CN115784211B - Method for in-situ construction of uniform mesoporous carbon on surface of carbon nano tube - Google Patents
Method for in-situ construction of uniform mesoporous carbon on surface of carbon nano tube Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 106
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 106
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 45
- 238000010276 construction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 26
- 241000252506 Characiformes Species 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229940045870 sodium palmitate Drugs 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 17
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 claims description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 10
- 229940099607 manganese chloride Drugs 0.000 claims description 10
- 235000002867 manganese chloride Nutrition 0.000 claims description 10
- 239000011565 manganese chloride Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010952 in-situ formation Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- -1 sodium palmitate modified carbon nano tube Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The invention provides a method for in-situ construction of uniform mesoporous carbon on the surface of a carbon nano tube, which uses a piranha acid solution to carry out surface modification on the carbon nano tube and introduces oxygen-containing functional groups; adding a metal ion aqueous solution into the sodium palmitate modified carbon nano tube, reacting the metal ion aqueous solution to separate out a quasi-solid, and then calcining the quasi-solid at a high temperature to obtain a precursor material; and etching the precursor material by using a hydrochloric acid aqueous solution to obtain the carbon nanotube with the surface coated with the uniform mesoporous carbon. The invention can construct uniform mesoporous carbon on the surfaces of the carbon nanotubes with different pipe diameters in situ and has high coverage. The existing research is difficult to realize the construction of uniform mesoporous carbon on the surface of a single carbon nano tube, so that only materials with the separated mesoporous carbon and carbon nano tubes can be prepared, and the synergistic effect between the carbon nano tube serving as a carrier and the mesoporous carbon cannot be realized. The invention fully expands the method for constructing the uniform mesoporous carbon on the surface of the carbon nano tube, is beneficial to realizing the synergistic effect between the carbon nano tube and the uniform mesoporous carbon constructed in situ, and greatly improves the application potential of the carbon nano tube.
Description
Technical Field
The invention relates to the fields of materials, inorganic chemistry, electrochemistry and the like, in particular to a method for in-situ construction of uniform mesoporous carbon on the surface of a carbon nano tube, in particular to a method for realizing the synergistic effect between the carbon nano tube and the in-situ constructed uniform mesoporous carbon at the molecular level and expanding the application prospect of the carbon nano tube in various fields.
Background
Nowadays, carbon nanotubes have very wide application prospects in the fields of energy storage and conversion and biological medicine due to high conductivity, high structural stability and good biocompatibility, and attract research interests of a plurality of researchers. However, carbon nanotubes often have the disadvantages of low specific surface area, lack of pore channels, single structure, high entanglement tendency, etc., which limit their practical application.
In recent years, researches on modified carbon nanotubes are endless, but the problems of low specific surface area, lack of pore channels and the like cannot be well solved. The formation of mesoporous carbon on the surface of the substrate is an emerging modification method developed at present. Because mesoporous carbon has high specific area, sufficient pore canal, sufficient conductivity and good biocompatibility, the specific surface area can be effectively improved, and the mass transfer can be enhanced without affecting other properties such as conductivity. However, at present, the research of introducing mesoporous carbon on the surface of a carbon nanotube is difficult to realize the construction of uniform mesoporous carbon on the surface of a single carbon nanotube, so that only a material with the mesoporous carbon separated from the carbon nanotube can be prepared, and the synergistic effect between the carbon nanotube as a carrier and the mesoporous carbon cannot be realized, and the main reason is that the carbon nanotube is fine, extremely easy to tangle and highly graphitized, and lacks the chemical force necessary for introducing the mesoporous carbon. Therefore, it is necessary to develop a method capable of constructing uniform mesoporous carbon on the surface of carbon nanotubes in situ.
Disclosure of Invention
The invention aims to provide a method for in-situ construction of uniform mesoporous carbon on the surface of a carbon nano tube.
The invention provides a method for in-situ construction of uniform mesoporous carbon on the surface of a carbon nano tube, which comprises the following steps:
(1) Preparing a piranha acid solution, adding the carbon nano tube into the piranha acid solution, heating and stirring the mixture, controlling the heating temperature to be 90-110 ℃, heating and stirring the mixture for 20-40min, and then diluting the mixture with water, carrying out suction filtration and drying the mixture;
(3) Adding a metal ion aqueous solution into the carbon nano tube dispersion liquid in the step (2) to react and separate out quasi-solid, and then carrying out suction filtration, drying and high-temperature calcination to obtain a precursor; the metal ion aqueous solution is any one of pure ferric chloride aqueous solution, pure manganese chloride aqueous solution, pure cobalt chloride aqueous solution, mixed solution of ferric chloride and manganese chloride in an equimolar ratio or mixed solution of ferric chloride, manganese chloride and cobalt chloride in an equimolar ratio; the molar ratio of the metal ion aqueous solution to the sodium palmitate is 1:1-4:1, a step of;
(2) Adding the carbon nano tube modified by the piranha acid into a sodium palmitate aqueous solution, and stirring to obtain a uniform carbon nano tube dispersion; the mass ratio of the carbon nano tube to the sodium palmitate is as follows: 1:10-1:50;
(3) Adding a metal ion aqueous solution into the carbon nano tube dispersion liquid in the step (2) to react and separate out quasi-solid, and then carrying out suction filtration, drying and high-temperature calcination to obtain a precursor; the metal ion aqueous solution is any one of pure ferric chloride aqueous solution, pure manganese chloride aqueous solution or pure cobalt chloride aqueous solution, mixed solution of ferric chloride and manganese chloride in an equimolar ratio or mixed solution of ferric chloride, manganese chloride and cobalt chloride in an equimolar ratio; the molar ratio of the metal ion aqueous solution to the sodium palmitate is 1:1-4:1, a step of;
(4) Etching the precursor obtained in the step (3) by using a hydrochloric acid aqueous solution to obtain the carbon nanotube with the surface coated with uniform mesoporous carbon, wherein: the concentration of the hydrochloric acid solution is 5-7 mol/L.
In the invention, the formula of the piranha acid solution in the step (1) is hydrogen peroxide (30%) and concentrated sulfuric acid with the volume ratio of 3:7.
in the invention, the temperature of the piranha acid solution modified carbon nano tube in the step (1) is 100 ℃, and the heating and stirring time is 30min.
In the invention, the diameter of the carbon nano tube used in the step (2) is 10-100 nm.
In the invention, the mass ratio of the carbon nano tube to the sodium palmitate in the step (2): 1:20-1:40.
in the invention, the pyrolysis atmosphere in the step (3) is nitrogen or argon.
In the invention, the pyrolysis temperature in the step (3) ranges from 350 ℃ to 500 ℃ and the time is 2 to 4 hours.
In the invention, the concentration range of the hydrochloric acid solution in the step (4) is 6 mol/L, and the etching time is 6-12 hours.
The invention uses piranha acid solution to modify the carbon nano tube, introduces oxygen-containing functional groups, then carries out hydrogen bond coordination on sodium palmitate and the oxygen-containing functional groups on the surface of the carbon nano tube, at the moment, a metal cation aqueous solution is added to form a palmitic acid metal salt complex, and then the uniform mesoporous carbon can be constructed on the surface of the carbon nano tube in situ by suction filtration, drying, high-temperature calcination under inert atmosphere and hydrochloric acid etching.
The invention has the beneficial effects that: the invention can construct uniform mesoporous carbon on the surfaces of carbon nanotubes with different pipe diameters in situ, and has strong stability and high coverage. However, the existing method can only prepare the material with the mesoporous carbon separated from the carbon nano tube, and cannot realize the synergistic effect between the carbon nano tube serving as a carrier and the mesoporous carbon. Therefore, the invention expands the method for constructing uniform mesoporous carbon on the surface of the carbon nano tube and realizing the synergistic effect of the carbon nano tube and the mesoporous carbon.
Drawings
FIG. 1 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a 40 nm caliber carbon nano tube prepared in example 1;
FIG. 2 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a 40 nm caliber carbon nano tube prepared in example 2;
FIG. 3 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a 40 nm caliber carbon nano tube prepared in example 3;
FIG. 4 is a transmission electron microscope image of the in-situ formation of uniform mesoporous carbon on the surface of a 10 nm caliber carbon nanotube prepared in example 4;
FIG. 5 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a 10 nm caliber carbon nanotube prepared in example 5;
FIG. 6 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a 10-nm-diameter carbon nanotube prepared in example 6.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 40 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with the tube diameter of 40 nm modified by piranha into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 340 mu L of 1 mol/L ferric chloride aqueous solution into the solution obtained in the step (2) to react and separate out quasi-solid, and then carrying out suction filtration, drying and calcining for 3 hours at 450 ℃ in nitrogen to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 12 hours by using 5 mol/L hydrochloric acid aqueous solution, so that uniform mesoporous carbon can be constructed on the surface of the carbon nano tube in situ;
fig. 1 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a carbon nanotube with a tube diameter of 40 nm prepared in example 1, and it can be seen that the in-situ construction of uniform mesoporous carbon with a pore diameter of 16 nm on the surface of the carbon nanotube shows that the method can in-situ construct uniform mesoporous carbon on the surface of a carbon nanotube with a tube diameter of 40 nm.
Example 2
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 40 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with the tube diameter of 40 nm modified by piranha into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 800 mu L of 1 mol/L ferric chloride aqueous solution into the solution obtained in the step (2) to react so as to separate out quasi-solid, and then carrying out suction filtration, drying and calcining at 400 ℃ in nitrogen for 3 hours to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 8 hours by using a 6 mol/L hydrochloric acid aqueous solution to form uniform mesoporous carbon on the surface of the carbon nano tube in situ;
fig. 2 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of the carbon nanotube with the pipe diameter of 40 nm prepared in example 2, and it can be seen that the in-situ construction of uniform mesoporous carbon with the pore diameter of 16 nm on the surface of the carbon nanotube shows that the method can in-situ construct uniform mesoporous carbon on the surface of the carbon nanotube with the pipe diameter of 40 nm.
Example 3
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 40 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with the tube diameter of 40 nm modified by piranha into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 1200 mul of 1 mol/L ferric chloride aqueous solution into the solution obtained in the step (2) to react so as to separate out quasi-solid, and then carrying out suction filtration, drying and calcining at 500 ℃ in argon for 2 hours to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 6 hours by using 7 mol/L hydrochloric acid aqueous solution to form uniform mesoporous carbon on the surface of the carbon nano tube in situ;
fig. 3 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of the carbon nanotube with the pipe diameter of 40 nm prepared in example 3, and it can be seen that the in-situ construction of uniform mesoporous carbon with the pore diameter of 16 nm on the surface of the carbon nanotube shows that the method can in-situ construct uniform mesoporous carbon on the surface of the carbon nanotube with the pipe diameter of 40 nm.
Example 4
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 10 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with 10 nm pipe diameters modified by piranha acid into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 340 mu L of 1 mol/L ferric chloride aqueous solution into the solution obtained in the step (2) to react and separate out quasi-solid, and then carrying out suction filtration, drying and calcining for 3 hours at 450 ℃ in nitrogen to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 12 hours by using 5 mol/L hydrochloric acid aqueous solution, so that uniform mesoporous carbon can be constructed on the surface of the carbon nano tube in situ;
fig. 4 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm prepared in example 4, and it can be seen that the in-situ construction of uniform mesoporous carbon with a pore diameter of 16 nm on the surface of the carbon nanotube shows that the method can in-situ construct uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm.
Example 5
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 10 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with 10 nm pipe diameters modified by piranha acid into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 800 mu L of 1 mol/L mixed solution of ferric chloride aqueous solution and cobalt chloride aqueous solution in an equimolar ratio into the solution obtained in the step (2), reacting to separate out quasi-solid, filtering, drying, and calcining at 400 ℃ in nitrogen for 3 hours to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 8 hours by using a 6 mol/L hydrochloric acid aqueous solution to form uniform mesoporous carbon on the surface of the carbon nano tube in situ;
fig. 5 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm, which is prepared in example 5, and it can be seen that the in-situ construction of uniform mesoporous carbon with a pore diameter of 16 nm on the surface of the carbon nanotube, which indicates that the method can in-situ construct uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm.
Example 6
(1) Preparing 40 ml piranha acid solution, adding 50 mg of 10 nm-diameter carbon nanotubes, heating and stirring at 100 ℃ for 30 minutes, diluting with 400 ml deionized water, carrying out suction filtration, washing the product to be neutral with deionized water and ethanol, and finally drying in a 75 ℃ oven;
(2) Adding 10 mg carbon nanotubes with 10 nm pipe diameters modified by piranha acid into a sodium palmitate aqueous solution with the concentration of 0.25 mol/L prepared in advance by 4 ml, and heating and stirring for 2 hours to obtain uniform carbon nanotube dispersion;
(3) Slowly adding 1200 mu L of 1 mol/L ferric chloride aqueous solution, cobalt chloride aqueous solution and manganese chloride aqueous solution mixed solution in an equimolar ratio into the solution obtained in the step (2), reacting to separate out quasi-solid, and then carrying out suction filtration, drying and calcining at 500 ℃ in argon for 2 hours to obtain a precursor;
(4) Etching the precursor obtained in the step (3) for 6 hours by using 7 mol/L hydrochloric acid aqueous solution to form uniform mesoporous carbon on the surface of the carbon nano tube in situ;
fig. 6 is a transmission electron microscope image of the in-situ construction of uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm, which is prepared in example 6, and it can be seen that the in-situ construction of uniform mesoporous carbon with a pore diameter of 16 nm on the surface of the carbon nanotube, which indicates that the method can in-situ construct uniform mesoporous carbon on the surface of a carbon nanotube with a diameter of 10 nm.
Claims (8)
1. The method for in-situ construction of uniform mesoporous carbon on the surface of the carbon nano tube is characterized by comprising the following specific operation steps:
(1) Preparing a piranha acid solution, adding the carbon nano tube into the piranha acid solution, heating and stirring the mixture, controlling the heating temperature to be 90-110 ℃, heating and stirring the mixture for 20-40min, and then diluting the mixture with water, carrying out suction filtration and drying the mixture;
(2) Adding the carbon nano tube modified by the piranha acid into a sodium palmitate aqueous solution, and stirring to obtain a uniform carbon nano tube dispersion; the mass ratio of the carbon nano tube to the sodium palmitate is as follows: 1:10-1:50;
(3) Adding a metal ion aqueous solution into the carbon nano tube dispersion liquid in the step (2) to react and separate out quasi-solid, and then carrying out suction filtration, drying and high-temperature calcination to obtain a precursor; the metal ion aqueous solution is any one of pure ferric chloride aqueous solution, pure manganese chloride aqueous solution, pure cobalt chloride aqueous solution, mixed solution of ferric chloride and manganese chloride in an equimolar ratio or mixed solution of ferric chloride, manganese chloride and cobalt chloride in an equimolar ratio; the molar ratio of the metal ion aqueous solution to the sodium palmitate is 1:1-4:1, a step of;
(4) Etching the precursor obtained in the step (3) by using a hydrochloric acid aqueous solution to obtain the carbon nanotube with the surface coated with uniform mesoporous carbon, wherein: the concentration of the hydrochloric acid solution is 5-7 mol/L.
2. The method for in-situ construction of uniform mesoporous carbon on a carbon nanotube surface according to claim 1, wherein the formula of the piranha acid solution in step (1) is that the volume ratio of 30% hydrogen peroxide to concentrated sulfuric acid is 3:7.
3. the method for in-situ construction of uniform mesoporous carbon on a carbon nanotube surface according to claim 1, wherein the temperature of the piranha acid solution modified carbon nanotube in the step (1) is 100 ℃, and the heating and stirring time is 30min.
4. The method for in-situ formation of uniform mesoporous carbon on a surface of a carbon nanotube as claimed in claim 1, wherein the diameter of the carbon nanotube used in the step (1) is 10-100 nm.
5. The method for in-situ construction of uniform mesoporous carbon on a carbon nanotube surface according to claim 1, wherein in the step (2), the mass ratio of carbon nanotube to sodium palmitate is as follows: 1:20-1:40.
6. the method for in-situ formation of uniform mesoporous carbon on a surface of a carbon nanotube as claimed in claim 1, wherein the pyrolysis atmosphere in the step (3) is nitrogen or argon.
7. The method for in-situ formation of uniform mesoporous carbon on a surface of a carbon nanotube according to claim 1, wherein the pyrolysis temperature in the step (3) is in a range of 350 ℃ to 500 ℃ for 2 to 4 hours.
8. The method for in-situ formation of uniform mesoporous carbon on a carbon nanotube surface according to claim 1, wherein the hydrochloric acid solution in the step (4) has a concentration of 6 mol/L and an etching time of 6-12 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046517A (en) * | 2008-05-28 | 2011-05-04 | 株式会社百奥尼 | Nanocomposites consisting of carbon nanotube and metal and a process for preparing the same |
| CN102295325A (en) * | 2011-07-21 | 2011-12-28 | 上海大学 | Preparation method of carbon nano-tube/mesoporous-carbon composite capacitance-type desalting electrode |
| KR20130063718A (en) * | 2011-12-07 | 2013-06-17 | 충남대학교산학협력단 | Method for manufacturing nanocomposites consisting of carbon and metal using plasma-solution system |
| CN114300863A (en) * | 2021-12-02 | 2022-04-08 | 烟台大学 | Carbon nanotube/mesoporous carbon/iron carbide composite wave-absorbing material and preparation method thereof |
| CN114852997A (en) * | 2022-05-26 | 2022-08-05 | 陕西科技大学 | Three-dimensional carbon nanotube-mesoporous carbon composite sponge, and preparation method and application thereof |
| CN115010117A (en) * | 2022-07-06 | 2022-09-06 | 中山大学 | Preparation method and application of active metal modified carbon nanotube brush material |
-
2022
- 2022-12-01 CN CN202211524759.0A patent/CN115784211B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102046517A (en) * | 2008-05-28 | 2011-05-04 | 株式会社百奥尼 | Nanocomposites consisting of carbon nanotube and metal and a process for preparing the same |
| CN102295325A (en) * | 2011-07-21 | 2011-12-28 | 上海大学 | Preparation method of carbon nano-tube/mesoporous-carbon composite capacitance-type desalting electrode |
| KR20130063718A (en) * | 2011-12-07 | 2013-06-17 | 충남대학교산학협력단 | Method for manufacturing nanocomposites consisting of carbon and metal using plasma-solution system |
| CN114300863A (en) * | 2021-12-02 | 2022-04-08 | 烟台大学 | Carbon nanotube/mesoporous carbon/iron carbide composite wave-absorbing material and preparation method thereof |
| CN114852997A (en) * | 2022-05-26 | 2022-08-05 | 陕西科技大学 | Three-dimensional carbon nanotube-mesoporous carbon composite sponge, and preparation method and application thereof |
| CN115010117A (en) * | 2022-07-06 | 2022-09-06 | 中山大学 | Preparation method and application of active metal modified carbon nanotube brush material |
Non-Patent Citations (4)
| Title |
|---|
| Mesoporous Carbon-dispersed Carbon Nanotube Film Electrode Incorporated with Sulfur for Long-Life Li–S Batteries;Ji Hoon Kang;BULLETIN OF THE KOREAN CHEMICAL SOCIETY;第412-417页 * |
| Multiwall carbon nanotube@mesoporous carbon with core-shell configuration: a well-designed composite-structure toward electrochemical capacitor application;Xufang Qian;Journal of Materials Chemistry;第13025-13031页 * |
| Synthesis of carbon nanotubes@mesoporous carbon core–shell structured electrocatalysts via a molecule-mediated interfacial co-assembly strategy;Xiaohang Zhu;Journal of Materials Chemistry A;第8975-8983页 * |
| 碳纳米管基非贵金属催化剂在电催化氧化还原中的应用研究进展;王启晨;王;雷永鹏;陈志彦;宋垚;罗世彬;;无机化学学报(05);全文 * |
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