CN115138388B - Cobalt-nitrogen-carbon catalyst with high dispersity and preparation method thereof - Google Patents

Cobalt-nitrogen-carbon catalyst with high dispersity and preparation method thereof Download PDF

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CN115138388B
CN115138388B CN202210775651.2A CN202210775651A CN115138388B CN 115138388 B CN115138388 B CN 115138388B CN 202210775651 A CN202210775651 A CN 202210775651A CN 115138388 B CN115138388 B CN 115138388B
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nitrogen
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carbon catalyst
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CN115138388A (en
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黄超
邓翔
龚志威
王凡
裴晓东
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Sinosteel New Materials Co Ltd
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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    • H01M4/90—Selection of catalytic material
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Abstract

The invention discloses a cobalt-nitrogen-carbon catalyst with high dispersity and a preparation method thereof, and belongs to the technical field of catalyst material preparation. The cobalt nitrogen carbon catalyst takes negatively charged carbon as a carrier, and is carbonized with a ligand connected with Co to form a Co-N-C structure. The preparation method of the cobalt nitrogen carbon catalyst comprises the following steps: mixing a carbon carrier dispersion with an organic ligand solution to enable the organic ligand to be adsorbed on the surface of the carbon carrier; adding cobalt metal salt solution to form a porous material with a periodic network structure, wherein metal ions are used as centers, and organic ligands adsorbed by a carbon carrier are bridged; calcining the purified sample under the protection of inert gas to obtain the cobalt nitrogen carbon catalyst with high dispersity. The invention selects a raw material system with special surface property, proposes to utilize the mutual binding force of electrostatic adsorption between the cobalt nitrogen carbon precursor with positive charges and the carbon carrier with negative charges, effectively improves the dispersity of CoNC on the carrier and can fully utilize the adsorption sites of the carrier with high specific surface.

Description

Cobalt-nitrogen-carbon catalyst with high dispersity and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a high-dispersity cobalt nitrogen carbon catalyst and a preparation method thereof.
Background
Cobalt nitrogen carbon (CoNC) catalytic materials have excellent catalytic activity and are often used for catalytic reactions of various batteries, the pore channel structure of the cobalt nitrogen carbon (CoNC) catalytic materials can provide enough space for oxygen and metal ion transmission, and the catalytic activity can be greatly improved due to the composite effect of a large number of chemical defects and active sites existing in the CoNC. The catalytic activity can be further improved to a certain extent through the shape and the component regulation, but in the liquid phase preparation process of the cobalt-nitrogen-carbon material, the problem that the grain size of microscopic particles of a product is large frequently occurs in the mass production process because the crystal nucleus grows fast in the mother solution, so that the specific surface area of the product is low, and the catalytic activity of the product cannot be fully exerted, so that the control of the dispersion degree and the grain size of the product is a key technology in the catalyst synthesis process.
The currently common synthesis methods of cobalt nitrogen carbon with high dispersity are mainly divided into two types, one type is to use a template method, such as the method reported in patent literature (201310280066.6) that orderly mesoporous silicon dioxide is adopted as a template, then the template is mixed with cobalt salt and phenanthroline, dried and calcined, and finally HF is used for removing SiO 2 The cobalt nitrogen carbon can be obtained by the template. However, the template method is generally complex in synthesis process, and hazardous chemicals such as HF and the like are needed to be adopted in the synthesis process to etch the template, so that the safe production is not facilitated. The other is to load cobalt nitrogen carbon precursor on a carrier with a high specific surface, for example, a carbon nano tube modified by nitrogen reported in patent document (201810035575.5) is used as a carrier, and the cobalt nitrogen carbon material is finally obtained by carrying out high-temperature pyrolysis after absorbing precursor salt of cobalt by an impregnation method. However, the loading method is limited by the surface property of the carrier and the mutual binding force between the carrier and the cobalt nitrogen carbon precursor, and the electrochemical performance of the cobalt nitrogen carbon precursor is reduced due to the common conditions of poor loading uniformity of cobalt nitrogen carbon active sites, low dispersity of cobalt elements and the like in industrial production.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the technical problems of poor loading uniformity, less loading capacity and low dispersity of active sites of cobalt nitrogen carbon in the prior art, the high-dispersity cobalt nitrogen carbon catalyst and the preparation method thereof are provided.
The first aspect of the invention provides a cobalt-nitrogen-carbon catalyst with high dispersity, which takes negatively charged carbon as a carrier and is carbonized with a ligand connected with Co to form a Co-N-C structure.
In some embodiments, the cobalt nitrogen carbon catalyst has a surface area of 600 to 700m 2 Per g, the diameter of the mesoporous is about 2.0-10.0 nm, and the pore volume is 0.1-0.5 cm 3 /g。
The second aspect of the invention provides a preparation method of a cobalt nitrogen carbon catalyst, which comprises the following steps:
mixing the carbon carrier dispersion with an organic ligand solution to enable the organic ligand to be adsorbed on the surface of the carbon carrier, and enabling the organic ligand to be fully contacted with carbon powder under the physical adsorption effect due to the fact that the selected carbon has a high specific surface area and a porous structure;
the cobalt metal salt solution is rapidly added under vigorous stirring, since Co is added as Co in solution 2+ The organic ligand adsorbed by the carbon carrier is a bridged periodic network structure porous material (ZIF-67);
the mixed solution is fully dispersed and uniformly mixed after being vigorously stirred for a period of time, then the uniformly mixed solution is kept stand for aging, because the carbon carrier is alkaline and has negative charge, the generated ZIF-67 has positive charge, and in the processes of full stirring and standing aging, the charge adsorption between the carrier and the cobalt-containing precursor (ZIF-67) is fully balanced, so that the carrier and the cobalt-containing precursor can be tightly combined, the aging time is controlled within the range of 20-30h, and the aged sample is purified;
calcining the purified sample under the protection of inert gas to obtain the cobalt nitrogen carbon catalyst with high dispersity.
In some embodiments, the carbon support dispersion is alkaline or Zeta potential is negative;
and/or, the cobalt metal salt is an acidic metal salt.
In some embodiments, the carbon support is selected from one or more of the group consisting of electro-carbon black XC-72R, EC, graphene;
and/or the cobalt metal salt is selected from one or more of cobalt nitrate, cobalt chloride and cobalt acetate;
and/or the organic ligand is 2-methylimidazole, which is effective and Co 2+ Form bidentate coordination, and has low costIs beneficial to mass production and preparation of samples.
In some embodiments, the concentration of the carbon support dispersion is 0.01 to 0.1mol/L and the concentration of the metal salt solution is 0.005 to 0.05mol/L;
the mass ratio of the addition amount of the carbon carrier to cobalt metal in the cobalt salt is 1:0.1-1, the mass ratio of the organic ligand to cobalt metal in the cobalt salt is 1:0.01-0.1.
In some embodiments, the solvent of the carbon support dispersion and the cobalt metal salt solution is ethanol;
and/or the organic ligand solvent is a mixture of ethanol and methanol, wherein the volume ratio of the ethanol to the methanol in the mixture is (0.5-2): 1.
In some embodiments, the step of purifying treatment described above comprises: the solid sample obtained after suction filtration is washed by ethanol for a plurality of times, because the porous structure of the cobalt-containing precursor can adsorb a small amount of unreacted cobalt salt and 2-methylimidazole, the solid sample is washed by ethanol for a plurality of times, redundant cobalt salt and 2-methylimidazole are removed, and the solid sample is dried under the condition of 60-80 ℃ after natural drying.
In some embodiments, the calcination is at a temperature of 800-1000 ℃ for a time of 1-4 hours. Because the precursor of CoNC has good thermal stability, calcination is needed under the condition of high temperature, the precursor of CoNC is thermally decomposed under the action of high temperature, the organic ligand connected with Co is carbonized to form a Co-N-C structure, and the original carbon carrier is not oxidized to form CO/CO under the protection of inert gas 2 Escape without loss.
The third aspect of the invention provides a catalyst, which is characterized by comprising the cobalt nitrogen carbon catalyst or the cobalt nitrogen carbon catalyst prepared by the preparation method.
Compared with the prior art, the invention has the following technical effects:
(1) The invention creatively selects a raw material system with special surface properties, and proposes that the mutual binding force of electrostatic adsorption between a cobalt nitrogen carbon (CoNC) precursor (ZIF-67) with positive charges and a carbon carrier with negative charges is utilized, so that the dispersity of the CoNC on the carrier is effectively improved, the adsorption sites of the carrier with high specific surface can be fully utilized, and the load effect is effectively improved compared with the prior art.
(2) The synergistic process of electrostatic adsorption-aging balance is added in the preparation process, so that on one hand, charge balance between the CoNC precursor crystal nucleus and the carbon carrier can be further fully completed, the CoNC precursor crystal nucleus is uniformly combined on the surface of the carbon carrier, and on the other hand, the CoNC precursor crystal nucleus can be enabled to have better crystallinity by virtue of the crystallization growth effect of the mother solution of the reaction liquid, and the catalytic activity of the catalyst oxygen reduction after the CoNC is obtained by carbonization is higher.
Drawings
FIG. 1 is an SEM image of sample C/CoNC-1 prepared according to example 1 of the invention;
FIG. 2 is an XRD pattern of sample C/CoNC-1 prepared in example 1 of the present invention.
FIG. 3 is an SEM image of a sample CoNC prepared according to comparative example 1 of the present invention;
FIG. 4 is a graph showing ORR activity test of samples prepared in examples 1, 2, 3& comparative examples in the present invention.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1
0.1g of EC300 was weighed and dispersed in 50mL of ethanol and recorded as solution A, tableThe flour pH is 8.8; 0.29g of cobalt nitrate (cobalt 0.059 g) was weighed out and dispersed in 50mL of ethanol (0.02 mol/L), designated as solution B, and the pH was 6.2. 3.2g of 2-methylimidazole (0.39 mol/L) was weighed and dissolved in 100mL of a mixed solution of methanol and ethanol (the volume ratio of methanol to ethanol is 1:1), and the mixture was designated as solution C; firstly pouring the solution A into the solution C, uniformly mixing, rapidly pouring the solution B into the solution C under intense stirring, continuously stirring for 1h, stopping stirring, standing and aging for 24h at normal temperature, and fully and uniformly dispersing formed Co complex crystal nuclei on an EC300 carbon carrier with a high specific surface through positive and negative electrostatic interaction; firstly, fully immersing an organic ligand into the surface of a carbon carrier, then adding a Co salt solution, which is favorable for forming uniformly distributed Co ligand crystal nuclei on the surface of the carbon carrier, wherein the generated crystal nuclei can be tightly combined with the carbon carrier under the action of static electricity, so that the stability is further improved, and if ZIF-67 is formed firstly and then mixed with the carbon carrier (firstly, mixed solution B, C and then mixed solution A/mixed solution A, B, C) the ZIF-67 is difficult to uniformly distribute on the carbon carrier without agglomeration; filtering and separating after aging, washing with ethanol, and drying with air blast at 70deg.C; part of the sample is spread at the bottom of the crucible, the crucible is transferred into a tube furnace for high-temperature calcination, and N is introduced in the calcination process 2 Protection, N 2 The flow rate of the mixture is kept at 200mL/min, the temperature is raised to 900 ℃ at 10 ℃/min and kept for 2 hours, and then the mixture is naturally cooled to room temperature, so that the EC300/CoNC composite material is obtained and is marked as C/CoNC-1.
The resulting microstructure of C/CoNC-1 is shown in a Scanning Electron Microscope (SEM) photograph of FIG. 1. As can be seen from FIG. 1, the EC300/CoNC composite material is a loose aggregate of particles with a particle size of around 200 nm. As can be seen from the X-ray diffraction analysis (XRD) results of example 1 (FIG. 2), the sample was pure carbon and cobalt phases, with diffraction peaks at 25.6℃corresponding to the carbon phase (PDF#08-0415), diffraction peaks at 44.1 °, 51.3℃and 75.8℃corresponding to the metallic cobalt phase (PDF#01-1255. Table 1 is N of example 1) 2 The adsorption and desorption test result shows that the specific surface area of the sample is 618.2m 2 Per g, the diameter of the mesoporous is about 4.0nm, and the pore volume is 0.21cm 3 The/g is a mesoporous material with high specific surface area, and the high specific surface area and the mesoporous structure are favorable for O 2 And ActivityFull contact of sites, facilitating O 2 An improvement in catalytic activity of the reduction reaction (ORR).
TABLE 1N of example 1 2 Adsorption and desorption test results
Example 2
0.1g of XC-72R was weighed and dispersed in 100mL of ethanol, designated as solution A, 0.29g of cobalt nitrate was dispersed in 100mL of ethanol, designated as solution B, and 3.2g of 2-methylimidazole was weighed and dissolved in 100mL of a mixed solution of methanol and ethanol (the volume ratio of methanol to ethanol was 1:1), designated as solution C. Pouring the solution A into the solution C, mixing uniformly, pouring the solution B into the solution C rapidly under vigorous stirring, keeping stirring for 1h, stopping stirring, standing and aging for 30h at normal temperature, and fully dispersing the formed Co complex crystal nucleus on an XC-72R carbon carrier with a high specific surface uniformly through positive and negative electrostatic interaction. Suction filtration and separation, washing with ethanol and drying with air at 70 ℃. Part of the sample is spread at the bottom of the crucible, the crucible is transferred into a tube furnace for high-temperature calcination, and N is introduced in the calcination process 2 Protection, N 2 The flow rate of the material is kept at 200mL/min, the temperature is raised to 900 ℃ at 10 ℃/min and kept for 2 hours, and then the material is naturally cooled to room temperature, so that the XC-72R/CoNC composite material is obtained and is marked as C/CoNC-2.
The results are consistent with example 1 and will not be described in detail here.
Example 3
0.1g of graphene is weighed and dispersed in 100mL of ethanol, and is marked as solution A, 0.29g of cobalt nitrate is dispersed in 100mL of ethanol and is marked as solution B, and 3.2g of 2-methylimidazole is weighed and dissolved in 100mL of mixed solution of methanol and ethanol (the volume ratio of methanol to ethanol is 1:1) and is marked as solution C. Pouring the solution A into the solution C, mixing uniformly, pouring the solution B into the solution C rapidly under vigorous stirring, keeping stirring for 1h, stopping stirring, standing and aging for 20h at normal temperature, and fully dispersing and uniformly forming Co complex crystal nuclei on a grapheme carbon carrier with a high specific surface through positive and negative electrostatic interaction. Filtering, separating, washing with ethanol,and (5) drying by blowing at 70 ℃. Part of the sample is spread at the bottom of the crucible, the crucible is transferred into a tube furnace for high-temperature calcination, and N is introduced in the calcination process 2 Protection, N 2 The flow rate of the mixture is kept at 200mL/min, the temperature is raised to 900 ℃ at 10 ℃/min and kept for 2 hours, and then the mixture is naturally cooled to room temperature, so that the GO/CoNC composite material is obtained and is marked as C/CoNC-3.
The results are consistent with example 1 and will not be described in detail here.
Comparative example
5.95g of Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 150mL of methanol to prepare solution A, 6.16g of 2-methylimidazole is weighed and dissolved in 150mL of methanol solution to prepare solution B; after the solution A and the solution B are mixed at room temperature and stirred for reaction for 24 hours, the product obtained by the reaction is centrifuged and washed with methanol for several times, and then dried in vacuum at 70 ℃ to obtain ZIF-8 powder. The obtained ZIF-8 powder was dissolved in 150mL of methanol and labeled as solution C, and 8.75g of Co (NO 3 ) 2 ·6H 2 O was dissolved in 200mL of methanol and labeled as solution D; 9.23g of 2-methylimidazole was weighed and dissolved in 50mL of methanol and labeled as solution E; solution D was then poured rapidly into solution C, and the resulting mixed solution was added to solution E, and after stirring at room temperature for 24h, centrifuged and washed several times with methanol, followed by drying under vacuum at 70 ℃. Putting the MOFs precursor obtained after drying in a tube furnace, and introducing N 2 And (3) performing heat treatment in the atmosphere, heating to 900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and naturally cooling to room temperature to obtain the cobalt-nitrogen-carbon material, which is marked as CoNC. Comparing the SEM pictures of example 1 and comparative example (FIG. 1&Fig. 3), it was found that the comparative example exhibited a significant particle agglomeration phenomenon, since the precursor was decomposed completely at a high temperature of 900 c, and sintering of cobalt nitrogen carbon particles was also caused. In example 1, no significant agglomeration occurred due to the inhibition of sintering by the interaction of EC300 and the cobalt-nitrogen-carbon precursor, which maintained good dispersion of the cobalt-nitrogen-carbon and the cobalt active site with O 2 Sufficient contact is beneficial to enhancing ORR activity.
Examples 1-3, comparative ORR LivingSexual testing
The results of the oxygen reduction electrochemical tests performed under the same conditions for examples 1, 2, 3 and comparative example, and the test results of fig. 4 show that the half-wave potentials of examples 1, 2, 3 are all significantly higher than that of comparative example 1, corresponding to higher ORR activity, indicating that the ORR activity of the cobalt nitrogen carbon can be effectively improved after carbon recombination is added.
Example 4
A catalyst comprising the cobalt nitrogen carbon catalyst prepared in example 1 for electrocatalytic oxygen reduction reactions.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. The cobalt-nitrogen-carbon catalyst with high dispersity is characterized in that the cobalt-nitrogen-carbon catalyst takes negatively charged carbon as a carrier and is carbonized with a ligand connected with Co to form a Co-N-C structure;
the preparation method of the cobalt nitrogen carbon catalyst comprises the following steps:
mixing a carbon carrier dispersion with an organic ligand solution to enable the organic ligand to be adsorbed on the surface of the carbon carrier;
adding cobalt metal salt solution to form a porous material ZIF-67 with a periodic network structure, wherein metal ions are used as centers, organic ligands adsorbed by a carbon carrier are bridged, the carbon carrier is alkaline and has negative charges, the generated ZIF-67 has positive charges, and in the stirring and standing aging processes, the charge adsorption between the carbon carrier and the ZIF-67 is fully balanced, and the aging time is controlled within a range of 20-30 hours;
calcining the purified sample under the protection of inert gas to obtain the cobalt nitrogen carbon catalyst with high dispersity.
2. The cobalt nitrogen carbon catalyst according to claim 1, wherein the cobalt nitrogen carbon catalyst has a surface area of 600 to 700m 2 Per g, the diameter of the mesoporous is 2.0-10.0 nm, and the pore volume is 0.1-0.5 cm 3 /g。
3. The cobalt nitrogen carbon catalyst according to claim 1, wherein the carbon support dispersion Zeta potential is negative;
and/or, the cobalt metal salt is an acidic metal salt.
4. A cobalt nitrogen carbon catalyst according to claim 3, wherein said carbon support is selected from one or more of electro-carbon black XC-72R, EC300, graphene;
and/or the cobalt metal salt is selected from one or more of cobalt nitrate, cobalt chloride and cobalt acetate;
and/or the organic ligand is 2-methylimidazole.
5. The cobalt nitrogen carbon catalyst according to claim 1, wherein the concentration of the carbon support dispersion is 0.01-0.1mol/L; the mass ratio of the addition amount of the carbon carrier dispersion liquid to cobalt metal in the cobalt salt is 1:0.1-1, wherein the mass ratio of the organic ligand to cobalt metal in the cobalt salt is 1:0.01-0.1;
and/or the concentration of the metal salt solution is 0.005-0.05mol/L.
6. The cobalt nitrogen carbon catalyst according to claim 1, wherein the carbon support dispersion and the cobalt metal salt solution are both ethanol in solvent.
7. The cobalt nitrogen carbon catalyst according to claim 1, wherein the organic ligand solvent is a mixture of ethanol and methanol; the volume ratio of ethanol to methanol in the mixture is (0.5-2): 1.
8. The cobalt nitrogen carbon catalyst according to claim 1, wherein the step of purifying treatment comprises: washing the solid sample obtained after suction filtration with ethanol for several times, naturally airing, and drying at 60-80 ℃.
9. The cobalt nitrogen carbon catalyst according to claim 1, wherein the calcination temperature is 800-1000 ℃ and the calcination time is 1-4 hours.
10. A catalyst comprising the cobalt nitrogen carbon catalyst of any one of claims 1-9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104953135A (en) * 2015-04-30 2015-09-30 北京化工大学 N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof
CN107275650A (en) * 2017-05-31 2017-10-20 华南理工大学 A kind of simple and convenient process for preparing of cobalt nitrogen CNT oxygen reduction catalyst
CN108963276A (en) * 2018-06-27 2018-12-07 中国科学技术大学 Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction
CN111672529A (en) * 2020-04-24 2020-09-18 中国科学院金属研究所 Nano-carbon-loaded cobalt nitrogen carbon catalytic material and preparation method and application thereof
CN111905793A (en) * 2020-08-17 2020-11-10 大连理工大学 Preparation method of nitrogen-doped carbon-supported non-noble metal monatomic catalyst
CN113371693A (en) * 2021-06-09 2021-09-10 中钢集团南京新材料研究院有限公司 Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104953135A (en) * 2015-04-30 2015-09-30 北京化工大学 N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof
CN107275650A (en) * 2017-05-31 2017-10-20 华南理工大学 A kind of simple and convenient process for preparing of cobalt nitrogen CNT oxygen reduction catalyst
CN108963276A (en) * 2018-06-27 2018-12-07 中国科学技术大学 Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction
CN111672529A (en) * 2020-04-24 2020-09-18 中国科学院金属研究所 Nano-carbon-loaded cobalt nitrogen carbon catalytic material and preparation method and application thereof
CN111905793A (en) * 2020-08-17 2020-11-10 大连理工大学 Preparation method of nitrogen-doped carbon-supported non-noble metal monatomic catalyst
CN113371693A (en) * 2021-06-09 2021-09-10 中钢集团南京新材料研究院有限公司 Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof

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