CN111498830A - Undoped one-dimensional porous carbon material and preparation method thereof - Google Patents
Undoped one-dimensional porous carbon material and preparation method thereof Download PDFInfo
- Publication number
- CN111498830A CN111498830A CN202010238322.5A CN202010238322A CN111498830A CN 111498830 A CN111498830 A CN 111498830A CN 202010238322 A CN202010238322 A CN 202010238322A CN 111498830 A CN111498830 A CN 111498830A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- undoped
- mof
- porous carbon
- dimensional porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/32—Specific surface area
Abstract
The invention discloses an undoped one-dimensional porous carbon material and a preparation method thereof, belonging to the field of nano carbon materials. The invention synthesizes a one-dimensional nanorod Zn-MOF-74 with good crystallinity by using an hydrothermal recrystallization method and amorphous nanoparticle Zn-MOF-74, and the one-dimensional nanorod Zn-MOF-74 is pyrolyzed and carbonized at high temperature under inert atmosphere to obtain a one-dimensional undoped porous carbon material with ultrahigh specific surface area dominated by a mesoporous structure, and the morphology regulation of a derived carbon material is realized by regulating and controlling a Zn-MOF-74 precursor, and meanwhile, the specific surface area and the mesoporous proportion of the metal organic framework compound (MOF) derived 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
One-dimensional carbon materials (such as carbon nanotubes, carbon nanofibers, carbon nanorods and the like) have large specific surface area and high conductivity, and are widely applied to the fields of energy storage and conversion (such as supercapacitors, electrocatalysis and batteries), but due to the difficulty in designing and constructing pore channels inside the materials, the specific surface area is difficult to further increase, and the mass transfer inside the materials is limited, so that the application performance of the materials is difficult to further increase.
The Metal-Organic Framework (MOF) is a material which is constructed by taking Metal ions as coordination centers 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 field of energy storage and transformation. However, the MOF derived carbon materials have the problem of single pore structure (mainly microporous structure), which severely limits their applications. Many methods, such as template method (adv. funct. mater. 2016, 26, 8334-.
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, the problem of single pore channel structure of an MOF derived carbon material is solved, and the simple and efficient preparation of the one-dimensional carbon material with the ultrahigh specific surface area is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an undoped one-dimensional porous carbon material comprises the following steps:
(1) respectively and fully dissolving metal salt and a ligand in a solvent to form a metal salt solution and a ligand solution, dropwise adding the ligand solution into the metal salt solution under vigorous stirring, continuously stirring to enable the ligand solution to fully react, and then separating and purifying to obtain MOF-74 nanoparticles;
(2) dispersing the MOF-74 nano particles obtained in the step (1) in distilled water, and adjusting the pH of a dispersion liquid to 5-9;
(3) carrying out hydrothermal reaction on the dispersion liquid obtained in the step (2) at the temperature of 165-175 ℃ for recrystallization growth, wherein the reaction time is 6-12 hours, and separating, purifying and drying to obtain MOF-74 nanorods;
(4) and (3) under the protection of inert gas, heating the MOF-74 nano rod obtained in the step (3) to 1000-1200 ℃, and preserving the heat for 2-3 hours to obtain the undoped one-dimensional porous carbon material.
In the above step, the ligand-to-methanol ratio in the ligand solution is (1.5-3mmol):50 m L, the metal salt-to-methanol ratio in the metal salt solution is 4mmol:150 m L, 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 non-doped one-dimensional porous carbon material obtained by the preparation method has a micropore, macropore and mesoporous structure, the mesoporous proportion is larger than the proportion of the micropore and the macropore, the carbon material has an ultrahigh specific surface area, and the specific surface area is larger than 2000 m2/g。
Has the advantages that: the invention provides an undoped one-dimensional porous carbon material and a preparation method thereof, wherein a MOF precursor with a one-dimensional ordered structure is prepared by using a hydrothermal recrystallization method, and the effective regulation of the one-dimensional MOF structure is realized through the regulation and control of the pH value of a hydrothermal dispersion liquid; according to the invention, the ligand containing only C, O, H is adopted, and almost all O, H elements are evaporated when the synthesized MOF is pyrolyzed and carbonized, so that the one-dimensional porous carbon material of the final product is doped without heteroatoms, and the application of the material in a specific field is realized; in the high-temperature pyrolysis process, the evaporation of elements such as Zn, H, O and the like enables the one-dimensional porous carbon material of the final product to have rich pore channel 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 except micropores, and solves the problem of single pore channel structure of the MOF derived carbon material.
Drawings
FIG. 1 is a flow chart of an ultra-high specific surface area undoped one-dimensional carbon material and a preparation method thereof according to an embodiment of the present 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 under pH 5 conditions in the example of the present invention;
FIG. 4 is a scanning electron microscope image of MOF-74 nanorods obtained under the condition of pH 7 in the example of the present invention;
FIG. 5 is a scanning electron microscope image of MOF-74 nanorods obtained under the condition of pH 9 in the example of the present invention;
FIG. 6 is a scanning electron microscope photograph of a one-dimensional porous carbon material obtained in an example of the present invention;
FIG. 7 is an X-ray photoelectron spectroscopy analysis chart of a one-dimensional porous carbon material obtained in example of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples:
example 1
As shown in fig. 1, a method for preparing an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a ligand for providing a metal coordination center for metal salt, 2, 5-dihydroxy terephthalic 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 both the zinc acetate dihydrate and the purity of the 2, 5-dihydroxyterephthalic acid are more than 98%;
step 102: adding the ligand solution into the 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 ratio of the ligand to the methanol in a ligand solution is 1.5 mmol:50 m L, the ratio of the metal salt to the methanol in a metal salt solution is 4mmol:150 m L, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
and (3) alternately cleaning with a polytetrafluoroethylene microporous filter membrane, distilled water and methanol as cleaning agents, performing suction filtration at room temperature under the vacuum degree of less than-0.1 Mpa, and performing suction filtration, separation and purification on the synthesized MOF-74 nanoparticles to obtain the MOF-74 nanoparticles as shown in figure 2.
Step 103: preparing the MOF-74 nano particles into water dispersion, adjusting the pH of the dispersion, carrying out hydrothermal recrystallization growth to obtain one-dimensional MOF-74 nano rods,
specifically, completely dispersing the MOF-74 nano particles obtained in the step 102 in 50M L distilled water, adjusting the pH of a dispersion solution to 5 by using a 1M HCl solution and a 1M NaOH solution, transferring the dispersion solution with the adjusted pH to a 75M L reaction kettle, carrying out hydrothermal reaction at 175 ℃ for 12 hours, purifying by using a suction filtration method, and drying in a vacuum drying oven at 40-80 ℃ for 12-16 hours to obtain MOF-74 nano rods;
step 104: pyrolyzing and carbonizing the MOF-74 nanorods obtained in the step 103 at high temperature to obtain a metal organic framework derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process comprises the following steps: under the protection of nitrogen or argon, heating to 1100 ℃ and preserving heat for 2 hours to obtain the undoped one-dimensional porous carbon material.
Example 2
As shown in fig. 1, a method for preparing an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a ligand for providing a metal coordination center for metal salt, 2, 5-dihydroxy terephthalic 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 both the zinc acetate dihydrate and the purity of the 2, 5-dihydroxyterephthalic acid are more than 98%;
step 102: adding the ligand solution into the 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 ratio of the ligand to the methanol in a ligand solution is 3 mmol:50 m L, the ratio of a metal salt solution to the methanol is 4mmol:150 m L, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
and (3) alternately cleaning with a polytetrafluoroethylene microporous filter membrane, distilled water and methanol as cleaning agents, performing suction filtration at room temperature under the vacuum degree of less than-0.1 Mpa, and performing suction filtration, separation and purification on the synthesized MOF-74 nanoparticles to obtain the MOF-74 nanoparticles as shown in figure 2.
Step 103: preparing the MOF-74 nano particles into water dispersion, adjusting the pH of the dispersion, carrying out hydrothermal recrystallization growth to obtain one-dimensional MOF-74 nano rods,
specifically, completely dispersing the MOF-74 nano particles obtained in the step 102 in 50M L distilled water, adjusting the pH of a dispersion solution to 7 by using a 1M HCl solution and a 1M NaOH solution, transferring the dispersion solution with the adjusted pH to a 75M L reaction kettle, carrying out hydrothermal reaction at the temperature of 170 ℃ for 10 hours, purifying by using a suction filtration method, and drying in a vacuum drying oven at the temperature of 40-80 ℃ for 12-16 hours to obtain MOF-74 nano rods;
step 104: pyrolyzing and carbonizing the MOF-74 nanorods obtained in the step 103 at high temperature to obtain a metal organic framework derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process comprises the following steps: under the protection of nitrogen or argon, heating to 1200 ℃ at the speed of 3 ℃/min and preserving the temperature for 3 hours to obtain the undoped one-dimensional porous carbon material.
Example 3
As shown in fig. 1, a method for preparing an undoped one-dimensional porous carbon material comprises the following steps:
step 101: zinc acetate dihydrate is used as a ligand for providing a metal coordination center for metal salt, 2, 5-dihydroxy terephthalic 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 both the zinc acetate dihydrate and the purity of the 2, 5-dihydroxyterephthalic acid are over 98 percent;
step 102: adding the ligand solution into the 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 ratio of the ligand to the methanol in a ligand solution is 2 mmol:50 m L, the ratio of a metal salt solution to the methanol is 4mmol:150 m L, the ligand solution is dropwise added into the metal salt solution under vigorous stirring, the stirring is carried out for 2 hours,
and (3) alternately cleaning with a polytetrafluoroethylene microporous filter membrane, distilled water and methanol as cleaning agents, performing suction filtration at room temperature under the vacuum degree of less than-0.1 Mpa, and performing suction filtration, separation and purification on the synthesized MOF-74 nanoparticles to obtain the MOF-74 nanoparticles as shown in figure 2.
Step 103: preparing the MOF-74 nano particles into water dispersion, adjusting the pH of the dispersion, carrying out hydrothermal recrystallization growth to obtain one-dimensional MOF-74 nano rods,
specifically, completely dispersing the MOF-74 nano particles obtained in the step 102 in 50M L distilled water, adjusting the pH of a dispersion solution to 9 by using a 1M HCl solution and a 1M NaOH solution, transferring the dispersion solution with the adjusted pH to a 75M L reaction kettle, carrying out hydrothermal reaction at 165 ℃ for 6 hours, purifying by using a suction filtration method, and drying in a vacuum drying oven at 40-80 ℃ for 12-16 hours to obtain MOF-74 nano rods;
step 104: pyrolyzing and carbonizing the MOF-74 nanorods obtained in the step 103 at high temperature to obtain a metal organic framework derived ultra-high specific surface area undoped one-dimensional porous carbon material,
specifically, the carbonization process comprises the following steps: 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 does not contain metal zinc as shown in figure 7, so that the undoped one-dimensional porous carbon material is obtained.
As shown in FIGS. 3-5, with the increase of the pH of the dispersion, the length-diameter ratio of the MOF-74 nanorods obtained after the hydrothermal reaction gradually increases, the lengths of the nanorods become longer, the diameters become smaller, and the prepared one-dimensional nanorod structures can be regulated.
The foregoing is directed to the preferred embodiment of the present invention and it is understood that various modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of an undoped one-dimensional porous carbon material is characterized by comprising the following steps:
(1) respectively and fully dissolving metal salt and a ligand in a solvent to form a metal salt solution and a ligand solution, dropwise adding the ligand solution into the metal salt solution under vigorous stirring, continuously stirring to enable the ligand solution to fully react, and then separating and purifying to obtain MOF-74 nanoparticles;
(2) dispersing the MOF-74 nano particles obtained in the step (1) in distilled water, and adjusting the pH of a dispersion liquid to 5-9;
(3) carrying out hydrothermal reaction on the dispersion liquid obtained in the step (2) at the temperature of 165-175 ℃ for recrystallization growth, wherein the reaction time is 6-12 hours, and separating, purifying and drying to obtain MOF-74 nanorods;
(4) and (3) under the protection of inert gas, heating the MOF-74 nano rod obtained in the step (3) to 1000-1200 ℃, and preserving the heat for 2-3 hours to obtain the undoped one-dimensional porous carbon material.
2. The method for producing an undoped one-dimensional porous carbon material as claimed in claim 1, wherein the ligand-to-solvent ratio in the ligand solution is (1.5-3mmol):50 m L, and the metal salt-to-solvent ratio in the metal salt solution is 4mmol:150 m L.
3. The method for producing an undoped one-dimensional porous carbon material as claimed in claim 1 or 2, wherein the solvent is methanol, the metal salt is zinc acetate dihydrate, and the ligand is 2, 5-dihydroxyterephthalic acid.
4. The method for producing an undoped one-dimensional porous carbon material as claimed in claim 3, wherein the molar ratio of zinc acetate dihydrate to 2, 5-dihydroxyterephthalic acid is 4 (1.5-3).
5. An undoped one-dimensional porous carbon material obtained by the production method according to claims 1 to 4.
6. The undoped one-dimensional porous carbon material as claimed in claim 5, wherein the carbon material has a microporous, macroporous, mesoporous structure.
7. The undoped one-dimensional porous carbon material as claimed in claim 6, wherein the proportion of mesopores is larger than the proportion of micropores and macropores.
8. The undoped one-dimensional porous carbon material as claimed in claim 5 or 6, wherein the carbon material has an ultra-high specific surface area, and the specific surface area is more than 2000 m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010238322.5A CN111498830B (en) | 2020-03-30 | 2020-03-30 | Undoped one-dimensional porous carbon material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010238322.5A CN111498830B (en) | 2020-03-30 | 2020-03-30 | Undoped one-dimensional porous carbon material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111498830A true CN111498830A (en) | 2020-08-07 |
| CN111498830B CN111498830B (en) | 2023-09-15 |
Family
ID=71872986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010238322.5A Active CN111498830B (en) | 2020-03-30 | 2020-03-30 | Undoped one-dimensional porous carbon material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111498830B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413919A (en) * | 2021-06-21 | 2021-09-21 | 四川大学 | Hedgehog shaped catalytic material with atom catalytic center and its use in preparing antibacterial medicine |
| CN114247425A (en) * | 2021-12-09 | 2022-03-29 | 南京大学 | Preparation method and application of carbon nanorod spherical superstructure material |
| CN115744876A (en) * | 2022-06-22 | 2023-03-07 | 江苏理工学院 | Synthetic method and application of two-dimensional layered hollow carbon nanoparticle array superstructure |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211040A (en) * | 2013-11-14 | 2014-12-17 | 中国石油大学(北京) | Preparation method of porous carbon nano rod with high specific area |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN105836858A (en) * | 2016-06-03 | 2016-08-10 | 华东师范大学 | Method for preparing capacitive desalination electrode |
| CN106829918A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable micropore carbon nano rod of size |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
-
2020
- 2020-03-30 CN CN202010238322.5A patent/CN111498830B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211040A (en) * | 2013-11-14 | 2014-12-17 | 中国石油大学(北京) | Preparation method of porous carbon nano rod with high specific area |
| CN106829918A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable micropore carbon nano rod of size |
| CN105668548A (en) * | 2016-03-29 | 2016-06-15 | 北京化工大学 | New method for customizing high-dispersion co-doping porous carbon with core-shell structure |
| CN105836858A (en) * | 2016-06-03 | 2016-08-10 | 华东师范大学 | Method for preparing capacitive desalination electrode |
| CN106829924A (en) * | 2017-03-15 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of one-dimensional porous CNT |
| CN110423358A (en) * | 2019-08-14 | 2019-11-08 | 合肥工业大学 | The preparation and application of the porous carbon nano-tube material of the preparation method and one-dimensional N doping of one-dimensional tubulose MOF material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413919A (en) * | 2021-06-21 | 2021-09-21 | 四川大学 | Hedgehog shaped catalytic material with atom catalytic center and its use in preparing antibacterial medicine |
| CN113413919B (en) * | 2021-06-21 | 2022-09-20 | 四川大学 | Hedgehog shaped catalytic material with atom catalytic center and its use in preparing antibacterial medicine |
| CN114247425A (en) * | 2021-12-09 | 2022-03-29 | 南京大学 | Preparation method and application of carbon nanorod spherical superstructure material |
| CN115744876A (en) * | 2022-06-22 | 2023-03-07 | 江苏理工学院 | Synthetic method and application of two-dimensional layered hollow carbon nanoparticle array superstructure |
| CN115744876B (en) * | 2022-06-22 | 2023-12-22 | 江苏理工学院 | Synthesis method and application of two-dimensional layered hollow carbon nanoparticle array superstructure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111498830B (en) | 2023-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111498830B (en) | Undoped one-dimensional porous carbon material and preparation method thereof | |
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| CN107459029B (en) | Nitrogen/metal atom doped hollow polyhedral nano carbon shell material and preparation method thereof | |
| CN108806998B (en) | Synthesis of ZIF-8-based ternary composite ZnO/ZnCo by solvothermal method2O4Method for producing NiO and use thereof | |
| CN107128926B (en) | Preparation method of self-supporting carbide derived carbon nanowire | |
| CN113005568B (en) | Method for preparing porous Co/C nano fiber by PVP (polyvinyl pyrrolidone) assisted ZIF (zinc-doped carbon) growth | |
| CN113908874A (en) | Nitrogen-rich porous composite carbon material, and preparation method and application thereof | |
| CN108996557B (en) | Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof | |
| CN110665484A (en) | Preparation method of self-supporting mesoporous metal organic framework material with cooperative growth | |
| US20230073650A1 (en) | Carbon nanotube (cnt)-based three-dimensional ordered macroporous (3dom) material and preparation method thereof | |
| CN102584215B (en) | Method for preparing classified porous tetragonal-phase barium titanate ceramics materials | |
| CN112234206A (en) | Method for preparing thin-layer graphene/transition metal fluoride composite positive active material by using antibiotic fungi residues | |
| CN108273533B (en) | Porous g-C with high specific surface area3N4Preparation method of (1) | |
| CN114100648A (en) | Synthetic method of ZnMo-MOF-derived carbon-coated molybdenum carbide | |
| CN109647477B (en) | Rapid preparation method and application of high-yield MOF (Metal organic framework) derivative catalyst | |
| CN113428855A (en) | Sulfur and phosphorus doped biomass porous carbon material and preparation method thereof | |
| CN111204741B (en) | Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material | |
| CN102776565B (en) | Method for preparing nano-structure single crystal silver | |
| CN111234245A (en) | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application | |
| CN108031481B (en) | Ultrathin bismuth oxyhalide nanosheet photocatalyst stripped by silver intercalation and preparation method thereof | |
| CN111137942A (en) | Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof | |
| CN116417594A (en) | Preparation method of negative electrode material of sodium ion battery | |
| CN107459028B (en) | Heteroatom-doped carbon aerogel and preparation method thereof | |
| CN111285350B (en) | Preparation method of micro-mesoporous carbon nanocapsule net | |
| CN101643357B (en) | Tetragonal phase converting process for superfine cubic phase barium titanate powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |