solution in the step (7), and drying at 60 ℃;
(9) and (3) at room temperature, placing the powder dried and collected in the step (8) in an environment filled with nitrogen, keeping the temperature for 1.5-3 hours when the temperature is raised to 600-1300 ℃, and then naturally cooling to room temperature to obtain the product.
2. The method for mass production of nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein the multi-walled carbon nanotubes obtained in step (1) have a purity of 95% or more and an adjustable diameter; the purity of the aniline monomer is more than or equal to 99 percent, and the water content is less than 0.1 percent; the purity of ammonium persulfate is more than or equal to 95 percent; the mass fraction of the phytic acid is 35-40%.
3. The method for mass production of nitrogen-rich and phosphorus-doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein in the mixed solution in the step (3), the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 4: 1; the mass fraction of the concentrated sulfuric acid is more than or equal to 70 percent; the mass fraction of the concentrated nitric acid is 68 percent.
4. The method for mass production of nitrogen-and phosphorus-rich doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein the temperature of the ice water bath in the step (7) is controlled to be 0-5 ℃.
5. The method for mass production of nitrogen-and phosphorus-rich doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein in the cleaning process in the step (8), the cleaning solvent is water and absolute ethyl alcohol, and the stirring and cleaning time of water and absolute ethyl alcohol is 2-4 hours and 2-3 hours respectively.
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