CN115138388A - High-dispersity cobalt nitrogen carbon catalyst and preparation method thereof - Google Patents
High-dispersity cobalt nitrogen carbon catalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000000243 solution Substances 0.000 claims abstract description 38
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- 239000012521 purified sample Substances 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 20
- 239000000523 sample Substances 0.000 claims description 15
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
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- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 7
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- 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
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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 discloses a high-dispersity cobalt nitrogen carbon catalyst and a preparation method thereof, and belongs to the technical field of preparation of catalyst materials. The cobalt-nitrogen-carbon catalyst takes carbon with negative charges 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 liquid 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 metal ions as a center and a bridged periodic network structure of organic ligands adsorbed by the carbon carrier; and 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 properties, provides a mutual binding force of electrostatic adsorption between a cobalt nitrogen carbon precursor with positive charge and a carbon carrier with negative charge, effectively improves the dispersion degree of the CoNC on the carrier and can fully utilize the adsorption sites of the carrier with high specific surface.
Description
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
The cobalt nitrogen carbon (CoNC) catalytic material has excellent catalytic activity, is often used for catalytic reaction of various batteries, has a pore structure which can provide enough space for oxygen and metal ion transmission, and can greatly improve the catalytic activity due to a composite effect formed by a large number of chemical defects and active sites in the CoNC. The catalytic activity can be further improved to a certain extent by regulating and controlling the shape and components, but in the process of liquid-phase preparation of the cobalt nitrogen carbon material, because the growth speed of crystal nuclei in the mother liquor is high, the problem that the grain size of microscopic grains of a product is large frequently occurs in the process of mass production, the specific surface area is low, and the catalytic activity cannot be fully exerted, so that the control of the dispersion degree and the grain size is a key technology in the synthesis process of the catalyst.
At present, the common synthesis methods of cobalt nitrogen carbon with high dispersity are mainly divided into two types, one type is to use a template method, for example, the method reported in patent literature (201310280066.6) adopts ordered mesoporous silica as a template, then mixes the template with cobalt salt and phenanthroline, dries and then calcines, and finally uses HF to remove SiO 2 Obtaining the cobalt nitrogen carbon by the template. However, the general synthesis process of the template method is complicated, and dangerous chemicals such as HF and the like are required to etch the template in the synthesis process, which is not favorable for safety production. The other is that a cobalt nitrogen carbon precursor is supported on a carrier with a high specific surface, for example, a carbon nanotube modified by nitrogen is used as a carrier reported in patent literature (201810035575.5), a precursor salt of cobalt is adsorbed by an impregnation method, and then high-temperature pyrolysis is carried out, so that the cobalt nitrogen carbon material is finally obtained. But the loading method is limited by the surface property of the carrier and the mutual bonding condition between the carrier and the cobalt nitrogen carbon precursor, and is used in industrial productionThe electrochemical performance of the cobalt nitrogen carbon is reduced due to the common conditions of poor load uniformity of the cobalt nitrogen carbon active site, low dispersion degree of the cobalt element and the like.
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 skilled in the art.
Disclosure of Invention
In order to solve the technical problems of poor load uniformity, small load amount and low dispersity of cobalt nitrogen carbon active sites in the prior art, a cobalt nitrogen carbon catalyst with high dispersity and a preparation method thereof are provided.
The invention provides a cobalt nitrogen carbon catalyst with high dispersity, which takes carbon with negative charge 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 The diameter of the mesopores is about 2.0 to 10.0nm, and the pore volume is 0.1 to 0.5cm 3 /g。
The second aspect of the present invention provides a method for preparing a cobalt nitrogen carbon catalyst, comprising:
mixing carbon carrier dispersion liquid with organic ligand solution to make the organic ligand adsorbed on the surface of the carbon carrier, wherein the selected carbon has high specific surface area and porous structure, so that the organic ligand can fully contact with carbon powder under the physical adsorption effect;
the cobalt metal salt solution is added rapidly with vigorous stirring, since Co is in solution as Co 2+ The catalyst exists in a form of being in an electron-deficient state, can coordinate with redundant lone-pair electrons of N in 2-methylimidazole to form a porous material (ZIF-67) with a periodic network structure, wherein metal ions are taken as a center, and an organic ligand adsorbed by a carbon carrier is a bridged periodic network structure;
keeping vigorous stirring for a period of time to fully disperse and uniformly mix the mixed solution, then standing and aging the uniformly mixed solution, wherein the carbon carrier is alkaline and has negative charges, and the generated ZIF-67 has positive charges, so that in the full stirring and standing and aging processes, the charge adsorption between the carrier and the cobalt-containing precursor (ZIF-67) is fully balanced, 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;
and 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 has a negative Zeta potential;
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 electrical 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 which is effective in neutralizing Co 2+ The bidentate coordination is formed, the price is low, and the mass production preparation of the sample is facilitated.
In some embodiments, the concentration of the carbon carrier dispersion liquid 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 the cobalt metal in the cobalt salt is 1:0.1-1, the mass ratio of the organic ligand to the cobalt metal in the cobalt salt is 1:0.01-0.1.
In some embodiments, the solvent of the carbon support dispersion liquid and the cobalt metal salt solution is ethanol;
and/or the organic ligand solvent is a mixture of ethanol and methanol, and the volume ratio of ethanol to methanol in the mixture is (0.5-2): 1.
In some embodiments, the step of purifying comprises: and washing the solid sample obtained after the suction filtration for a plurality of times by using ethanol, wherein a small amount of unreacted cobalt salt and 2-methylimidazole can be adsorbed by a porous structure of the cobalt-containing precursor, so that the solid sample is washed by using ethanol for a plurality of times, redundant cobalt salt and 2-methylimidazole are removed, and the solid sample is dried at the temperature of 60-80 ℃ after being naturally dried.
In some embodimentsThe calcining temperature is 800-1000 ℃, and the calcining time is 1-4 hours. Because the precursor of the CoNC has good thermal stability, the precursor of the CoNC needs to be calcined under the condition of high temperature, the precursor of the CoNC is pyrolyzed 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 cannot be oxidized to form CO/CO under the protection of inert gas 2 Escape without loss.
The third aspect of the present invention provides a catalyst, which is characterized by comprising the cobalt nitrogen carbon catalyst or the cobalt nitrogen carbon catalyst prepared by the above preparation method.
Compared with the prior art, the invention achieves the following technical effects:
(1) The invention creatively selects a raw material system with special surface properties, provides a mutual bonding force of electrostatic adsorption between a cobalt nitrogen carbon (CoNC) precursor (ZIF-67) with positive charge and a carbon carrier with negative charge, effectively improves the dispersion degree of the CoNC on the carrier, can fully utilize the adsorption sites of the carrier with high specific surface area, and effectively improves the loading effect compared with the prior art.
(2) The preparation method has the advantages that the electrostatic adsorption-aging balance cooperation process 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, 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 reaction liquid mother liquor, and the catalyst obtained after carbonization of the CoNC has higher oxygen reduction catalytic activity.
Drawings
FIG. 1 is an SEM image of sample C/CoNC-1 prepared in example 1 of the present 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 CoNC, a sample prepared in comparative example 1 of the present invention;
FIG. 4 is a graph showing ORR activity tests of samples prepared in examples 1, 2, 3& comparative examples of the present invention.
Detailed Description
The technical solution of the present invention is described below by specific examples. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.
Example 1
0.1g of EC300 is weighed and dispersed in 50mL of ethanol to be marked as solution A, and the surface pH is 8.8; 0.29g of cobalt nitrate (0.059 g of cobalt) was weighed out and dispersed in 50mL of ethanol (0.02 mol/L) as solution B, and the pH was 6.2. Weighing 3.2g of 2-methylimidazole (0.39 mol/L) and dissolving in 100mL of mixed solution of methanol and ethanol (the volume ratio of methanol to ethanol is 1; pouring the solution A into the solution C, uniformly mixing, quickly pouring the solution B into the solution C under vigorous stirring, continuously stirring for 1h, stopping stirring, standing at normal temperature and aging for 24h to ensure that the formed Co complex crystal nuclei are fully and uniformly dispersed on the EC300 carbon carrier with high specific surface through positive and negative electrostatic interaction; fully immersing the organic ligand on the surface of the carbon carrier, adding Co salt solution, which is beneficial to forming evenly 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 electrostatic action, so as to further improve the stability, if ZIF-67 is formed first and then mixed with the carbon carrier (solution B and solution C are mixed first and then mixed with solution A/solution A, B and C are mixed simultaneously), the former is difficult to be evenly distributed on the carbon carrier without agglomeration; after aging, performing suction filtration and separation, washing with ethanol, and drying by blowing at 70 ℃; taking part of the sample, spreading the sample on the bottom of a crucible, transferring the crucible to a tube furnace for high-temperature calcinationIntroducing N during the calcination process 2 Carry out protection of N 2 The flow rate is kept at 200mL/min, the temperature is increased to 900 ℃ at the speed of 10 ℃/min and kept for 2h, and then the temperature is naturally reduced to room temperature, thus obtaining the EC300/CoNC composite material which is marked as C/CoNC-1.
The resulting microstructure of C/CoNC-1 is shown in the Scanning Electron Microscope (SEM) photograph in FIG. 1. As can be seen in FIG. 1, the EC300/CoNC composite is a loose aggregate of particles with a particle size around 200 nm. From the X-ray diffraction analysis (XRD) results (FIG. 2) of example 1, it can be seen that the sample is pure two phases of carbon and cobalt, with diffraction peaks at 25.6 ℃ corresponding to the carbon phase (PDF # 08-0415) and diffraction peaks at 44.1 DEG, 51.3 DEG and 75.8 ℃ corresponding to the metallic cobalt phase (PDF #01-1255. Table 1 is N of example 1 2 The absorption and desorption test result shows that the specific surface area of the sample is 618.2m 2 The diameter of the mesopores is about 4.0nm, and the pore volume is 0.21cm 3 Is a mesoporous material with high specific surface area, and the high specific surface area and the mesoporous structure are beneficial to O 2 Fully contact with active site, and is favorable to O 2 An increase in the 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 is weighed and dispersed in 100mL of ethanol to be recorded as solution A, 0.29g of cobalt nitrate is weighed and dispersed in 100mL of ethanol to be recorded 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). Pouring the solution A into the solution C, uniformly mixing, quickly pouring the solution B into the solution C under vigorous stirring, continuously stirring for 1h, stopping stirring, standing at normal temperature and aging for 30h, so that formed Co complex crystal nuclei are fully and uniformly dispersed on XC-72R carbon carriers with high specific surface through positive and negative electrostatic interaction. Suction filtering, washing with alcohol, and air drying at 70 deg.C. Taking part of the sample, spreading it on the bottom of the crucible, transferring the crucible into a tube furnaceHigh-temperature calcining, introducing N during calcining 2 To carry out protection, N 2 The flow rate is kept at 200mL/min, the temperature is increased to 900 ℃ at the speed of 10 ℃/min and kept for 2h, and then the temperature is naturally reduced to room temperature, thus obtaining the XC-72R/CoNC composite material which is marked as C/CoNC-2.
The results are the same as in example 1 and are not described in detail here.
Example 3
0.1g of graphene is weighed and dispersed in 100mL of ethanol to be recorded as solution A, 0.29g of cobalt nitrate is dispersed in 100mL of ethanol to be recorded 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. Pouring the solution A into the solution C, uniformly mixing, quickly pouring the solution B into the solution C under vigorous stirring, continuously stirring for 1h, stopping stirring, standing at normal temperature and aging for 20h, so that the formed Co complex crystal nucleus is fully and uniformly dispersed on the graphene carbon carrier with high specific surface through positive and negative electrostatic interaction. Suction filtering, washing with alcohol, and air drying at 70 deg.C. Taking part of the sample to be laid on the bottom of the crucible, transferring the crucible to a tubular furnace for high-temperature calcination, and introducing N in the calcination process 2 Carry out protection of N 2 The flow rate is kept at 200mL/min, the temperature is raised to 900 ℃ at the rate of 10 ℃/min and kept for 2h, and then the temperature is naturally reduced to the room temperature, thus obtaining the GO/CoNC composite material which is marked as C/CoNC-3.
The results are the same as in example 1 and are not described in detail here.
Comparative example
5.95g of Zn (NO) are weighed out 3 ) 2 ·6H 2 Dissolving O in 150mL of methanol to prepare a solution A, weighing 6.16g of 2-methylimidazole, and dissolving in 150mL of methanol solution to prepare a solution B; and mixing the solution A and the solution B at room temperature, stirring for reacting for 24 hours, centrifuging a product obtained by the reaction, washing the product with methanol for a plurality of times, and then drying the product in vacuum at 70 ℃ to obtain ZIF-8 powder. The resulting ZIF-8 powder was sufficiently dissolved in 150mL of methanol and labeled as solution C, and 8.75g of Co (NO) was weighed 3 ) 2 ·6H 2 Dissolving O in 200mL of methanol, and marking as a solution D; weighing 9.23g of 2-methylimidazole, dissolving in 50mL of methanol, and marking as a solution E;then, the solution D was quickly poured into the solution C, and the resulting mixed solution was added to the solution E, and stirred at room temperature for 24 hours, centrifuged, and washed with methanol several times, followed by drying at 70 ℃ under vacuum. Putting the dried MOFs precursor into a tube furnace, and introducing N 2 And (3) carrying out heat treatment in the atmosphere, heating to 900 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2h, and then naturally cooling to room temperature to obtain the cobalt-nitrogen-carbon material, which is marked as CoNC. SEM pictures of example 1 and comparative example were compared (FIG. 1)&Fig. 3), it can be seen that the comparative example shows a significant particle agglomeration phenomenon, since not only the precursor is completely decomposed at a high temperature of 900 ℃, but also sintering of cobalt nitrogen carbon particles is caused. While no obvious agglomeration occurs in the embodiment 1, because the mutual acting force of the EC300 and the cobalt nitrogen carbon precursor inhibits the sintering, the cobalt nitrogen carbon can still keep better dispersity, and the cobalt active site and O are enabled to be in contact with each other 2 The full contact is favorable for improving ORR activity.
Examples 1-3, comparative example ORR Activity test
The oxygen reduction electrochemical test was performed on examples 1, 2, 3 and comparative example under the same conditions, and the test results of fig. 4 show that the half-wave potentials of examples 1, 2, 3 are significantly higher than that of comparative example 1, corresponding to higher ORR activity, which indicates that after carbon recombination is added, the ORR activity of cobalt nitrogen carbon can be effectively improved.
Example 4
A catalyst comprising the cobalt nitrogen carbon catalyst prepared in example 1 for use in an electrocatalytic oxygen reduction reaction.
The foregoing description of specific exemplary embodiments of the invention has been presented for the 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 certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and 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 carbon with negative charges is used as a carrier of the cobalt nitrogen carbon catalyst and is carbonized with a ligand connected with Co to form a Co-N-C structure.
2. The cobalt nitrogen carbon catalyst as claimed in claim 1, wherein the cobalt nitrogen carbon catalyst has a surface area of 600 to 700m 2 The diameter of the mesopores is between 2.0 and 10.0nm, and the pore volume is between 0.1 and 0.5cm 3 /g。
3. A preparation method of a cobalt nitrogen carbon catalyst is characterized by comprising the following steps:
mixing a carbon carrier dispersion liquid 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 taken as a center, and organic ligands adsorbed by the carbon carrier are bridged;
and calcining the purified sample under the protection of inert gas to obtain the cobalt nitrogen carbon catalyst with high dispersity.
4. The production method according to claim 3, wherein the carbon support dispersion liquid is alkaline or has a negative Zeta potential;
and/or the cobalt metal salt is an acidic metal salt.
5. The preparation method according to claim 4, wherein the carbon support is selected from one or more of electrical 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.
6. The production method according to claim 3, wherein the concentration of the carbon support dispersion liquid is 0.01 to 0.1mol/L; preferably, the mass ratio of the added amount of the carbon carrier dispersion liquid to the cobalt metal in the cobalt salt is 1:0.1-1, wherein the mass ratio of the organic ligand to the 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.
7. The production method according to claim 3, wherein the solvent for the carbon carrier dispersion liquid and the cobalt metal salt solution is ethanol;
and/or the organic ligand solvent is a mixture of ethanol and methanol; preferably, the volume ratio of ethanol to methanol in the mixture is (0.5-2): 1.
8. The method of claim 3, wherein the step of purifying comprises: and washing the solid sample obtained after suction filtration for a plurality of times by using ethanol, naturally airing, and drying at the temperature of 60-80 ℃.
9. The method according to claim 3, wherein the calcination temperature is 800-1000 ℃ and the calcination time is 1-4 hours.
10. A catalyst comprising the cobalt nitrogen carbon catalyst according to any one of claims 1 to 2 or the cobalt nitrogen carbon catalyst obtained by the production method according to any one of claims 3 to 9.
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