CN109160504B - 3D porous spiral polyhedral material, preparation method and application - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000011975 tartaric acid Substances 0.000 claims description 16
- 235000002906 tartaric acid Nutrition 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008247 solid mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
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- 229910052786 argon Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
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- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
The invention provides a 3D porous spiral polyhedral material, which is provided with micropores, mesopores and/or macropores, wherein the structural unit of the 3D porous spiral polyhedral material is a 2D carbon nanosheet. The invention also provides a preparation method of the 3D porous spiral polyhedral material. The raw materials and precursors of the invention are commonly and easily available, and the synthesized 3D porous spiral polyhedral material has a carbon structure similar to a spiral icosahedron, and the specific surface area is up to 2034.2m2And/g, the preparation process is not complex, the preparation conditions are not harsh, a 3D porous spiral polyhedron can be fired by controlling the pressure intensity by utilizing a simple one-step synthesis method, and the 3D porous spiral polyhedron material disclosed by the invention can be widely applied to the fields of macromolecule catalysis, adsorption and separation.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a 3D porous spiral polyhedral material, a preparation method and application.
Background
Graphene is considered to be the strongest material in its two-dimensional form, and researchers have desired to be able to take advantage of the strong strength of its two-dimensional form in three-dimensional materials by pressing graphene platelets together with the application of heat and pressure to create a complex stable structure, named "gyroid", that resembles the structure of coral and diatoms organisms with a large surface area relative to volume, a density of only 5% of iron, and a strength of 10 times or more that of iron, which is one of the lightest and strong materials to date. Researchers also use 3D printers to simulate and enlarge the structure, and similar structures which are expanded by thousands of times are manufactured and tested to prove the excellent mechanical properties of the structure.
The excellent properties of the structure are mainly due to this unique construction rather than the material itself, which means that if other materials can be made into the same geometry, the same strength of light materials can be obtained, however, the structure is difficult to manufacture by conventional methods and graphene, and therefore, there is still a need to develop a new material and preparation method.
Disclosure of Invention
In order to solve the problem that the conventional method and graphene cannot be used for preparing the spiral icosahedron in the prior art, the invention aims to provide a 3D porous spiral polyhedron.
The invention also aims to provide a preparation method of the 3D porous spiral polyhedron.
In order to achieve the purpose, the invention adopts the following technical scheme:
A3D porous spiral polyhedral material is provided with micropores, mesopores and/or macropores, and the structural unit of the 3D porous spiral polyhedral material is a 2D carbon nanosheet.
Preferably, the thickness of the 2D carbon nano sheet is 1-12 nm.
Preferably, the specific surface area of the 3D porous spiral polyhedral material is 400-2500 m2/g。
Preferably, the pore volume of the 3D porous spiral polyhedral material is 0.1-1.5 cm3/g。
Preferably, the pore diameter of micropores in the 3D porous spiral polyhedral material is less than 1 nm.
The preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing.
Preferably, the precursor in step (1) includes at least one of ammonium chloride, zinc chloride, potassium hydroxide, sodium hydroxide and phosphoric acid, and the solvent is deionized water.
Further preferably, the precursor in step (1) is ammonium chloride.
Preferably, the mass ratio of the tartaric acid, the precursor and the solvent in the step (1) is (1: 1: 15) to (1: 1: 50).
Further preferably, the mass ratio of the tartaric acid, the precursor and the deionized water in the step (1) is 1: 1: 15.
preferably, the heating temperature in the step (2) is 70-80 ℃, the drying temperature is 70-80 ℃, and the drying time is 10-15 h.
Further preferably, the heating temperature in the step (2) is 75 ℃, the drying temperature is 75 ℃, and the drying time is 12 h.
Preferably, the inert gas is argon or nitrogen.
Preferably, the grinding device in the step (3) is an agate mortar, and the grinding time is more than 10 min.
Preferably, the method for heating carbonization is as follows: heating at the speed of 10 ℃/min under the pressure of 0.2-0.5 MPa, heating to 480-550 ℃, preserving heat for 0.5h, continuously heating to 800-1200 ℃, and preserving heat for 3 h.
Further preferably, the method for heating carbonization is as follows: heating up to 500 ℃ at the speed of 10 ℃/min under the pressure of 0.4MPa, preserving heat for 0.5h, continuously heating up to 800-1200 ℃ and preserving heat for 3 h.
Still more preferably, the method of heating carbonization is: heating up to 500 ℃ at the speed of 10 ℃/min under the pressure of 0.4MPa, preserving heat for 0.5h, continuously heating up to 800-1000 ℃ and preserving heat for 3 h.
The 3D porous spiral polyhedral material is applied to the fields of macromolecule catalysis, adsorption and separation.
Tartaric acid is an organic weak acid with both hydroxyl and carboxyl, is extracted from a fermentation by-product of wine, namely tartaric acid, has a structure similar to that of hydroxyl-containing carboxylic acids such as citric acid, malic acid and the like, has strong reaction activity under various conditions, and is widely applied to industries such as food, pharmacy, light industry, chemical industry and the like due to unique physicochemical properties. Tartaric acid can be condensed in molecules and esterified by hydroxyl groups, and has excellent coordination and complexation properties.
The invention has the advantages of
1. The raw materials and precursors of the invention are commonly and easily available, and the synthesized 3D porous spiral polyhedral material has a carbon structure similar to a spiral icosahedron, and the specific surface area is up to 2034.2m2/g；
2. The preparation process is not complex, the preparation conditions are not harsh, and the 3D porous spiral polyhedron can be fired by controlling the pressure intensity by utilizing a simple one-step synthesis method;
3. it is expected that the 3D porous spiral polyhedral material can be widely applied to the fields of macromolecule catalysis, adsorption and separation.
Drawings
FIG. 1 is a scanning electron micrograph of a 3D porous spiral polyhedral material of the present invention.
Fig. 2 is a schematic structural diagram of a gyroid.
FIG. 3 is a transmission electron micrograph of a 3D porous spiral polyhedral material of the present invention.
FIG. 4 is a scanning electron microscope image of a 3D porous spiral polyhedral material prepared by heating and carbonizing at 800 ℃.
FIG. 5 is a scanning electron microscope image of a 3D porous spiral polyhedral material prepared by heating and carbonizing at 900 ℃.
FIG. 6 is a scanning electron microscope image of a 3D porous spiral polyhedral material prepared by heating and carbonizing at 950 ℃.
FIG. 7 is a scanning electron micrograph of a polyhedral material prepared by heat carbonization at 1000 ℃.
FIG. 8 is a graph showing the pore size distribution of the samples of examples 2 to 4.
FIG. 9 is a graph showing the results of the oxygen reduction electrocatalysis performance tests of the samples of examples 2 to 4.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
A3D porous spiral polyhedral material is shown in figure 1, and the structural unit of the 3D porous spiral polyhedral material is a 2D carbon nano sheet. Fig. 2 is a schematic structural diagram of a spiral icosahedron, fig. 3 is a projection electron microscope image of the 3D porous spiral polyhedral material of the present invention, and the difference between light and dark in the image indicates that the nanosheet is distorted and deformed into a 3D structure at high temperature and high pressure.
Example 2
The preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing.
The precursor in the step (1) is ammonium chloride, and the mass ratio of tartaric acid to the precursor to the solvent is 1: 1: 15.
and (3) heating at 75 ℃, drying at 75 ℃ for 12h, and using argon as inert gas.
The heating carbonization method in the step (3) comprises the following steps: heating to 500 deg.C at a speed of 10 deg.C/min under 0.4MPa, maintaining for 0.5 hr, heating to 800 deg.C, and maintaining for 3 hr.
The schematic drawing of the scanning electron microscope of the prepared 3D porous spiral polyhedral material is shown in figure 4.
Example 3
The preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing.
The precursor in the step (1) is ammonium chloride, and the mass ratio of tartaric acid to the precursor to the solvent is 1: 1: 15.
and (3) heating at 75 ℃, drying at 75 ℃ for 12h, and using argon as inert gas.
The heating carbonization method in the step (3) comprises the following steps: heating at a speed of 10 ℃/min under a pressure of 0.4MPa, heating to 500 ℃, keeping the temperature for 0.5h, continuously heating to 900 ℃, and keeping the temperature for 3 h.
The schematic scanning electron microscope of the prepared 3D porous spiral polyhedral material is shown in figure 5.
Example 4
The preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing.
The precursor in the step (1) is ammonium chloride, and the mass ratio of tartaric acid to the precursor to the solvent is 1: 1: 15.
and (3) heating at 75 ℃, drying at 75 ℃ for 12h, and using argon as inert gas.
The heating carbonization method in the step (3) comprises the following steps: heating at a speed of 10 ℃/min under a pressure of 0.4MPa, heating to 500 ℃, keeping the temperature for 0.5h, continuously heating to 950 ℃ and keeping the temperature for 3 h.
The schematic drawing of the scanning electron microscope of the prepared 3D porous spiral polyhedral material is shown in FIG. 6.
Comparative example 1
The preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing.
The precursor in the step (1) is ammonium chloride, and the mass ratio of tartaric acid to the precursor to the solvent is 1: 1: 15.
and (3) heating at 75 ℃, drying at 75 ℃ for 12h, and using argon as inert gas.
The heating carbonization method in the step (3) comprises the following steps: heating to 500 deg.C at a rate of 10 deg.C/min under 0.4MPa, maintaining for 0.5 hr, heating to 1000 deg.C, and maintaining for 3 hr.
The schematic drawing of a scanning electron microscope of the prepared 3D porous spiral polyhedral material is shown in FIG. 7, and the scattering of the structure of the polyhedral material can be seen in the drawing.
Example of detection
In this example, the specific surface area and the pore volume of the 3D porous spiral polyhedral material prepared in examples 2 to 4 were measured, and the results are shown in table 1, and the pore size distribution is shown in fig. 8.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (cm)3/g) |
| Example 2 | 404.9 | 0.21 |
| Example 3 | 931.4 | 0.49 |
| Example 4 | 2034.2 | 1.13 |
In this example, the 3D porous spiral polyhedral material prepared in examples 2 to 4 was further tested for oxygen reduction electrocatalytic performance, as shown in fig. 9, wherein the 950 degree fired sample had oxygen reduction performance close to that of platinum carbon, wherein the initial potential reached 1v (Pt/C ═ 0.96 v).
Claims (4)
1. A3D porous spiral polyhedral material is characterized in that the 3D porous spiral polyhedral material is provided with micropores, mesopores and/or macropores, and the structural unit of the 3D porous spiral polyhedral material is a 2D carbon nanosheet;
the preparation method of the 3D porous spiral polyhedral material comprises the following steps:
(1) adding tartaric acid and a precursor into a solvent, and stirring for dissolving;
(2) heating and stirring the solution obtained in the step (1) until the solvent is completely evaporated and drying;
(3) grinding the solid mixture obtained in the step (2), and putting the ground solid mixture into a tubular furnace protected by inert gas for heating and carbonizing;
the precursor in the step (1) is ammonium chloride, and the solvent is deionized water;
the thickness of the 2D carbon nanosheet is 1-12 nm;
the mass ratio of the tartaric acid, the precursor and the solvent in the step (1) is (1: 1: 15) - (1: 1: 50);
the heating temperature in the step (2) is 70-80 ℃, the drying temperature is 70-80 ℃, and the drying time is 10-15 h;
the method for heating carbonization comprises the following steps: heating at the speed of 10 ℃/min under the pressure of 0.2-0.5 MPa, heating to 480-550 ℃, preserving heat for 0.5h, continuously heating to 800-1200 ℃, and preserving heat for 3 h.
2. The 3D porous spiral polyhedral material of claim 1, wherein the specific surface area of the 3D porous spiral polyhedral material is 400-2500 m2/g。
3. The 3D porous spiral polyhedral material of claim 1The material is characterized in that the pore volume of the 3D porous spiral polyhedral material is 0.1-1.5 cm3/g。
4. Use of a 3D porous helical polyhedral material according to any of the claims 1 to 3 in the field of macromolecular catalysis, adsorption or separation.
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| JP2000342671A (en) * | 1999-06-02 | 2000-12-12 | Kunio Suzuki | Botanical deodorizing agent |
| CN104724693A (en) * | 2015-03-06 | 2015-06-24 | 苏州大学 | Organic-salt-based 3D porous carbon material, and preparation method and application thereof |
| WO2016002668A1 (en) * | 2014-07-03 | 2016-01-07 | 東レ株式会社 | Porous carbon material and method for manufacturing porous carbon material |
| WO2016032915A1 (en) * | 2014-08-23 | 2016-03-03 | Entegris, Inc. | Microporous carbon adsorbent from natural carbohydrates |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN107394212A (en) * | 2017-07-07 | 2017-11-24 | 杨军 | A kind of three-dimensional porous electrode, its preparation method and application |
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Patent Citations (6)
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| JP2000342671A (en) * | 1999-06-02 | 2000-12-12 | Kunio Suzuki | Botanical deodorizing agent |
| WO2016002668A1 (en) * | 2014-07-03 | 2016-01-07 | 東レ株式会社 | Porous carbon material and method for manufacturing porous carbon material |
| WO2016032915A1 (en) * | 2014-08-23 | 2016-03-03 | Entegris, Inc. | Microporous carbon adsorbent from natural carbohydrates |
| CN104724693A (en) * | 2015-03-06 | 2015-06-24 | 苏州大学 | Organic-salt-based 3D porous carbon material, and preparation method and application thereof |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| CN107394212A (en) * | 2017-07-07 | 2017-11-24 | 杨军 | A kind of three-dimensional porous electrode, its preparation method and application |
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