CN113224335A - Cobalt-nitrogen co-doped porous carbon material and preparation method and application thereof - Google Patents
Cobalt-nitrogen co-doped porous carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 34
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 25
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 19
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical group [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 26
- 229910020676 Co—N Inorganic materials 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
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- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
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- 230000010757 Reduction Activity Effects 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/96—Carbon-based electrodes
-
- 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
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- B01J35/33—
-
- B01J35/60—
-
- B01J35/615—
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- B01J35/635—
-
- B01J35/638—
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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 belongs to the technical field of porous carbon materials, and discloses a cobalt-nitrogen co-doped porous carbon material and a preparation method and application thereof. The method comprises the following steps: 1) mixing a cobalt source and melamine to obtain a mixture powder; 2) and carrying out pyrolysis treatment on the mixture powder to obtain the cobalt-nitrogen co-doped porous carbon material. The method is simple and convenient, the operation is simple, and the obtained cobalt-nitrogen co-doped porous carbon material has good porosity, high cobalt and nitrogen doping amount, more defect sites and active sites, and excellent catalytic activity of oxygen reduction reaction. The cobalt-nitrogen co-doped porous carbon material disclosed by the invention is applied to electrocatalytic oxygen reduction reaction and is used as an electrocatalyst of the oxygen reduction reaction.
Description
Technical Field
The invention belongs to the technical field of porous carbon materials, and particularly relates to a cobalt-nitrogen co-doped porous carbon material and a preparation method and application thereof.
Background
The fuel cell has a wide development prospect as a clean energy conversion device, the oxygen reduction reaction is a reaction generated on the cathode of various fuel cells, the reaction rate of the oxygen reduction reaction is slow, and an effective electrocatalyst is required to be used for promoting the reaction process. However, catalysts based on high platinum content are expensive, and catalysts with low platinum content have poor efficiency, which seriously hinders the commercialization process of fuel cell mass application. At present, various types of catalysts have been developed to accelerate the progress of oxygen reduction reaction, and among them, carbon-based nanomaterials have attracted much attention because of their advantages of high activity, high electrical conductivity, easily controllable structure and surface properties, and low synthesis cost.
However, the catalytic activity of the carbon-based nano material to the oxygen reduction reaction still needs to be improved, and the synthesis steps of most of the materials are complicated, which is not beneficial to carrying out an amplification experiment to increase the yield, thereby limiting the wide-range application of the fuel cell.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a cobalt-nitrogen co-doped porous carbon material and a preparation method thereof. The preparation method takes the melamine and the cobalt phthalocyanine as the carbon source, the nitrogen source and the cobalt source, prepares the cobalt-nitrogen co-doped porous carbon material by a one-step direct pyrolysis method, uses the raw materials which are harmless to human bodies, has simple and convenient operation in the preparation process, and is easy for industrial production.
The invention also aims to provide application of the cobalt-nitrogen co-doped porous carbon material. The cobalt-nitrogen co-doped porous carbon material has high electrocatalytic oxygen reduction reaction activity. The cobalt-nitrogen co-doped porous carbon material is applied to oxygen reduction reaction and is used as an electrocatalyst of the oxygen reduction reaction, in particular to a catalyst in a cathode of a fuel cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt-nitrogen co-doped porous carbon material comprises the following steps:
1) mixing cobalt phthalocyanine and melamine to obtain mixture powder;
2) and carrying out pyrolysis treatment on the mixture powder to obtain the cobalt-nitrogen co-doped porous carbon material.
The mass ratio of the melamine to the cobalt phthalocyanine is (30-90) to 1, and preferably (50-90) to 1.
The mixing is to perform ball milling treatment on cobalt phthalocyanine and melamine, wherein the ball milling time is 1-6 hours.
And the pyrolysis treatment is to roast the mixture at high temperature.
The heating rate of the pyrolysis treatment is 2-8 ℃/min.
The temperature of the pyrolysis treatment is 600-1100 ℃.
The time of the pyrolysis treatment is 2-6 h.
The pyrolysis treatment is carried out under a protective atmosphere (e.g., nitrogen).
A cobalt-nitrogen co-doped porous carbon material prepared by any one of the preparation methods.
The pore volume of the cobalt-nitrogen co-doped porous carbon material is 0.7-1.4 cm3A pore diameter of 14.1 to 29.7nm and a specific surface area of 185 to 430m2/g。
The cobalt-nitrogen co-doped porous carbon material is applied to an electrocatalytic oxygen reduction reaction and is used as an electrocatalyst of the oxygen reduction reaction, in particular to a catalyst in a cathode of a fuel cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method is simple and convenient in preparation process, simple in operation, free of any solvent and environment-friendly.
(2) The invention generates the carbon carrier in situ in the pyrolysis process as a load substance without adding any carbon carrier additionally.
(3) The metal cobalt is highly dispersed and doped in the carbon skeleton of the material, so that the material has higher oxygen reduction activity.
(4) The invention adopts cobalt phthalocyanine and melamine as raw materials, has low price, is convenient and easy to obtain, has no obvious toxicity to human bodies, and does not generate intermediate products harmful to the environment.
(5) The preparation process of the invention has short flow, and can amplify the raw material dosage in a certain range in equal proportion, thereby increasing the material yield without changing the properties of the material in various aspects.
Drawings
FIG. 1 is a graph of the nitrogen adsorption/desorption isotherm and pore size distribution curve of the product obtained in examples 1 to 4, wherein A corresponds to the nitrogen adsorption/desorption isotherm graph and B corresponds to the pore size distribution curve;
FIG. 2 is a linear scan plot of the products obtained in examples 1-4 and Pt/C.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
Example 1
A preparation method of a cobalt-nitrogen Co-doped porous carbon material (marked as Co-N/C-30, wherein 30 represents the proportion of melamine to cobalt phthalocyanine of 30) specifically comprises the following steps:
weighing 0.1g of cobalt phthalocyanine and 3.0g of melamine, adding into a ball milling tank containing ball milling beads, and putting into a ball mill for ball milling and mixing for 1h (the rotation speed of the ball milling is 500 r/min); and then placing the obtained blue powder mixture into a porcelain boat, placing the porcelain boat in a tube furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, calcining for 6h, and naturally cooling to room temperature to obtain a black solid, namely the Co-N/C-30.
The pore volume of the Co-N/C-30 synthesized in this example was 0.7cm3A pore diameter of 15.8nm and a specific surface area of 185m2/g。
Example 2
A preparation method of a cobalt-nitrogen Co-doped porous carbon material (marked as Co-N/C-50, wherein 50 represents the proportion of melamine to cobalt phthalocyanine of 50) specifically comprises the following steps:
weighing 0.1g of cobalt phthalocyanine and 5.0g of melamine, adding into a ball milling tank containing ball milling beads, and putting into a ball mill for ball milling and mixing for 2 hours (the rotation speed of the ball milling is 500 r/min); and then placing the obtained blue powder mixture into a porcelain boat, placing the porcelain boat in a tube furnace, heating to 800 ℃ at a heating rate of 4 ℃/min under the nitrogen atmosphere, calcining for 3h, and naturally cooling to room temperature to obtain a black solid, namely the Co-N/C-50.
The pore volume of the Co-N/C-50 synthesized in this example was 0.8cm3A pore diameter of 15.9nm and a specific surface area of 228m2/g。
Example 3
A preparation method of a cobalt-nitrogen Co-doped porous carbon material (marked as Co-N/C-70, wherein 70 represents the proportion of melamine to cobalt phthalocyanine of 70) specifically comprises the following steps:
weighing 0.1g of cobalt phthalocyanine and 7.0g of melamine, adding into a ball milling tank containing ball milling beads, and putting into a ball mill for ball milling and mixing for 4 hours (the rotation speed of the ball mill is 500 r/min); and then placing the obtained blue powder mixture into a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 900 ℃ at the heating rate of 6 ℃/min under the nitrogen atmosphere, calcining the porcelain boat for 3 hours, and naturally cooling the porcelain boat to room temperature to obtain a black solid, namely the Co-N/C-70.
The pore volume of the Co-N/C-70 synthesized in this example was 1.2cm3A pore diameter of 29.7nm and a specific surface area of 294m2/g。
Example 4
A preparation method of a cobalt-nitrogen Co-doped porous carbon material (marked as Co-N/C-90, wherein 90 represents the proportion of melamine to cobalt phthalocyanine of 90) specifically comprises the following steps:
weighing 0.1g of cobalt phthalocyanine and 9.0g of melamine, adding into a ball milling tank containing ball milling beads, and putting into a ball mill for ball milling and mixing for 6 hours (the rotation speed of the ball milling is 500 r/min); and then placing the obtained blue powder mixture into a porcelain boat, placing the porcelain boat in a tube furnace, heating to 1100 ℃ at the heating rate of 8 ℃/min under the nitrogen atmosphere, calcining for 2h, and naturally cooling to room temperature to obtain a black solid, namely the Co-N/C-90.
The pore volume of the Co-N/C-90 synthesized in this example was 1.4cm3A pore diameter of 14.1nm and a specific surface area of 429m2/g。
N treatment of the products obtained in examples 1 to 42Physical adsorption-desorption characterization and pore size distribution characterization were performed by using a full-automatic specific surface area and pore size analyzer model TriStar II 3020, Micromeritics, usa, and the results are shown in fig. 1. FIG. 1 is a chart showing the nitrogen adsorption/desorption isotherm and pore size distribution curve of the product obtained in examples 1 to 4, in which A corresponds to the nitrogen adsorption/desorption isotherm spectrum and B corresponds to the pore size distribution curveThe pore size distribution curve spectrum is used.
As is apparent from a diagram in fig. 1, all samples exhibited typical type IV adsorption isotherms and H3 hysteresis loops, mainly resulting from slab slit pores formed by stacking sheet materials, and also indicating the presence of micropores and mesopores in the materials. It can be known from the parameters of pore volume, pore diameter and specific surface area of comparative examples 1 to 4 that the appropriate increase of the proportion of the melamine is beneficial to increasing the pore volume and specific surface area of the material, so as to enhance the oxygen reduction activity of the material, but for the pore diameter, the too large amount of the melamine leads to the reduction of the pore diameter of the material, and the adverse effect is generated on the oxygen reduction performance. According to the pore size distribution result (as shown in the B diagram in FIG. 1), the pore sizes of the mesopores of the sample are uniformly distributed within the range of less than 10nm, and the mesopores of the samples are distributed in larger ranges of 40 to 50nm in examples 1 to 3, but the mesopores are not distributed in example 4, which indicates that the excessive use of melamine is not favorable for the formation of secondary mesopores.
The surface element content of the products obtained in examples 1 to 4 was characterized by X-ray photoelectron spectroscopy, and analyzed by a K-Alpha type X-ray photoelectron spectrometer from Thermo Fisher Scientific, USA, and the results are shown in Table 1.
TABLE 1 atomic percent (at%) of surface element of the product obtained in examples 1 to 4
As can be seen from table 1, in the materials obtained in examples 1 to 4, the cobalt content on the surface of the material is greater than 2 at%, and the cobalt content increases with the increase of the amount of melamine, which indicates that the carbon carriers generated in situ in the pyrolysis process of melamine are beneficial to the loading of cobalt therein, thereby promoting the formation of active sites for oxygen reduction reaction.
The products obtained in examples 1-4 were characterized by Linear Scanning (LSV) and analyzed using the IGS-6030 electrochemical workstation of Guangzhou Yingsi sensing technology, Inc., the results of which are shown in FIG. 2 and Table 2. The test was performed in a neutral condition of 50mmol/L Phosphate Buffered Saline (PBS), at a scan rate of 10mV/s and at a rotating disk electrode speed of 1600rpm, and the half-wave potential of the curve and the diffusion-controlled current density were selected as comparative criteria for measuring electrochemical oxygen reduction performance.
FIG. 2 is a linear scan plot of the products obtained in examples 1-4 and Pt/C, corresponding to the oxygen reduction performance of each material, compared to the performance of a commercial catalyst Pt/C. The potential value on the abscissa is based on the Reversible Hydrogen Electrode (RHE). In FIG. 2, the products of examples 1 to 4 all have a half-wave potential greater than Pt/C, and the diffusion control current densities of the products of examples 2 to 4 are all greater than Pt/C, indicating that these catalysts have excellent catalytic performance for oxygen reduction reactions. On the other hand, comparing the linear scanning curves of Co-N/C-70 (example 3) and Co-N/C-90 (example 4) shows that the curves of the two are approximately overlapped in the kinetic control region of 0.65-0.9V, while the diffusion control current density of Co-N/C-70 is higher, resulting in that the half-wave potential of Co-N/C-90 is higher than that of Co-N/C-70. However, the oxygen reduction activity of the material should integrate two factors of half-wave potential and diffusion control current density, so that the Co-N/C-70 has higher oxygen reduction catalytic performance. Meanwhile, the reason that the catalytic activity of the material for oxygen reduction can be enhanced by properly increasing the consumption of the melamine, and the optimization of the catalytic performance of the material for oxygen reduction is not facilitated by excessively increasing the consumption of the melamine is probably because the adsorption and desorption processes of oxygen are limited due to the reduction of the pore diameter of the material, thereby affecting the catalytic activity.
TABLE 2 half-wave potential and diffusion-controlled current density of the products of examples 1 to 4 in 50mM phosphate buffer solution
In the cobalt-nitrogen co-doped carbon nanomaterial, co-doping of cobalt and nitrogen atoms changes electrons and a geometric structure in a carbon skeleton, and functional groups, defect sites and the like generated on the surface of the material are beneficial to oxygen reduction catalysis. The cobalt-nitrogen co-doped porous carbon material has the advantages of good porosity, high cobalt and nitrogen doping amount, more defect sites and active sites, and good catalytic activity of oxygen reduction reaction.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The preparation method of the cobalt-nitrogen co-doped porous carbon material is characterized by comprising the following steps of:
1) mixing a cobalt source and melamine to obtain a mixture powder;
2) carrying out pyrolysis treatment on the mixture powder to obtain a cobalt-nitrogen co-doped porous carbon material;
the cobalt source is cobalt phthalocyanine; the mass ratio of the melamine to the cobalt source is (30-90) to 1; the temperature of the pyrolysis treatment is 600-1100 ℃.
2. The preparation method of the cobalt-nitrogen co-doped porous carbon material according to claim 2, characterized in that:
the mass ratio of the melamine to the cobalt source is (50-90) to 1.
3. The preparation method of the cobalt-nitrogen co-doped porous carbon material according to claim 1, characterized in that: the pyrolysis treatment time is 2-6 h; the heating rate of the pyrolysis treatment is 2-8 ℃/min; the pyrolysis treatment is carried out in a protective atmosphere.
4. The preparation method of the cobalt-nitrogen co-doped porous carbon material according to claim 1, characterized in that:
the mixing means that a cobalt source and melamine are subjected to ball milling treatment, and the ball milling time is 1-6 h.
5. A cobalt-nitrogen co-doped porous carbon material obtained by the preparation method of any one of claims 1 to 4.
6. The application of the cobalt-nitrogen co-doped porous carbon material in the electrocatalytic oxygen reduction reaction according to claim 5, wherein the cobalt-nitrogen co-doped porous carbon material is characterized in that: the cobalt-nitrogen co-doped porous carbon material is used as an oxygen reduction reaction electrocatalyst.
7. Use according to claim 6, characterized in that: the electrocatalyst is a catalyst in the cathode of the fuel cell.
8. Use according to claim 6, characterized in that: the cobalt-nitrogen co-doped porous carbon material is used for electrocatalysis of neutral solution.
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