CN116093348A - Preparation method of cobalt-nitrogen-carbon material with high electrocatalytic performance - Google Patents
Preparation method of cobalt-nitrogen-carbon material with high electrocatalytic performance Download PDFInfo
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- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000013110 organic ligand Substances 0.000 claims abstract description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 150000001868 cobalt Chemical class 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 4
- -1 zeolite imidazole ester Chemical class 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009295 crossflow filtration Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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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
- H01M4/90—Selection of catalytic material
-
- 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
- H01M4/88—Processes of manufacture
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a preparation method of a cobalt-nitrogen-carbon material with high electrocatalytic performance, and belongs to the technical field of catalyst material preparation. The preparation method comprises the following steps: (1) taking polyalcohol as a solvent to prepare cobalt salt solution; (2) Preparing an organic ligand solution, wherein the solvent is ethanol or methanol; (3) mixing the organic ligand solution with cobalt salt solution for reaction; (4) Solid-liquid separation is carried out to obtain zeolite imidazole ester skeleton structure material; (5) Impregnating the zeolite imidazole ester framework structure material with inorganic salt solution; (6) Under the protection of inert gas, calcining and decomposing the impregnated zeolite imidazole ester skeleton structure material at high temperature to obtain a Co-N-C crude product; (7) Purifying the Co-N-C crude product to remove inorganic salt and impurities therein, thereby obtaining Co-N-C pure product powder. The cobalt-nitrogen-carbon material prepared by the preparation method has the advantages of small particle size, large specific surface area, high pore volume and high electrocatalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a preparation method of a cobalt-nitrogen-carbon material with high electrocatalytic performance.
Background
In clean energy, a hydrogen fuel cell directly chemically reacts hydrogen (H 2 ) The energy conversion device for converting chemical energy into electric energy has the advantages of high energy conversion efficiency, high power density, small occupied area, wide application range, clean energy conversion process and the like, and has wide application prospect in convenience of heavy trucks, buses, portable electrical equipment and the like. Although there are currently no previous advances in hydrogen fuel cells, there are still many urgent problems to be solved, one of which is an electrocatalyst for the cathode of a fuel cell. At present, the commercial electrocatalyst mainly uses platinum-carbon catalyst, but the platinum as noble metal cannot meet the requirement of large-scale industrialization of the electrocatalyst in terms of yield and price. Therefore, the development of the non-noble metal electrocatalyst is significant, and the non-noble metal is adopted to replace noble metal platinum, so that the cost can be reduced, the catalyst performance can be improved, and the commercialization process of the hydrogen fuel cell can be further promoted.
In the existing non-noble metal system, the cobalt-nitrogen-carbon (Co-N-C) catalyst has the advantages of large specific surface area, reasonable pore size distribution, good stability, high active site density, methanol resistance and the like, and is a catalyst with very good application prospect and commercial potential. At present, the technical route for synthesizing Co-N-C mainly comprises the following four steps: (1) Mixing melamine/dicyandiamide with water to form a mixed solution, carrying out hydrothermal reaction on a precursor, mixing the precursor with an ethanol solution of cobalt acetate, carrying out solid-liquid separation, and calcining to obtain a cobalt nitrogen carbon catalyst (CN 114534759A); (2) Firstly, decomposing precursors such as urea, melamine and the like at high temperature to obtain a nitrogen-doped carbon carrier (C) 3 N 4 Etc.), then dipping the carbon carrier in cobalt salt solution such as cobalt nitrate, cobalt chloride, etc. by dipping method, finally obtaining Co-N-C material (CN 106925330A) by further pyrolysis; (3) The acrylonitrile reacts with cobalt chloride hexahydrate, ethyl acetate is used as solvent, after the reaction is finished, the filtration and the washing are carried out, and the obtained solid and colloid SiO are reacted 2 Stirring thoroughly in mixed solvent, filtering, oven drying, and placing in tube furnaceAnnealing, treating with HF aqueous solution to remove SiO 2 A cotc sample (CN 114345387 a) was obtained; (4) Cobalt salt and ligands such as 2-methylimidazole, phenanthroline and the like are mixed in ethanol and methanol solvents to form metal organic frame Materials (MOFs), and then the MOFs are subjected to pyrolysis in an inert gas atmosphere to obtain cobalt nitrogen carbon (CN 114713259A).
However, the above synthetic schemes have a certain problem at present. In the scheme (1), a hydrothermal reaction is needed to synthesize the precursor, the reaction is needed to be carried out in an autoclave, the reaction temperature is 160-180 ℃, the requirement on a reaction device for amplified preparation is high, and the method is not suitable for large-scale production and preparation. In the scheme (2), the cobalt salt precursor is firstly immersed on a carrier with a high specific surface and then pyrolyzed, the carrier can limit the number of active sites, and the excessive loading capacity can lead to uneven distribution of the active sites, so that the promotion of catalytic activity is not facilitated. According to the scheme (3), the cobalt-nitrogen-carbon material is prepared by adopting a template method, the aperture of the cobalt-nitrogen-carbon material can be regulated and controlled by changing the size of the template, so that the active site of the cobalt-nitrogen-carbon material can be fully contacted with reactants, but the synthesis process is relatively complex, HF used in the synthesis process belongs to dangerous chemicals, and the requirements on the operation flow and equipment in large-scale production are high. The synthesis process of the scheme (4) is simple, the obtained cobalt nitrogen carbon sites are uniformly distributed, the specific surface area is large, the requirements on synthesis conditions and equipment are low, the method has the potential of amplifying synthesis preparation, and is an ideal technical route for preparing cobalt nitrogen carbon, but in the synthesis process, the adjustment and control of the dispersibility and the size of MOFs precursors still have certain problems, and further research and optimization are needed to improve the electrocatalytic activity of the MOFs precursors.
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
The invention aims to solve the problem that the dispersibility and the size of MOFs precursor are difficult to regulate and control in the process of preparing cobalt nitrogen carbon in the prior art, and provides a preparation method of a cobalt nitrogen carbon material with high electrocatalytic performance.
The first aspect of the invention provides a preparation method of a cobalt-nitrogen-carbon material with high electrocatalytic performance, which comprises the following steps:
(1) Preparing cobalt salt solution by taking polyalcohol as a solvent;
(2) Preparing an organic ligand solution, wherein the solvent is ethanol or methanol;
(3) Mixing the organic ligand solution with the cobalt salt solution for reaction;
(4) Carrying out solid-liquid separation on the reacted reaction system to obtain a zeolite imidazole ester skeleton structure material;
(5) Impregnating the obtained zeolite imidazole ester skeleton structure material with an inorganic salt solution;
(6) Under the protection of inert gas, calcining and decomposing the impregnated zeolite imidazole ester skeleton structure material at high temperature to obtain a Co-N-C crude product;
(7) Purifying the Co-N-C crude product to remove inorganic salt and impurities to obtain Co-N-C pure product powder.
In an embodiment of the present invention, the cobalt salt in the step (1) is at least one selected from cobalt nitrate, cobalt chloride, cobalt bromide, cobalt acetate and cobalt sulfate.
In one embodiment of the present invention, the cobalt ion concentration in the cobalt salt is 0.05 to 0.5mol/L.
In one embodiment of the present invention, the polyol in step (1) is at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and butylene glycol.
In one embodiment of the present invention, the organic ligand in the step (2) is at least one selected from 2-methylimidazole and 5, 6-dimethylbenzimidazole.
In one embodiment of the present invention, the concentration of the organic ligand in the solution is 0.01 to 0.1g/mL.
In one embodiment of the present invention, the mixing reaction in the step (3) specifically includes:
the organic ligand solution and the metal cobalt salt solution are fully mixed for 0.5 to 1.5 hours by vigorous stirring to obtain a mixed solution, and then the mixed solution is reacted for 0.5 to 4 hours in a water bath with the temperature of 60 to 80 ℃.
In an embodiment of the present invention, the solid-liquid separation in the step (4) is at least one selected from centrifugal separation, vacuum filtration, and cross-flow filtration.
In one embodiment of the present invention, after the solid-liquid separation, the obtained solid zeolite imidazole ester framework structure material is further washed with ethanol.
In one embodiment of the present invention, the solid zeolite imidazole ester framework structure material is air-dried at 50 to 70 ℃. The forced air drying may be performed after the solid-liquid separation, or may be performed after the solid-liquid separation and the ethanol washing.
In an embodiment of the present invention, the inorganic salt in step (5) is at least one selected from potassium chloride and sodium chloride.
In one embodiment of the present invention, the concentration of the inorganic salt in the solution is 0.01 to 0.1g/mL.
In one embodiment of the present invention, the solvent of the inorganic salt solution is at least one selected from methanol and ethanol.
In one embodiment of the present invention, the time for the immersing treatment is 2 to 4 hours.
In an embodiment of the present invention, the inert gas in the step (6) is at least one selected from argon, nitrogen and helium.
In one embodiment of the present invention, the high temperature calcination temperature is 800 to 900 ℃.
In one embodiment of the present invention, the purification treatment in step (7) specifically includes: dispersing the Co-N-C crude product in water, standing for 1-2 h, separating solid from liquid, and drying to obtain the final product.
Compared with the prior art, the invention has the following technical effects:
(1) The mixed solvent of ethanol/methanol and polyalcohol is selected for synthesizing the Co-N-C precursor, the glycol and the glycerol have certain viscosity, and the migration rate of metal ions is reduced after the reaction solvent is added, so that overgrowth of crystals is restrained, the obtained crystals are prevented from being oversized, the particle size of the precursor can be stabilized in a smaller particle size range of 100nm, and the nano particles with the size can expose enough active sites, so that the catalytic activity is promoted.
(2) Before high-temperature calcination and decomposition, the zeolite imidazole ester skeleton structure material (ZIF) crystal precursor is subjected to impregnation treatment by using an inorganic salt solution, and inorganic salt can be melted to form molten salt to be coated on the surfaces of Co-N-C nano particles under inert atmosphere and high temperature, so that agglomeration and sintering among nano crystals can be effectively inhibited, the nano crystals can always keep a highly dispersed state, and the obtained cobalt-nitrogen-carbon material has small particle size, large specific surface area, high pore volume and high electrocatalytic performance.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of a sample CoNC-1 prepared according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a sample CoNC-ET prepared according to comparative example 1 of the invention;
FIG. 3 is a scanning electron microscope image of a sample CoNC-EG prepared according to comparative example 2 of the present invention;
FIG. 4 is an X-ray diffraction pattern (XRD) of sample CoNC-1 prepared in accordance with example 1 of the invention;
FIG. 5 is the results of electrochemical testing of Co-N-C catalysts prepared according to examples and comparative examples of the present invention: FIG. 5A is a Linear Sweep Voltammetry (LSV); FIG. 5B is a Cyclic Voltammetry (CV).
Detailed Description
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
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:
cobalt nitrate 4.4g was weighed and dissolved in 150mL of ethylene glycol solution to obtain a cobalt salt solution. 7.5g of organic ligand 2-methylimidazole was weighed and dissolved in 150mL of ethanol to obtain an organic ligand solution. Adding the organic ligand solution into the cobalt salt solution, fully and uniformly mixing and dispersing the organic ligand solution by intense stirring, and keeping the intense stirring for 1h to obtain a mixed solution, transferring the mixed solution into a water bath kettle, and reacting in the water bath at the temperature of 60 ℃ for 2h. The sample after the water bath was centrifuged and washed several times with ethanol to remove excess 2-methylimidazole and precursor salts and air dried at 60 ℃. The dried sample was immersed in 100mL of a methanol solution of potassium chloride having a concentration of 0.06g/mL for 2 hours, followed by air drying at 60 ℃ to obtain a pale purple solid powder. Spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas Ar for protection, and performing high-temperature calcination decomposition at 900 ℃. Finally dispersing the obtained carbonized sample in water, standing for 1h, removing potassium chloride, filtering, and drying by air blast to obtain a Co-N-C sample, and marking as CoNC-1.
Example 2:
cobalt chloride 2.1g was weighed and dissolved in 150mL of propylene glycol solution to obtain cobalt salt solution. 3g of the organic ligand 5, 6-dimethylbenzoimidazole was weighed and dissolved in 150mL of methanol to obtain an organic ligand solution. The organic ligand solution was added to the cobalt salt solution, and thoroughly mixed and uniformly dispersed by vigorous stirring, and maintained under vigorous stirring for 0.5h, followed by transferring the mixed solution to a water bath kettle, and reacting in a water bath at 60℃for 3h. And (3) carrying out vacuum filtration and separation on the sample after the water bath is finished, adding ethanol for washing for a plurality of times, removing redundant 2-methylimidazole and precursor salt, and carrying out forced air drying at 50 ℃. The dried sample was immersed in 100mL of an ethanol solution of potassium chloride, wherein the concentration of potassium chloride was 0.02g/mL, the immersion time was 3 hours, and then air-dried at 60 ℃ to obtain a pale purple solid powder. Spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas Ar for protection, and calcining and decomposing at a high temperature of 800 ℃. Finally dispersing the obtained carbonized sample in water, standing for 1.5h, removing potassium chloride, filtering, and drying by air blast to obtain a Co-N-C sample, and marking as CoNC-2.
Example 3:
10.6g of cobalt acetate was weighed and dissolved in 150mL of glycerol solution to obtain a cobalt salt solution. 15g of organic ligand 2-methylimidazole was weighed and dissolved in 150mL of ethanol to obtain an organic ligand solution. The organic ligand solution was added to the cobalt salt solution, thoroughly mixed and uniformly dispersed by vigorous stirring, and kept vigorously stirred for 1.5 hours, then the mixed solution was transferred to a water bath kettle, and reacted in a water bath at 60 ℃ for 4 hours. And carrying out cross-flow filtration separation on the sample after the water bath is finished, adding ethanol for washing for a plurality of times, removing redundant 2-methylimidazole and precursor salt, and carrying out forced air drying at 70 ℃. The dried sample was immersed in 100mL of a methanol solution of sodium chloride, wherein the concentration of potassium chloride was 0.1g/mL, for 4 hours, and then air-dried at 60℃to obtain a pale purple solid powder. Spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas Ar for protection, and carrying out high-temperature calcination decomposition at 850 ℃. Finally dispersing the obtained carbonized sample in water, standing for 2 hours, removing potassium chloride, filtering, and drying by air blast to obtain a Co-N-C sample, and marking as CoNC-3.
Comparative example 1: (differing from example 1 in that molten salt protection treatment was not added)
Cobalt nitrate 4.4g was weighed and dissolved in 150mL of ethylene glycol solution to obtain a cobalt salt solution. 7.5g of organic ligand 2-methylimidazole was weighed and dissolved in 150mL of ethanol to obtain an organic ligand solution. Adding the organic ligand solution into the cobalt salt solution, fully and uniformly mixing and dispersing the organic ligand solution by intense stirring, and keeping the intense stirring for 1h to obtain a mixed solution, transferring the mixed solution into a water bath kettle, and reacting in the water bath at the temperature of 60 ℃ for 2h. The sample after the water bath was centrifuged and washed several times with ethanol to remove excess 2-methylimidazole and precursor salts and air dried at 60 ℃. Spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas Ar for protection, and calcining and decomposing at 900 ℃ at high temperature to obtain a Co-N-C sample, which is marked as CoNC-ET.
Comparative example 2: (the solvent distinguished from example 1 as the organic ligand solution is ethylene glycol instead of ethanol)
Cobalt nitrate 4.4g was weighed and dissolved in 150mL of ethylene glycol solution to obtain a cobalt salt solution. 7.5g of organic ligand 2-methylimidazole was weighed and dissolved in 150mL of ethylene glycol to obtain an organic ligand solution. The organic ligand solution was added to the cobalt salt solution, and was thoroughly mixed and uniformly dispersed by vigorous stirring, and kept vigorously stirred for 1 hour, then the mixed solution was transferred to a water bath, and reacted in a water bath at 60 ℃ for 2 hours. The sample after the water bath was centrifuged and washed several times with ethanol to remove excess 2-methylimidazole and precursor salts and air dried at 60 ℃. The dried sample was immersed in 100mL of a methanol solution of potassium chloride having a concentration of 0.06g/mL for 2 hours, followed by air drying at 60 ℃ to obtain a pale purple solid powder. Spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas Ar for protection, and performing high-temperature calcination decomposition at 900 ℃. Finally dispersing the obtained carbonized sample in water, standing for 1h, removing potassium chloride, filtering, and drying by air blast to obtain a Co-N-C sample, which is marked as CoNC-EG.
Test results
1. Scanning electron microscope result
As shown in FIGS. 1 to 3, scanning electron micrographs of CoNC-1, coNC-ET and CoNC-EG obtained by the methods of example 1, comparative example 1 and comparative example 2, respectively. As can be seen from fig. 1 to 3, the cotc-1 sample (fig. 1) prepared in example 1 has a uniform size, a particle diameter concentrated at about 100nm, and a highly dispersed state, no obvious agglomeration occurs, and has a good crystallinity, which is beneficial to the improvement of catalytic performance; comparative example 1 preparationIs larger in size and has a particle diameter of CoNC-ET (FIG. 2)>400nm, far above the size of the example samples, and severe inter-particle sintering agglomeration, which is detrimental to active sites and O 2 Is sufficient to affect catalytic activity; the CoNC-EG (FIG. 3) prepared in comparative example 2 was smaller in particle size than the CoNC-ET of comparative example 1, but had poor crystallinity and non-uniform particle size. The comparison of the scanning electron microscope results shows that the dispersion and crystallinity of the nano particles can be effectively improved by adopting the mixed solvent of ethanol/methanol and polyalcohol and the inorganic salt solution for dipping treatment, so that the electrocatalytic performance of the nano particles is improved.
2.N 2 Adsorption and desorption test results
Further N is carried out on CoNC-1, coNC-ET and CoNC-EG 2 The adsorption and desorption tests, the test results are shown in the following table 1:
table 1N of example 1 and comparative examples 1, 2 2 Adsorption and desorption test results.
The above test results show that the specific surface area of CoNC-1 prepared in example 1 is much higher than that of the sample CoNC-ET of comparative example 1, which is consistent with the test results of SEM while possessing a higher pore volume (0.19 cm 3 /g), in favor of O 2 Fully contacts with active sites in the catalyst to improve the catalytic efficiency. Comparative example 2 also has a higher specific surface area (352.7 m 2 /g), but the pore volume is relatively low, which is detrimental to mass transfer during catalysis.
3.X ray diffraction results
FIG. 4 shows the X-ray diffraction pattern (XRD) of CoNC-1 prepared in example 1. The diffraction peaks according to FIG. 4 can be used to determine that CoNC-1 only comprises pure two phases of carbon and cobalt, wherein cobalt is in a metallic cobalt phase state, which indicates that the precursor is completely decomposed during calcination, no precursor residue exists, and the purity of the obtained Co-N-C product is higher.
4. Results of oxygen reduction Activity test
The oxygen reduction activity test was further performed on the CoNC prepared in examples and comparative examples, mainly byThe electrochemical test was performed, and the results are shown in fig. 5, wherein fig. 5A is a Linear Sweep Voltammetry (LSV) test result and fig. 5B is a Cyclic Voltammetry (CV) test result. As can be seen from FIG. 5, examples 1, 2, 3 produced CoNC-1, coNC-2, coNC-3 each had a higher half-wave potential than the comparative examples, corresponding to a higher electrocatalytic oxygen reduction (ORR) activity, while it can be seen that the limiting current of the examples was also much higher than that of the comparative examples, due to the small particle size and high dispersion of the examples, better able to react with O 2 Contact can effectively improve the catalytic activity of Co-N-C, and the catalyst can be used with SEM and N 2 The adsorption and desorption test results are consistent.
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 preparation method of the cobalt-nitrogen-carbon material with high electrocatalytic performance is characterized by comprising the following steps of:
(1) Preparing cobalt salt solution by taking polyalcohol as a solvent;
(2) Preparing an organic ligand solution, wherein the solvent is ethanol or methanol;
(3) Mixing the organic ligand solution with the cobalt salt solution for reaction;
(4) Carrying out solid-liquid separation on the reacted reaction system to obtain a zeolite imidazole ester skeleton structure material;
(5) Impregnating the obtained zeolite imidazole ester skeleton structure material with an inorganic salt solution;
(6) Under the protection of inert gas, calcining and decomposing the impregnated zeolite imidazole ester skeleton structure material at high temperature to obtain a Co-N-C crude product;
(7) And (3) purifying the Co-N-C crude product to remove inorganic salt and impurities in the Co-N-C crude product to obtain Co-N-C pure product powder.
2. The method according to claim 1, wherein the cobalt salt in step (1) is at least one selected from the group consisting of cobalt nitrate, cobalt chloride, cobalt bromide, cobalt acetate, and cobalt sulfate;
and/or the concentration of cobalt ions in the cobalt salt is 0.05-0.5 mol/L.
3. The method according to claim 1, wherein the polyol in the step (1) is at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and butanediol.
4. The process according to claim 1, wherein the organic ligand in the step (2) is at least one selected from the group consisting of 2-methylimidazole and 5, 6-dimethylbenzimidazole,
and/or the concentration of the organic ligand in the solution is 0.01-0.1 g/mL.
5. The method according to claim 1, wherein the mixing reaction in step (3) specifically comprises:
and (3) fully mixing the organic ligand solution and the metal cobalt salt solution for 0.5-1.5 h through vigorous stirring to obtain a mixed solution, and then reacting the mixed solution in a water bath at 60-80 ℃ for 0.5-4 h.
6. The method according to claim 1, wherein the solid-liquid separation in step (4) is at least one selected from the group consisting of centrifugal separation, vacuum filtration, and cross-flow filtration.
7. The process according to claim 1, wherein after the solid-liquid separation in step (4), the obtained solid zeolite imidazole ester framework structure material is further washed with ethanol;
and/or drying the solid zeolite imidazole ester skeleton structure material by blowing at 50-70 ℃.
8. The method according to claim 1, wherein the inorganic salt in step (5) is at least one selected from potassium chloride and sodium chloride;
and/or the concentration of the inorganic salt in the solution is 0.01-0.1 g/mL;
and/or the solvent of the inorganic salt solution is selected from at least one of methanol and ethanol;
and/or the time of the dipping treatment is 2-4 h.
9. The method according to claim 1, wherein the inert gas in step (6) is at least one selected from the group consisting of argon, nitrogen and helium;
and/or the high-temperature calcination temperature is 800-900 ℃.
10. The method according to claim 1, wherein the purification treatment in step (7) specifically comprises: dispersing the Co-N-C crude product in water, standing for 1-2 h, separating solid from liquid, and drying to obtain the final product.
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