CN111498830B - Undoped one-dimensional porous carbon material and preparation method thereof - Google Patents
Undoped one-dimensional porous carbon material and preparation method thereof Download PDFInfo
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- CN111498830B CN111498830B CN202010238322.5A CN202010238322A CN111498830B CN 111498830 B CN111498830 B CN 111498830B CN 202010238322 A CN202010238322 A CN 202010238322A CN 111498830 B CN111498830 B CN 111498830B
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Abstract
The invention discloses an undoped one-dimensional porous carbon material and a preparation method thereof, which belong to the field of nano carbon materials, wherein the carbon material has an ultrahigh specific surface area, the problem of single pore structure of MOF-derived carbon materials is solved, and the simple and efficient preparation of the one-dimensional carbon material with the ultrahigh specific surface area is realized. According to the invention, amorphous nano particles Zn-MOF-74 are utilized to synthesize one-dimensional nano rod Zn-MOF-74 with good crystallinity through a hydrothermal recrystallization method, and the one-dimensional undoped porous carbon material with ultrahigh specific surface area is obtained through high-temperature pyrolysis and carbonization under inert atmosphere, wherein the shape regulation of the derivative carbon material is realized through the regulation and control of Zn-MOF-74 precursor, and meanwhile, the specific surface area and mesoporous proportion of the metal organic framework compound (MOF) derivative carbon material are obviously improved.
Description
Technical Field
The invention belongs to the field of nano carbon materials, and particularly relates to an undoped one-dimensional porous carbon material and a preparation method thereof.
Background
The one-dimensional carbon material (carbon nano tube, carbon nano fiber, carbon nano rod and the like) has large specific surface area and high conductivity, and has wide application in the fields of energy storage and conversion (such as super capacitor, electrocatalysis and battery), but the specific surface area is difficult to further increase due to the difficulty in designing and constructing the internal pore canal of the material, and the mass transfer in the material is limited, so that the application performance of the material is difficult to further improve.
The Metal organic framework (English: metal-Organic Framework, MOF for short) is a material which is formed by taking Metal ions as coordination centers and constructing the Metal ions and organic ligands through coordination bonds and has rich gaps. The carbon material prepared by taking the MOF as the precursor inherits the characteristic of rich pore channels on the MOF structure, and has good application prospect in the fields of energy storage and conversion. However, the MOF-derived carbon material has a problem of single pore structure (mainly microporous structure), which severely limits its application. Various methods, such as template method (adv. Function. Mate. 2016, 26, 8334-8344), etching method (j. Power Sources 2016, 302, 174) are used to improve the pore structure of MOF-derived carbon materials, but template method steps are cumbersome, and etching method results in loss of pore structure while controlling the pore structure.
Disclosure of Invention
The invention provides an undoped one-dimensional porous carbon material and a preparation method thereof, wherein the carbon material has an ultrahigh specific surface area, solves the problem of single pore structure of MOF derived carbon materials, and realizes simple and efficient preparation of the one-dimensional carbon material with the ultrahigh specific surface area.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the undoped one-dimensional porous carbon material comprises the following steps:
(1) Dissolving metal salt and ligand in solvent to form metal salt solution and ligand solution, adding the ligand solution into the metal salt solution drop by drop under intense stirring, continuously stirring to react fully, and separating and purifying to obtain MOF-74 nanometer particles;
(2) Dispersing MOF-74 nano particles obtained in the step (1) in distilled water, and regulating the pH of the dispersion to be 5-9;
(3) Carrying out hydrothermal reaction on the dispersion liquid obtained in the step (2) at 165-175 ℃ to carry out recrystallization growth, wherein the reaction time is 6-12 hours, and separating, purifying and drying to obtain the MOF-74 nanorod;
(4) And (3) heating the MOF-74 nanorod obtained in the step (3) to 1000-1200 ℃ under the protection of inert gas, and preserving heat for 2-3 hours to obtain the undoped one-dimensional porous carbon material.
In the steps, the ratio of the ligand to methanol in the ligand solution is (1.5-3 mmol) 50 mL, the ratio of the metal salt to methanol in the metal salt solution is 4 mmol/150 mL, the solvent is methanol, the metal salt is zinc acetate dihydrate, the ligand is 2, 5-dihydroxyterephthalic acid, and the molar ratio of the zinc acetate dihydrate to the 2, 5-dihydroxyterephthalic acid is 4 (1.5-3).
The undoped one-dimensional porous carbon material obtained by the preparation method has a micropore, macropore and mesopore structure, the mesopore proportion is larger than the proportion of micropores and macropores, the carbon material has an ultrahigh specific surface area, and the specific surface area is larger than 2000 m 2 /g。
The beneficial effects are that: the invention provides an undoped one-dimensional porous carbon material and a preparation method thereof, wherein a one-dimensional ordered structure MOF precursor is prepared by a hydrothermal technology recrystallization method, and the effective regulation and control of a one-dimensional MOF structure are realized through the regulation and control of the pH of a hydrothermal dispersion liquid; according to the invention, the ligand only containing C, O, H is adopted, and almost all O, H elements are evaporated when the synthesized MOF is subjected to pyrolysis carbonization, so that the one-dimensional porous carbon material of the final product is doped without hetero atoms, and the application of the one-dimensional porous carbon material in the specific field is realized; the evaporation of Zn, H, O and other elements in the pyrolysis process ensures that the one-dimensional porous carbon material of the final product has rich pore canal structures and ultrahigh specific surface area, thereby being beneficial to the application of the material in the fields of supercapacitors, electrocatalysis and the like; the one-dimensional porous carbon material prepared by the method has a large number of mesoporous and macroporous structures besides micropores, and solves the problem of single pore structure of the MOF derivative carbon material.
Drawings
FIG. 1 is a flow chart of an undoped one-dimensional carbon material with ultrahigh specific surface area and a preparation method thereof provided by an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of MOF-74 nanoparticles obtained in an example of the present invention;
FIG. 3 is a scanning electron microscope image of MOF-74 nanorods obtained at pH 5 in an example of the invention;
FIG. 4 is a scanning electron microscope image of MOF-74 nanorods obtained at pH 7 in an example of the invention;
FIG. 5 is a scanning electron microscope image of MOF-74 nanorods obtained at pH 9 in an example of the invention;
FIG. 6 is a scanning electron microscope image of a one-dimensional porous carbon material obtained in the example of the present invention;
FIG. 7 is an X-ray photoelectron spectroscopy analysis of a one-dimensional porous carbon material obtained in the example of the present invention.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments below:
example 1
As shown in fig. 1, a preparation method of an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a metal coordination center for providing metal salt, 2, 5-dihydroxyterephthalic acid is used as a ligand,
the molar ratio of the zinc acetate dihydrate to the 2, 5-dihydroxyterephthalic acid is 4:1.5, and the purity of the zinc acetate dihydrate and the 2, 5-dihydroxyterephthalic acid are above 98%;
step 102: adding ligand solution into metal salt solution, simply synthesizing amorphous MOF-74 nano particles, cleaning and purifying,
methanol is used as a reaction solvent, the purity of the methanol is more than 98 percent, metal salt and ligand are respectively and fully dissolved in the methanol, the proportion of the ligand to the methanol in the ligand solution is 1.5 mmol to 50 mL, the proportion of the metal salt to the methanol in the metal salt solution is 4 mmol to 150 mL, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
the polytetrafluoroethylene microporous filter membrane, distilled water and methanol are used as cleaning agents to be alternately cleaned, the suction filtration temperature is room temperature, the vacuum degree is less than-0.1 Mpa, and the synthesized MOF-74 nano particles are separated and purified by suction filtration, so that the obtained MOF-74 nano particles are shown in figure 2.
Step 103: preparing MOF-74 nano particles into aqueous dispersion, regulating pH of the dispersion, performing hydrothermal recrystallization to grow to obtain one-dimensional MOF-74 nano rods,
specifically, all MOF-74 nano particles obtained in the step 102 are dispersed in 50 mL distilled water, the pH of the dispersion liquid is regulated to 5 by using 1M HCl solution and 1M NaOH solution, then the dispersion liquid after regulating the pH is transferred to a 75 mL reaction kettle for hydrothermal reaction, the hydrothermal reaction temperature is 175 ℃, the reaction time is 12 hours, and the MOF-74 nano rod is obtained by drying the purified MOF-74 nano particles in a vacuum drying oven at 40-80 ℃ for 12-16 hours by using a suction filtration method;
step 104: performing high-temperature pyrolysis carbonization on the MOF-74 nanorods obtained in the step 103 to obtain the metal-organic framework-derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process is as follows: under the protection of nitrogen or argon, the temperature is raised to 1100 ℃ and kept for 2 hours, and the undoped one-dimensional porous carbon material is obtained.
Example 2
As shown in fig. 1, a preparation method of an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a metal coordination center for providing metal salt, 2, 5-dihydroxyterephthalic acid is used as a ligand,
the molar ratio of the zinc acetate dihydrate to the 2, 5-dihydroxyterephthalic acid is 4:3, and the purity of the zinc acetate dihydrate and the 2, 5-dihydroxyterephthalic acid are both above 98%;
step 102: adding ligand solution into metal salt solution, simply synthesizing amorphous MOF-74 nano particles, cleaning and purifying,
methanol is used as a reaction solvent, the purity of the methanol is more than 98 percent, metal salt and ligand are respectively and fully dissolved in the methanol, the proportion of the ligand in the ligand solution to the methanol is 3mmol to 50 mL, the proportion of the metal salt solution to the methanol is 4 mmol to 150 mL, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
the polytetrafluoroethylene microporous filter membrane, distilled water and methanol are used as cleaning agents to be alternately cleaned, the suction filtration temperature is room temperature, the vacuum degree is less than-0.1 Mpa, and the synthesized MOF-74 nano particles are separated and purified by suction filtration, so that the obtained MOF-74 nano particles are shown in figure 2.
Step 103: preparing MOF-74 nano particles into aqueous dispersion, regulating pH of the dispersion, performing hydrothermal recrystallization to grow to obtain one-dimensional MOF-74 nano rods,
specifically, all MOF-74 nano particles obtained in the step 102 are dispersed in 50 mL distilled water, the pH of the dispersion is regulated to 7 by using 1M HCl solution and 1M NaOH solution, then the dispersion after the pH regulation is transferred to a 75 mL reaction kettle for hydrothermal reaction, the hydrothermal reaction temperature is 170 ℃, the reaction time is 10 hours, and the MOF-74 nano rod is obtained by drying in a vacuum drying oven at 40-80 ℃ for 12-16 hours after purification by using a suction filtration method;
step 104: performing high-temperature pyrolysis carbonization on the MOF-74 nanorods obtained in the step 103 to obtain the metal-organic framework-derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process is as follows: under the protection of nitrogen or argon, the temperature is raised to 1200 ℃ at 3 ℃/min and the temperature is kept for 3 hours, so as to obtain the undoped one-dimensional porous carbon material.
Example 3
As shown in fig. 1, a preparation method of an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a metal coordination center for providing metal salt, 2, 5-dihydroxyterephthalic acid is used as a ligand,
the molar ratio of the zinc acetate dihydrate to the 2, 5-dihydroxyterephthalic acid is 4:2.5, and the purity of the zinc acetate dihydrate and the 2, 5-dihydroxyterephthalic acid are above 98%;
step 102: adding ligand solution into metal salt solution, simply synthesizing amorphous MOF-74 nano particles, cleaning and purifying,
methanol is used as a reaction solvent, the purity of the methanol is more than 98 percent, metal salt and ligand are respectively and fully dissolved in the methanol, the proportion of the ligand in the ligand solution to the methanol is 2 mmol to 50 mL, the proportion of the metal salt solution to the methanol is 4 mmol to 150 mL, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
the polytetrafluoroethylene microporous filter membrane, distilled water and methanol are used as cleaning agents to be alternately cleaned, the suction filtration temperature is room temperature, the vacuum degree is less than-0.1 Mpa, and the synthesized MOF-74 nano particles are separated and purified by suction filtration, so that the obtained MOF-74 nano particles are shown in figure 2.
Step 103: preparing MOF-74 nano particles into aqueous dispersion, regulating pH of the dispersion, performing hydrothermal recrystallization to grow to obtain one-dimensional MOF-74 nano rods,
specifically, all MOF-74 nano particles obtained in the step 102 are dispersed in 50 mL distilled water, the pH of the dispersion liquid is regulated to 9 by using 1M HCl solution and 1M NaOH solution, then the dispersion liquid after regulating the pH is transferred to a 75 mL reaction kettle for hydrothermal reaction, the hydrothermal reaction temperature is 165 ℃, the reaction time is 6 hours, and the MOF-74 nano rod is obtained by drying the purified MOF-74 nano particles in a vacuum drying oven at 40-80 ℃ for 12-16 hours by using a suction filtration method;
step 104: performing high-temperature pyrolysis carbonization on the MOF-74 nanorods obtained in the step 103 to obtain the metal-organic framework-derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process is as follows: under the protection of nitrogen or argon, heating to 1000 ℃ at 3 ℃/min and preserving heat for 2 hours to obtain the undoped one-dimensional porous carbon material shown in figure 6, wherein the one-dimensional porous carbon material is free of metallic zinc and the undoped one-dimensional porous carbon material is obtained as shown in figure 7.
As shown in fig. 3-5, with the increase of the pH of the dispersion, the aspect ratio of the MOF-74 nanorods obtained after the hydrothermal reaction gradually increases, the length of the nanorods becomes longer, the diameter of the nanorods is reduced, and the one-dimensional nanorod structure can be regulated and controlled.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications could be made by those skilled in the art without departing from the principles of the invention, which modifications would also be considered to be within the scope of the invention.
Claims (6)
1. The preparation method of the undoped one-dimensional porous carbon material is characterized by comprising the following steps of:
(1) The metal salt zinc acetate dihydrate and ligand 2, 5-dihydroxyterephthalic acid with the molar ratio of 4 (1.5-3) are respectively and fully dissolved in a solvent to form a metal salt solution and a ligand solution, the ligand solution is dropwise added into the metal salt solution under intense stirring, continuous stirring is carried out to fully react, and then the MOF-74 nano particles are obtained through separation and purification;
(2) Dispersing MOF-74 nano particles obtained in the step (1) in distilled water, and regulating the pH of the dispersion to be 5-9;
(3) Carrying out hydrothermal reaction on the dispersion liquid obtained in the step (2) at 165-175 ℃ to carry out recrystallization growth, wherein the reaction time is 6-12 hours, and separating, purifying and drying to obtain the MOF-74 nanorod;
(4) Under the protection of inert gas, the MOF-74 nanorod obtained in the step (3) is heated to 1000-1200 ℃, the temperature is kept for 2-3 hours, and Zn, H and O elements are evaporated to form rich pore channel structures in the high-temperature pyrolysis process, so that the undoped one-dimensional porous carbon material is obtained.
2. The method for preparing undoped one-dimensional porous carbon material according to claim 1, wherein the ratio of the ligand to the solvent in the ligand solution is (1.5-3 mmol): 50 mL, and the ratio of the metal salt to the solvent in the metal salt solution is 4 mmol:150 mL.
3. The method for producing an undoped one-dimensional porous carbon material according to claim 1 or 2, wherein the solvent is methanol.
4. An undoped one-dimensional porous carbon material prepared by the method according to any one of claims 1 to 3, wherein the material has a microporous, macroporous or mesoporous structure.
5. The undoped one-dimensional porous carbon material of claim 4, wherein the mesoporous fraction is greater than the fraction of micropores and macropores.
6. The undoped one-dimensional porous carbon material according to claim 4 or 5, wherein said material has a specific surface area of more than 2000 m 2 /g。
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