CN108002378B - Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure - Google Patents
Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure Download PDFInfo
- Publication number
- CN108002378B CN108002378B CN201711234794.8A CN201711234794A CN108002378B CN 108002378 B CN108002378 B CN 108002378B CN 201711234794 A CN201711234794 A CN 201711234794A CN 108002378 B CN108002378 B CN 108002378B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- cluster
- phosphorus
- hypophosphite
- zno
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to the field of inorganic materials, and aims to provide a preparation method of a nitrogen-phosphorus co-doped carbon tube cluster with a reinforced structure. In an organic solvent, performing polymerization crosslinking reaction on hypophosphite and a metal organic framework with surface active hydroxyl; after the reaction product is carbonized, removing metal atoms by acid washing; and then carrying out graphitization treatment to obtain the nitrogen-phosphorus co-doped carbon tube cluster with enhanced mechanical properties. According to the invention, after the metal organic framework is modified by hypophosphite, the nitrogen-phosphorus co-doped carbon material can be obtained. The mechanical property of the graphitized carbon material is enhanced, and the phenomena of agglomeration, structure collapse and the like are effectively avoided. The product modified by hypophosphite has obviously improved electrocatalytic performance, and not only shows excellent catalytic activity in the aspect of oxygen reduction reaction, but also shows better performance in the aspect of oxygen precipitation reaction.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to preparation and application of a porous nitrogen-phosphorus co-doped carbon tube cluster.
Background
The metal-air battery (such as a zinc-air battery) has the advantages of high energy conversion efficiency, cleanness, environmental protection and high energy density, and is a clean and efficient power generation device. The development of Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) on the cathode of a high efficiency catalytic metal-air battery is the key to the development of this battery technology. Currently, platinum is a high-efficiency catalyst for catalyzing ORR, but the OER catalytic activity is poor, and ruthenium and iridium are high-efficiency catalysts for catalyzing OER reaction, but the ORR activity is low. Therefore, the development of a bifunctional catalyst for simultaneously catalyzing ORR and OER is of great significance. The porous carbon material obtained by taking the metal organic framework as a precursor and carbonizing at high temperature has the advantages of large specific surface area and more active sites, and is an electrocatalytic material which can potentially replace noble metals. Particularly, the porous carbon material with the three-dimensional communicated hollow structure is more beneficial to the transportation of substances, so that the porous carbon material has higher electrocatalytic activity. However, most porous carbon materials are easy to collapse and agglomerate at high temperature, so that the material transmission channel of the porous carbon is damaged to influence the catalytic activity. However, the porous carbon material having a hollow structure is more likely to collapse due to lack of support inside the material.
ZnO is used as a hard template and a zinc source, zinc ions are provided to react with 2-methylimidazole, ZIF-8(ZIF-8, a zeolite imidazole ester framework material) can uniformly grow on the surface of ZnO to form a ZnO @ ZIF-8 core-shell structure, ZnO is removed through high-temperature carbonization and acid washing, and finally, the nitrogen-doped porous carbon tube with a hollow structure can be obtained through graphitization treatment. And (4) obtaining the nitrogen-doped carbon tube cluster with the hollow structure by taking the ZnO cluster as a template. However, during the high-temperature graphitization treatment, the nitrogen-doped carbon tube cluster can have structural collapse and shrinkage phenomena, thereby affecting the electrocatalytic performance. Therefore, the development of a method capable of strengthening the structure of the porous carbon material and obviously improving the electrocatalytic performance of the carbon material has important practical significance. According to the invention, surface chemical modification is carried out on the metal organic framework before carbonization, so that the mechanical property of the carbon material is enhanced, the carbon material keeps good structural morphology in high-temperature treatment, and meanwhile, a nitrogen-phosphorus co-doped product is obtained, so that the electrocatalytic performance of the carbon material is obviously improved.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of collapse and shrinkage of a carbon tube in the prior art and providing a preparation method of a nitrogen-phosphorus co-doped carbon tube bundle with a reinforced structure and high-efficiency ORR and OER catalysis. According to the invention, the surface of the metal organic framework is modified, so that covalent bonds are formed between the surface hydroxyl groups and the hypophosphite, and the aim of enhancing the mechanical strength of the carbon material in the carbonization process is achieved.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the nitrogen-phosphorus co-doped carbon tube cluster with the reinforced structure is characterized in that in an organic solvent, hypophosphite and a metal organic framework with surface active hydroxyl are subjected to polymerization crosslinking reaction; after the reaction product is carbonized, removing metal atoms by acid washing; then carrying out graphitization treatment to obtain a nitrogen-phosphorus co-doped carbon tube cluster with enhanced mechanical properties;
the preparation method of the metal organic framework with the surface active hydroxyl comprises the following steps: adding the ZnO cluster into a methanol solution of 2-methylimidazole, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying for later use.
In the invention, the structural formula of the hypophosphite is shown as the formula (I):
wherein R1 and R2 are each independently C1-C4 alkyl.
In the present invention, the organic solvent is any one of acetone, butanone, tetrahydrofuran, and toluene.
In the invention, the mass ratio of the hypophosphite to the metal organic framework added at the beginning of the polymerization crosslinking reaction is 1: 2.5-25; the temperature of the polymerization crosslinking reaction is controlled to be 80-150 ℃, and the reaction time is 5-48 hours.
In the invention, the mass concentration of the added hypophosphite solution is 0.1-1%.
In the invention, the carbonization temperature is 450-550 ℃.
In the invention, the graphitization temperature is 700-1100 ℃, and the time for graphitization treatment is 2-4 hours.
In the invention, when the metal organic framework is prepared, the ratio of the ZnO cluster to the methanol solution of the 2-methylimidazole is 1 g: 20-50ml, and the concentration of the methanol solution of the 2-methylimidazole is 0.1M/L.
Description of the inventive principles:
the invention utilizes active hydroxyl groups on the surface of a metal organic framework to react and polymerize with high-activity P-H, P-O bonds in hypophosphite to form interlaced phosphorus-containing polymers on the surface, and then the phosphorus-containing polymers are carbonized at high temperature and are arranged on the surface of a molecular layer to be more than oneThe mechanical properties of the porous carbon material are strengthened, so that the porous carbon material effectively avoids the phenomena of structural collapse and agglomeration under the high-temperature condition (figures 4 and 5). In addition, a phosphorus source is provided by the phosphorus-containing polymer, and a rich nitrogen source is provided by the 2-methylimidazole in the ZIF-8, so that a nitrogen-phosphorus co-doped porous carbon material is obtained at a high temperature (shown in the attached figures 7 and 8). The two factors jointly cause that the nitrogen-phosphorus co-doped carbon tube cluster has more outstanding ORR catalytic performance than platinum-carbon (figure 9), and the limiting current density (5.3 mA/cm)2) Compared with the product without hypophosphite modification (4.1 mA/cm)2) Obviously increased, even surpassed the platinum carbon; the initial reduction potential (0.92) was shifted by 90mV in comparison with the unmodified product (0.83). In the aspect of OER, the modified nitrogen-phosphorus co-doped product has lower catalytic overpotential and higher current density, and shows obvious OER catalytic activity.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the product which is directly graphitized without modification in the prior art, the nitrogen-phosphorus co-doped carbon material can be obtained after the metal organic framework is modified by the hypophosphite. The mechanical property of the graphitized carbon material is enhanced, and the phenomena of agglomeration, structure collapse and the like are effectively avoided (figure 4). The carbon tube cluster with the same mass has larger volume of the modified product (the volume after modification is almost one time larger than that before modification), which shows that the phenomena of shrinkage, collapse and the like are obviously improved.
2. The product modified by hypophosphite has obviously improved electrocatalytic performance, and not only shows excellent catalytic activity in the aspect of oxygen reduction reaction, but also shows better performance in the aspect of oxygen precipitation reaction.
Drawings
FIG. 1 is a scanning electron micrograph of a ZnO cluster;
FIG. 2 is a scanning electron micrograph of the ZnO @ ZIF-8 cluster;
FIG. 3 is a scanning electron micrograph of a nitrogen-doped carbon tube cluster without hypophosphite modification;
FIG. 4 is a scanning electron microscope image of nitrogen and phosphorus co-doped carbon tube clusters prepared after hypophosphite modification;
FIG. 5 is a hollow structure diagram of a nitrogen-phosphorus co-doped carbon tube cluster prepared after hypophosphite modification;
FIG. 6 is a Transmission Electron Microscope (TEM) image of a nitrogen-phosphorus co-doped carbon tube cluster hollow structure;
FIG. 7 is a nitrogen and phosphorus co-doped carbon tube cluster X-ray photoelectron spectroscopy (XPS) broad spectrum;
FIG. 8 is an X-ray photoelectron spectroscopy (XPS) plot of the P element of a nitrogen and phosphorus co-doped carbon tube cluster;
fig. 9 is a graph showing comparison of electrocatalytic activities of nitrogen-doped carbon tube clusters prepared without hypophosphite modification and nitrogen-phosphorus co-doped carbon tube clusters prepared according to the present invention. In the figure, (a) is a linear scanning curve of oxygen reduction reaction, and (b) is a linear scanning curve of oxygen evolution reaction, and the loading of all catalysts is 0.1mg/cm2。
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
0.5g of ZnO cluster (figure 1) and 30mL of 0.1M/L methanol solution of 2-methylimidazole are added into a 50mL of tetra-polyfluoro reaction kettle and reacted for 3 hours at the temperature of 80 ℃ to obtain ZnO @ ZIF-8 cluster, and the ZnO @ ZIF-8 cluster is washed by alcohol and water in sequence and then dried.
Adding the obtained ZnO @ ZIF-8 cluster (0.5g, shown in the attached figure 2) and 20g of acetone solution of 0.1 mass percent of monobutyl hypophosphite into a tetrapolyfluoro reactor, carrying out closed reaction at 110 ℃ for 24 hours to obtain a chemically modified ZnO @ ZIF-8 cluster, then carbonizing the modified ZnO @ ZIF-8 cluster in a nitrogen atmosphere at 550 ℃ for 3 hours to obtain ZnO @ C, carrying out acid pickling with 1M/L hydrochloric acid solution to remove a ZnO template and other Zn-containing substances in the ZnO @ C, and carrying out freeze-drying treatment to obtain the metal-free nitrogen-phosphorus co-doped carbon tube cluster. And finally, graphitizing the nitrogen-phosphorus co-doped carbon tube bundle at 850 ℃ in an inert atmosphere for 3 hours to obtain the nitrogen-phosphorus co-doped carbon tube bundle with high electrocatalytic activity.
As can be seen from FIG. 4, the morphology of the porous carbon tube cluster modified by hypophosphite and then graphitized at high temperature is completely consistent with that of the ZnO cluster, and no obvious structural collapse and agglomeration phenomena occur, and FIGS. 5 and 6 illustrate that nitrogen and phosphorus obtained after modification are used togetherThe doped carbon tube cluster has a complete hollow structure, and the wall thickness of the carbon tube is about 5 nm. FIG. 7 shows that after hypophosphite modification, nitrogen and phosphorus co-doped product is obtained after graphitization treatment, and P can be seen on XPS broad spectrum2sThe peak of (2) and the P-C bond and the P-O bond formed after doping the P element can be seen in figure 8.
Example 2
Adding 0.5g ZnO cluster and 30mL of 0.1M/L methanol solution of 2-methylimidazole into a 50mL tetra-polyfluoro reaction kettle, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying.
And (2) carrying out closed reaction on the product ZnO @ ZIF-8 cluster (0.5g) and 20g tetrahydrofuran solution of 0.2 mass percent isobutyl hypophosphite at 110 ℃ in a polyfluortetraethylene reaction kettle for 24 hours to obtain chemically modified ZnO @ ZIF-8 cluster, carbonizing the modified ZnO @ ZIF-8 cluster at 550 ℃ in a nitrogen atmosphere for 3 hours to obtain ZnO @ C, pickling with 1M/L hydrochloric acid solution to remove a ZnO template and other Zn-containing substances in the ZnO @ C, and carrying out freeze-drying treatment to obtain the metal-free nitrogen-phosphorus co-doped carbon tube cluster. And finally, graphitizing the nitrogen-phosphorus co-doped carbon tube bundle at 1100 ℃ in an inert atmosphere for 4 hours to obtain the nitrogen-phosphorus co-doped carbon tube bundle with high electrocatalytic activity.
Example 3
Adding 0.5g ZnO cluster and 20mL of 0.1M/L methanol solution of 2-methylimidazole into a 50mL tetra-polyfluoro reaction kettle, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying.
And (2) carrying out closed reaction on the product ZnO @ ZIF-8 cluster (0.5g) and 20g of methyl hypophosphite solution with the mass concentration of 0.5% in a tetrapolyfluoro reaction kettle at the temperature of 80 ℃ for 48 hours to obtain chemically modified ZnO @ ZIF-8 cluster, carbonizing the modified ZnO @ ZIF-8 cluster at the temperature of 500 ℃ in a nitrogen atmosphere for 3 hours to obtain ZnO @ C, carrying out acid pickling on the ZnO template and other Zn-containing substances in the ZnO @ C by using 1M/L hydrochloric acid solution, and carrying out freeze-drying treatment to obtain the metal-free nitrogen-phosphorus co-doped carbon tube cluster. And finally, graphitizing the nitrogen-phosphorus co-doped carbon tube bundle at 950 ℃ in an inert atmosphere for 2 hours to obtain the nitrogen-phosphorus co-doped carbon tube bundle with high electrocatalytic activity.
Example 4
Adding 0.5g ZnO cluster and 50mL of 0.1M/L methanol solution of 2-methylimidazole into a 100mL tetra-polyfluoro reaction kettle, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying.
And (2) carrying out closed reaction on the product ZnO @ ZIF-8 cluster (0.5g) and 20g of toluene solution of ethyl hypophosphite with the mass concentration of 1% in a tetrapolyfluoro reaction kettle at the temperature of 150 ℃ for 5 hours to obtain chemically modified ZnO @ ZIF-8 cluster, carbonizing the modified ZnO @ ZIF-8 cluster at the temperature of 450 ℃ in a nitrogen atmosphere for 3 hours to obtain ZnO @ C, carrying out acid pickling on the ZnO template and other Zn-containing substances in the ZnO @ C by using 1M/L hydrochloric acid solution, and carrying out freeze-drying treatment to obtain the metal-free nitrogen-phosphorus co-doped carbon tube cluster. And finally, graphitizing the nitrogen-phosphorus co-doped carbon tube bundle at 700 ℃ in an inert atmosphere for 3 hours to obtain the nitrogen-phosphorus co-doped carbon tube bundle with high electrocatalytic activity.
Comparative examples
Adding 0.5g ZnO cluster and 30mL of 0.1M/L2-methylimidazole methanol solution into a 50mL tetra-polyfluoro reaction kettle, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying.
And carbonizing the obtained ZnO @ ZIF-8 cluster for 3 hours at 550 ℃ in a nitrogen atmosphere to obtain ZnO @ C, then removing a ZnO template and other Zn-containing substances in the ZnO @ C by using 1M/L hydrochloric acid solution, and then performing freeze-drying treatment to obtain the nitrogen-doped carbon tube cluster. And finally, graphitizing the nitrogen-doped carbon tube cluster for 3 hours at 850 ℃ in an inert atmosphere to obtain the nitrogen-doped carbon tube cluster.
As can be seen from the attached figure 3, the porous carbon tube cluster obtained without hypophosphite modification obviously generates the structure collapse phenomenon, the morphology of the porous carbon tube cluster is greatly different from that of a ZnO cluster, and the volume of the porous carbon tube cluster is much smaller than that of a product modified by hypophosphite (the volume of the porous carbon tube cluster is almost twice as large as that of the product modified by hypophosphite after modification) under the same mass, so that the problems of shrinkage and collapse are further explained; as shown in fig. 9, compared with the nitrogen-phosphorus co-doped product, the product obtained without modifying hypophosphite has the minimum ORR limiting current density and the maximum overpotential of the initial reduction potential, and the OER catalytic performance of the product is also inferior to that of the nitrogen-phosphorus co-doped product.
Claims (8)
1. A preparation method of a nitrogen-phosphorus co-doped carbon tube cluster with a reinforced structure is characterized in that hypophosphite and a metal organic framework with surface active hydroxyl are subjected to a polymerization crosslinking reaction in an organic solvent; after the reaction product is carbonized, removing metal atoms by acid washing; then carrying out graphitization treatment to obtain a nitrogen-phosphorus co-doped carbon tube cluster with enhanced mechanical properties;
the preparation method of the metal organic framework with the surface active hydroxyl comprises the following steps: adding the ZnO cluster into a methanol solution of 2-methylimidazole, reacting for 3 hours at 80 ℃ to obtain ZnO @ ZIF-8 cluster, washing with alcohol and water in sequence, and drying for later use.
2. The method of claim 1, wherein the hypophosphite ester has the formula (I):
wherein R1 and R2 are each independently C1-C4 alkyl.
3. The method according to claim 1, wherein the organic solvent is any one of acetone, butanone, tetrahydrofuran, or toluene.
4. The process according to claim 1, wherein the mass ratio of the hypophosphite to the metal-organic framework added at the beginning of the polymeric crosslinking reaction is 1: 2.5-25; the temperature of the polymerization crosslinking reaction is controlled to be 80-150 ℃, and the reaction time is 5-48 hours.
5. The method according to claim 1, wherein the hypophosphite solution is added at a mass concentration of 0.1% to 1%.
6. The method as claimed in claim 1, wherein the carbonization temperature is 450-550 ℃.
7. The method as claimed in claim 1, wherein the graphitization temperature is 700 ℃ and 1100 ℃, and the time for graphitization treatment is 2-4 hours.
8. The method according to claim 1, wherein the ratio of the ZnO cluster to the methanol solution of 2-methylimidazole is 1 g: 40-100ml, and the concentration of the methanol solution of 2-methylimidazole is 0.1M/L in the preparation of the metal-organic framework.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711234794.8A CN108002378B (en) | 2017-11-30 | 2017-11-30 | Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711234794.8A CN108002378B (en) | 2017-11-30 | 2017-11-30 | Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108002378A CN108002378A (en) | 2018-05-08 |
| CN108002378B true CN108002378B (en) | 2020-11-13 |
Family
ID=62055249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711234794.8A Active CN108002378B (en) | 2017-11-30 | 2017-11-30 | Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108002378B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105752960A (en) * | 2016-03-08 | 2016-07-13 | 兰州理工大学 | Sulfur and phosphorus co-doped mesoporous carbon material and preparation method thereof |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106475122A (en) * | 2016-10-14 | 2017-03-08 | 中国石油大学(华东) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst |
| CN106629671A (en) * | 2017-01-04 | 2017-05-10 | 苏州金泉新材料股份有限公司 | Preparation method of multifunctional nanocluster |
| CN106992076A (en) * | 2017-03-08 | 2017-07-28 | 北京化工大学 | A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material |
| CN107346825A (en) * | 2017-06-30 | 2017-11-14 | 北京化工大学 | Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294133B2 (en) * | 2011-03-18 | 2019-05-21 | Css Nanotech, Inc. | Methods of synthesizing three-dimensional heteroatom-doped carbon nanotube macro materials and compositions thereof |
| TWI537997B (en) * | 2013-05-21 | 2016-06-11 | 國立清華大學 | Supercapacitor and method for manufacturing electrode thereof |
-
2017
- 2017-11-30 CN CN201711234794.8A patent/CN108002378B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003368A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof |
| CN104003367A (en) * | 2014-05-06 | 2014-08-27 | 北京理工大学 | Phosphor-nitrogen exotic atom-doped porous carbon material and synthesis method thereof |
| CN105006375A (en) * | 2015-06-04 | 2015-10-28 | 郑州大学 | Nitrogen and phosphor co-doped porous carbon nanotube, and preparation method and application thereof |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN105752960A (en) * | 2016-03-08 | 2016-07-13 | 兰州理工大学 | Sulfur and phosphorus co-doped mesoporous carbon material and preparation method thereof |
| CN106000438A (en) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials |
| CN106475122A (en) * | 2016-10-14 | 2017-03-08 | 中国石油大学(华东) | A kind of Ni of low temperature preparation three-dimensional step pore structure2The method of P catalyst |
| CN106629671A (en) * | 2017-01-04 | 2017-05-10 | 苏州金泉新材料股份有限公司 | Preparation method of multifunctional nanocluster |
| CN106992076A (en) * | 2017-03-08 | 2017-07-28 | 北京化工大学 | A kind of nitrogen, phosphorus, the preparation method of fluorin-doped carbon-based mixing capacitance material |
| CN107346825A (en) * | 2017-06-30 | 2017-11-14 | 北京化工大学 | Carbon-based nonmetallic hydrogen reduction/precipitation dual purpose catalyst of a kind of nitrogen, phosphor codoping and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Interlocked multi-armed carbon for stable oxygen;Yiming Li etal;《Chem. Commun》;20161231;第5520页右栏第3段至第5522页右栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108002378A (en) | 2018-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110052282B (en) | Preparation and application of transition metal phosphide/core-shell type nitrogen-doped carbon nanofiber composite material | |
| CN107346825B (en) | Nitrogen and phosphorus co-doped carbon-based nonmetal oxygen reduction/precipitation double-effect catalyst and preparation method thereof | |
| CN110911697B (en) | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof | |
| CN112941669B (en) | Metal-nitrogen co-doped carbon nanofiber material and preparation method and application thereof | |
| CN113060719A (en) | Wood-based carbon foam and preparation method thereof, cathode electrocatalyst, cathode and metal-air battery | |
| CN107871876B (en) | Preparation method of bifunctional catalytic carbon material for zinc-air battery | |
| CN111659439A (en) | Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof | |
| CN111883785B (en) | Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof | |
| Chen et al. | Enhanced electrochemical performance in microbial fuel cell with carbon nanotube/NiCoAl-layered double hydroxide nanosheets as air-cathode | |
| CN113611878A (en) | Nitrogen-rich bio-oil-based porous carbon and preparation method and application thereof | |
| He et al. | Performance of nitrogen-containing macroporous carbon supported cobalt catalyst synthesized through in-situ construction of catalytic sites for oxygen reduction reaction | |
| CN112968184A (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| Liu et al. | Carbothermal redox reaction in constructing defective carbon as superior oxygen reduction catalysts | |
| CN108002378B (en) | Preparation method of nitrogen-phosphorus co-doped carbon tube cluster with reinforced structure | |
| CN110055556A (en) | Evolving hydrogen reaction catalyst and its preparation method and application | |
| CN113054209A (en) | Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof | |
| CN110668417A (en) | Preparation method of hollow cactus-shaped carbon sheet-carbon nano tube | |
| Zeng et al. | Fabrication of hierarchical porous carbon for oxygen reduction reaction by selective hydrolysis of hemicelluloses and lignin from eucalyptus wood | |
| CN115228496A (en) | Rice hull biochar-nano iron-nitrogen composite catalytic material and preparation method thereof | |
| CN112675897B (en) | Preparation method of asphalt-based oxygen reduction electrocatalyst | |
| CN112725830B (en) | Preparation method of multistage pore cobalt phosphide/nitrogen-doped carbon network electrocatalyst | |
| CN114725328A (en) | Nitrogen-doped biomass-derived porous carbon-supported Fe3O4Fe composite material and preparation method and application thereof | |
| CN114188549B (en) | Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode | |
| CN115094432B (en) | Preparation method of transition metal carbide/single-walled carbon nanotube composite film with integrated structure and function | |
| CN116581306B (en) | Plant fiber derived transition metal porous nitrogen-doped carbon catalyst and preparation method and application thereof |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 314001 No.2 Photovoltaic Science and Technology Park, no.1288 Kanghe Road, Xiuzhou District, Jiaxing, Zhejiang Province Applicant after: JIAXING University Address before: 314001 Yuexiu South Road, Nanhu District, Zhejiang, China, No. 56, No. Applicant before: JIAXING University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |