CN116435528A - Preparation method of Pt-supported ZIF-67-based hydrogen fuel cell catalyst - Google Patents
Preparation method of Pt-supported ZIF-67-based hydrogen fuel cell catalyst Download PDFInfo
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- CN116435528A CN116435528A CN202310703981.5A CN202310703981A CN116435528A CN 116435528 A CN116435528 A CN 116435528A CN 202310703981 A CN202310703981 A CN 202310703981A CN 116435528 A CN116435528 A CN 116435528A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000002245 particle Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- -1 platinum ions Chemical class 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 104
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000001603 reducing effect Effects 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229940072107 ascorbate Drugs 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
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- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
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- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 238000013508 migration Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 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
- H01M4/88—Processes of manufacture
-
- 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
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- 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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- Manufacturing & Machinery (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention provides a preparation method of a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst, which relates to the technical field of catalyst materials, and is characterized in that a carrier with a ZIF-67 pore structure is prepared by firstly based on a ZIF-67 metal organic framework material, and oxygen-containing functional groups (such as OH ‑ ) The carrier is modified by the solution of (2), then the carrier is immersed in a chloroplatinic acid solution, so that the chloroplatinic acid solution is fully immersed in the carrier, platinum ions in the solution are converted into a platinum salt compound capable of being thermally reduced and decomposed, and the platinum salt compound is thermally reduced and decomposed into simple substance Pt, so that Pt particles are loaded on the carrier. The specific surface area of the catalyst prepared by the method is up to 458m 2 Per gram, the average particle diameter of the supported Pt particles is as low as 3.2nm, and the electrochemical active area is 108m 2 /g, and the catalysis of the catalystThe active and stability are high, and the material is suitable for being used as a cathode material of a hydrogen fuel cell.
Description
Technical Field
The invention relates to the technical field of catalyst materials, in particular to a preparation method of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst.
Background
Proton Exchange Membrane Fuel Cells (PEMFC) are considered as new energy power conversion devices with high conversion, high energy density, zero emission, and zero pollution, and the oxidation or reduction reaction rate in the cell largely depends on the electrocatalyst, whose performance determines the conversion efficiency of fuel storage chemical energy into electric energy. Research has shown that platinum (Pt) -based catalysts are useful in hydrogen fuel cells (H 2 -PEMFC) the most effective high-activity catalyst, the Pt-based catalyst may dissolve, migrate, agglomerate nano Pt particles during the operation of the battery, so that the catalytic activity is reduced, thereby resulting in reduced output efficiency and reduced performance of the battery. At present, the main method for improving the stability and catalytic activity of the Pt-based catalyst is to adjust the component structure in the Pt-based catalyst, such as modifying nano Pt particles by metal with high oxidation-reduction potential, increasing the dispersity of the Pt particles on a carrier to improve the stability of the catalyst, or adjusting the electronic structure on the surface of Pt atoms to improve the utilization rate of Pt atoms, thereby improving the electrocatalytic conversion efficiency.
In the prior art, the application number is CN202110701002.3, the publication date is 2021, 9 and 21, the invention patent with the name of a preparation method of a cobalt-modified carbon-supported ultrafine platinum nano alloy catalyst discloses a cobalt-modified carbon-supported ultrafine platinum nano alloy catalyst. However, when the platinum nanoparticles are loaded into the catalyst, and the loading amount of the platinum nanoparticles exceeds the loading limit of the carrier, the platinum nanoparticles are agglomerated, so that the particle size distribution range of the platinum nanoparticles in the catalyst is too wide, and the catalytic efficiency of the catalyst is affected.
Secondly, in the prior art, the application number is CN202110701002.3, the publication date is 2021, 9 and 21, and the patent application document of the preparation method of the cobalt-modified carbon-supported ultrafine platinum nano alloy catalyst is that a carrier cobalt carbon material is prepared firstly, and then platinum nano particle particles are loaded on the surface of the carrier by utilizing liquid phase reduction, impregnation and adsorption so as to improve the catalytic activity of the catalyst. However, the platinum nanoparticles loaded in the above process are combined with the carrier in an electrostatic adsorption manner, the combination effect between the platinum nanoparticles and the carrier is limited, and the migration of the platinum nanoparticles cannot be avoided in the using process.
In view of the foregoing, there is a need for an improved Pt-supported ZIF-67-based hydrogen fuel cell catalyst preparation method that solves the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a preparation method of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst.
In order to achieve the above object, the present invention provides a preparation method of a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst, comprising the steps of:
s1, respectively dissolving cobalt nitrate and 2-methylimidazole in a first organic solution to obtain a cobalt nitrate solution and a 2-methylimidazole solution, slowly pouring the 2-methylimidazole solution into the cobalt nitrate solution, and performing hydrothermal reaction for 10-24 hours in an environment with the temperature of 120-150 ℃; washing the product obtained by the reaction with a second organic solution, centrifuging, and drying at 50-80 ℃ for 3-5 hours to obtain ZIF-67 powder; under the protection of inert gas, carrying out heat treatment on ZIF-67 powder for 2-5h in an environment with the temperature of 300-700 ℃, grinding a product after calcining, mixing the ground powder with an oxidizing solution, magnetically stirring for 1-3h, filtering, washing, and freeze-drying to obtain a pretreated carrier;
s2, adding the carrier prepared in the step S1 into a chloroplatinic acid solution, and carrying out ultrasonic treatment for 1-3 hours to ensure that the carrier is completely dispersed in the solution; then slowly adding the first reducing solution, magnetically stirring for 1-3h to convert platinum ions in the chloroplatinic acid solution into a platinum salt compound capable of being thermally reduced and decomposed, and then slowly dropwise adding a mixed solution of the second reducing solution and a dispersing agent into a reaction system for 2-30min; after the reaction is finished, freeze-drying and grinding the collected solid product, and performing heat treatment for 2-5 hours in an environment with the temperature of 300-700 ℃ under the protection of inert gas, so that the platinum salt compound is thermally reduced and decomposed into simple substance Pt, and the ZIF-67-based hydrogen fuel cell catalyst for loading Pt is prepared, wherein the particle size of Pt particles in the catalyst is 3.0-5.0nm.
Preferably, in the step S1, the oxidizing solution is one or more of hydrogen peroxide, peracetic acid and ammonium persulfate, and the mass percentage of the oxidizing solution is 10-30%.
Preferably, in step S1, the ZIF-67 powder is added in an amount of 5-10mg/mL during the mixing of the ZIF-67 powder with the oxidizing solution.
Preferably, in step S2, the concentration of the first reducing solution and the second reducing solution is 1.5-5.0mg/mL; the first reducing solution and the second reducing solution are one or more of ascorbic acid, ascorbate, formaldehyde, hydrazine hydrate, metal borohydride and ammonium chloride, and the content of substances which play a role in reduction in the added first reducing solution and the added second reducing solution is 1.0-1.2 times of the theoretical use amount.
Preferably, in the step S2, the dispersing agent is one or more of gelatin, polyethylene glycol, polyvinyl alcohol, PVP, PVA, citrate and quaternary ammonium salt, and the concentration of the dispersing agent is 1.5-2.5mg/mL.
Preferably, in the step S1, the concentration of the 2-methylimidazole solution is 0.005-50mg/mL, and the concentration of the cobalt nitrate solution is 0.5-30mg/mL.
Preferably, in step S1, the first organic solution is one or more of methanol, ethanol, propanol, ethylene glycol, isopropanol and N, N-dimethylformamide, N-dimethylacetamide and diethylformamide.
Preferably, the inert gas is one or more of argon, nitrogen and helium.
Preferably, the heat treatment is performed as follows: heating from 25 ℃ to 300 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h at 300 ℃; then heating from 300 ℃ to 500 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h; finally, the temperature is increased from 500 ℃ to 700 ℃ at a heating rate of 5-30 ℃/min, and the temperature is kept for 1.0-3.0h.
Preferably, in step S1, the second organic solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and diethylformamide.
The beneficial effects of the invention are as follows:
1. the preparation method of the Pt-loaded ZIF-67-based hydrogen fuel cell catalyst provided by the invention prepares the carrier with the ZIF-67 pore structure by firstly based on the ZIF-67 metal organic framework material, and utilizes oxygen-containing functional groups (such as OH - ) The carrier is treated, then the carrier is immersed in a chloroplatinic acid solution, so that the chloroplatinic acid solution completely infiltrates the carrier, platinum ions in the solution are converted into a platinum salt compound capable of being thermally reduced and decomposed, and the platinum salt compound is thermally reduced and decomposed into elemental Pt, so that the loading amount of Pt particles is controlled in a manner of loading the Pt particles on the carrier, and the controllable loading of the Pt particles on the carrier is effectively realized. By the above method, the specific surface area of the prepared catalyst is up to 458m 2 Per gram, the average particle diameter of the supported Pt particles is as low as 3.2nm, and the electrochemical active area is 108m 2 And the catalyst has high catalytic activity and stability, and is suitable for being used as a cathode material of a hydrogen fuel cell.
2. The preparation method of the Pt-supported ZIF-67-based hydrogen fuel cell catalyst provided by the invention utilizes oxygen-containing functional groups (such as OH - ) After the carrier is treated with the solution of (2), pt particles are loaded on the carrier, OH can be used - The binding force between Pt particles and a carrier is enhanced, migration of the Pt particles in the catalyst is avoided, meanwhile, the dispersity of the Pt particles in the catalyst is improved, aggregation of the Pt particles is avoided, and the utilization rate of the Pt particles is effectively improved; after the chloroplatinic acid solution fully infiltrates the carrier, the pore structure of the carrier can be utilized to generate a limiting domain effect on the growth of Pt particles so as to limit the size of the Pt particles, so that the particle size of the loaded Pt particles is smaller, and the catalytic activity of the catalyst is effectively improved. By the mode, the problems that nanoparticles are easy to aggregate, the activity of the catalyst is low and the like in the preparation of the catalyst in the prior art are effectively solved.
Drawings
FIG. 1 is a TEM image of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the specific surface area and pore size distribution of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph showing the size distribution of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst prepared in example 1;
FIG. 4 is a distribution diagram of the size of the catalyst prepared in comparative example 2;
FIG. 5 is an XRD pattern of a Pt-supported ZIF-67-based hydrogen fuel cell catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph of electrochemical cyclic voltammetry and linear sweep voltammetry of a Pt-supported ZIF-67 based hydrogen fuel cell catalyst prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the preparation method of the Pt-loaded ZIF-67-based hydrogen fuel cell catalyst provided by the invention comprises the following steps:
s1, respectively dissolving cobalt nitrate and 2-methylimidazole in a first organic solution to obtain a cobalt nitrate solution and a 2-methylimidazole solution, slowly pouring the 2-methylimidazole solution into the cobalt nitrate solution, and performing hydrothermal reaction for 10-24 hours in an environment with the temperature of 120-150 ℃; washing the product obtained by the reaction with a second organic solution, centrifuging, and drying at 50-80 ℃ for 3-5 hours to obtain ZIF-67 powder; performing heat treatment on ZIF-67 for 2-5h in an environment with the temperature of 300-700 ℃ under the protection of inert gas, grinding the product after calcining, mixing the ground powder with an oxidizing solution, magnetically stirring for 1-3h, filtering, washing, and freeze-drying to obtain a pretreated carrier;
s2, loading Pt particles on the carrier prepared in the step S1 by adopting a dipping-reduction mode, wherein the specific operation method is as follows: adding the carrier into the chloroplatinic acid solution, and carrying out ultrasonic treatment on the obtained mixed solution for 1-3 hours so as to ensure that the carrier is completely dispersed in the solution; then slowly adding the first reducing solution, magnetically stirring for 1-3h to convert platinum ions in the solution into a platinum salt compound (such as ammonium chloroplatinate) capable of being thermally reduced and decomposed, and loading the platinum salt compound on the surface of a carrier and the pore structure in the carrier, wherein in the reaction process, a mixed solution of the second reducing solution and a dispersing agent is slowly dropwise added into a reaction system for 2-30min; after the reaction is finished, the collected solid product is freeze-dried and ground, and then is heat-treated for 2-5 hours in the environment with the temperature of 300-700 ℃ under the protection of inert gas, so that the platinum salt compound is thermally reduced and decomposed into simple substance Pt, and the ZIF-67-based hydrogen fuel cell catalyst for loading Pt is prepared, wherein the particle size of Pt particles in the catalyst is 3.0-5.0nm, and under the condition, the activity and the stability of the catalyst are optimal.
Preferably, in step S1, the first organic solution is one or more of methanol, ethanol, propanol, ethylene glycol, isopropanol and N, N-dimethylformamide, N-dimethylacetamide and diethylformamide.
Preferably, in step S1, the concentration of the 2-methylimidazole solution is 0.005-50mg/mL, and the concentration of the cobalt nitrate solution is 0.5-30mg/mL.
Preferably, in step S1, the second organic solution is one or more of N, N-dimethylformamide, N-dimethylacetamide and diethylformamide.
Preferably, in the step S1, the oxidizing solution is one or more of hydrogen peroxide, peracetic acid and ammonium persulfate, the mass percent of the oxidizing solution is 10-30%, and the adding amount of the ZIF-67 powder in the mixing process of the ZIF-67 powder and the oxidizing solution is 5-10mg/mL.
Preferably, in step S1 and step S2, the inert gas is one or more of argon, nitrogen and helium.
Preferably, in step S1 and step S2, the heat treatment is performed as follows: heating from 25 ℃ to 300 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h at 300 ℃; then heating from 300 ℃ to 500 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h; finally, the temperature is increased from 500 ℃ to 700 ℃ at a heating rate of 5-30 ℃/min, and the temperature is kept for 1.0-3.0h.
Preferably, in step S2, the concentration of the first and second reducing solutions is 1.5-5.0mg/mL, and both are one or more of ascorbic acid, ascorbate, formaldehyde, hydrazine hydrate, metal borohydride and ammonium chloride, and the content of the substance exerting the reducing effect in the added first and second reducing solutions is 1.0-1.2 times the theoretical use amount, and it should be noted that the theoretical use amount herein is the use amount determined according to the chemical reaction equation.
Preferably, in the step S2, the dispersing agent is one or more of gelatin, polyethylene glycol, polyvinyl alcohol, PVP, PVA, citrate and quaternary ammonium salt, the concentration of the dispersing agent is 1.5-2.5mg/mL, and the dispersing agent can be added to effectively improve the dispersity of Pt particles and avoid aggregation of the Pt particles.
The preparation method of the Pt-supported ZIF-67-based hydrogen fuel cell catalyst of the present invention is further described below with reference to specific examples:
example 1
S1, 2.0g Co (NO) 3 ) 2 ·6H 2 O and 2.0g of 2-methylimidazole are respectively dissolved in 100mL of methanol solution to obtain a cobalt nitrate solution and a 2-methylimidazole solution, the 2-methylimidazole solution is slowly poured into the cobalt nitrate solution, and hydrothermal reaction is carried out for 12h under the environment of 120 ℃; washing the reaction product with N, N-dimethylformamide for 3-5 times, centrifuging, anddrying at 60deg.C for 3 hr to obtain ZIF-67 powder; heating ZIF-67 from 25deg.C to 300deg.C at a heating rate of 5deg.C/min under the protection of argon atmosphere for 3 hr, grinding the product after calcining, and adding 80mg of powder obtained by grinding into 30% H 2 O 2 In the solution, magnetic stirring is carried out for 3 hours to mix the two materials uniformly, and then the mixture is filtered, washed and freeze-dried to obtain the carrier with a pore structure;
s2, adding 80mg of the carrier prepared in the step S1 into 1.0mL of chloroplatinic acid/ethylene glycol solution with the concentration of 0.02g/mL, and carrying out ultrasonic treatment for 3 hours to ensure that the carrier is completely dispersed in the solution; then, 15mL of 0.5mol/L ammonium chloride solution is slowly added, and magnetically stirred for 3 hours, so that platinum ions in the solution are converted into ammonium chloroplatinate and are loaded on the surface of the carrier and the pore structure in the carrier, and the chemical equation of the reaction process is H 2 PtCl 6 +2NH 4 Cl=(NH 4 ) 2 PtCl 6 Slowly dropwise adding a mixed solution of hydrazine hydrate and PVP dispersant into the reaction system for 10min in the reaction process of ∈2HCl to convert platinum ions into a platinum salt compound capable of being thermally reduced and decomposed, wherein the chemical equation in the reaction process is as follows, 2NH 2 NH 2 +(NH 4 ) 2 PtCl 6 =(NH 4 ) 2 PtCl 4 +2N 2 +3H 2 +2HCl; after the reaction is finished, the collected solid product is freeze-dried and ground, and then is heat-treated for 3 hours in an environment with the temperature of 500 ℃ under the protection of argon gas, and ammonium chloroplatinate is thermally decomposed to obtain elemental platinum, so that the Pt-loaded ZIF-67-based hydrogen fuel cell catalyst is prepared.
The TEM image of the catalyst prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that there is no obvious aggregation phenomenon in the catalyst, and Pt particles are uniformly distributed, and the average particle size of the Pt particles is 3.2nm; the specific surface area and pore size distribution of the catalyst prepared in this example and the commercial Pt/C catalyst are shown in the graphs (a) and (b) of FIG. 2. As can be seen from the graph (b) of FIG. 2, the catalyst prepared in this example has pore structures with sizes of 2.0-5.0nm and 10.0-70.0nm, and the formula is used
And->
The specific surface area of the catalyst was calculated to be +.>
Wherein P represents the pressure of the gas at adsorption equilibrium, < >>
Represents the saturated vapor pressure of the adsorbate at the experimental temperature, V represents the volume of the adsorbate gas, +.>
Represents the single-layer adsorption gas capacity, C represents a constant related to the heat of adsorption and the heat of vaporization, ++>
Represents the A Fu Jiade Luo constant,>
represents the cross-sectional area of the adsorbed gas, +.>
Representing the volume per gram of molecule in a standard state; the XRD pattern of the catalyst prepared in this example is shown in fig. 5, and it can be seen from the XRD pattern of fig. 5 that the catalyst detects 4 typical diffraction peaks corresponding to the (fcc) face-centered cubic structure Pt-Co alloy (111), (200), (220), and (311) respectively at the 2θ angles of 41.3 °, 48.2 °, 70.3 °, and 84.4 °, and no diffraction peak of Co or Co oxide is found, because Co exists in amorphous form, pt and Co exist in the catalyst in alloy form, and the result shows that the Pt-loaded ZIF-67-based hydrogen fuel cell catalyst was successfully prepared; the electrochemical cyclic voltammetry and linear sweep voltammogram of the catalyst prepared in this example are shown in FIG. 6 (a) and (b), respectively, and it can be seen from the graph (a) that the catalyst prepared in this example exhibits a hydrogen adsorption-desorption peak and a Pt oxidation-reduction peak similar to those of a commercial Pt/C catalyst, using the conventional methodsEcsa=qh/(0.21×[Pt]) Example 1 was calculated to have a larger electrochemically active area ecsa=108m 2 ·g -1 Wherein +.>
Representing the charge generated by hydrogen adsorption/desorption, [ Pt ]]Representing the loading of platinum on the working electrode; the higher the current density by linear sweep voltammetry versus current density at 0.9V, the higher the activity, and as can be seen from fig. 6 (b), the catalyst prepared in example 1 had a higher current density than commercial Pt/C at 0.9V, and the half-wave potential shifted in the forward direction, with better oxygen reduction catalytic performance than commercial Pt/C catalysts.
Comparative example 1
Comparative example 1 differs from example 1 in that: in step S2, the secondary reduction is performed without adding the mixed solution of the second reducing solution and the dispersing agent, and other steps are substantially the same as those in example 1, and will not be described herein.
Comparative example 2
Comparative example 2 differs from example 1 in that: in step S2, instead of immersing the carrier in a chloroplatinic acid/ethylene glycol solution and then reducing the platinum ions in the solution to load platinum particles on the carrier, the same reducing agent is used to reduce chloroplatinic acid with the same concentration, and then the carrier is immersed in the reduced solution and magnetically stirred for 3 hours, so that the reduced Pt particles are deposited on the pore structure loaded on the surface and inside of the carrier, and other steps are basically the same as those of example 1 and will not be repeated here. The size distribution diagram of the catalyst material prepared by the method is shown in fig. 4, and is compared with the size distribution diagram of the catalyst prepared by the method shown in fig. 3, it can be seen from fig. 4 that the average particle size of Pt particles in the catalyst is 4.5nm, which is far greater than 3.2nm of the present application, because: the above-described manner of first reduction and then loading does not control the nucleation growth process of Pt particles, so that the size of Pt particles is larger than the Pt particles of the manner of growing Pt particles in the pore structure of the carrier of example 1; secondly, the process of supporting Pt particles in comparative example 2 was achieved by means of electrostatic adsorption between Pt particles and a carrier, so that the binding force between Pt particles having a large particle diameter and a carrier was weak and the loading amount of Pt particles was limited, and the above two reasons led to the catalyst prepared in comparative example 2 having lower catalytic activity than that in example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that: in step S1, H is not used 2 O 2 The solution was used to treat the milled powder, but the milled powder was directly added to the chloroplatinic acid/ethylene glycol solution for Pt particle loading, and the other steps were substantially the same as in example 1 and will not be described again. The electrochemical active areas of the catalysts prepared in comparative examples 1 to 3 and example 1 are shown in table 1, and it can be seen from the table that the catalysts prepared in example 1 have an electrochemical active area greater than that of comparative examples 1 to 3 because: in the preparation of the catalyst by the method of example 1, the milled powder was impregnated with H 2 O 2 Unstable H when in solution 2 O 2 The solution can release oxygen-containing functional groups, and in the subsequent process of loading Pt particles, the Pt particles can be tightly combined with the carrier, so that the stability of the Pt particles loaded on the carrier is ensured; the method is characterized in that the carrier is dispersed in the chloroplatinic acid solution, after the chloroplatinic acid solution enters the pore structure in the carrier, secondary reduction is carried out to load Pt particles on the carrier, on one hand, the pore structure of the carrier can be utilized to enable the chloroplatinic acid solution to enter the carrier so as to improve the loading capacity of the Pt particles as much as possible, on the other hand, the reduction process of Pt ions is controlled in a secondary reduction mode, excessive Pt particles are prevented from being generated, meanwhile, the pore structure of the carrier can limit the growth of the Pt particles, so that the size of the Pt particles is limited, the binding force between the Pt particles and the carrier and the dispersion degree of the Pt particles in the carrier are effectively improved, the occurrence of agglomeration phenomenon caused by migration of the Pt particles in the use process is reduced, and the utilization rate of the Pt particles in the catalyst is improved.
Table 1 electrochemically active areas of the catalysts of comparative examples 1 to 3 and example 1
In summary, the preparation method of the Pt-supported ZIF-67-based hydrogen fuel cell catalyst provided by the invention prepares the carrier with the ZIF-67 pore structure by firstly based on the ZIF-67-metal organic framework material, and utilizes oxygen-containing functional groups (such as OH - ) The carrier is treated by the solution of (2), then the carrier is immersed in the chloroplatinic acid solution, so that the chloroplatinic acid solution is fully immersed in the carrier, platinum ions in the solution are converted into platinum salt compounds which can be thermally reduced and decomposed, and the platinum salt compounds are thermally reduced and decomposed into simple substance Pt, so that the loading of Pt particles on the carrier is controlled in a manner of loading the Pt particles on the carrier, and the controllable loading of the Pt particles on the carrier is effectively realized. The specific surface area of the catalyst prepared by the method is up to 458m 2 Per gram, the average particle diameter of the supported Pt particles is as low as 3.2nm, and the electrochemical active area is 108m 2 And the catalyst has high catalytic activity and stability, and is suitable for being used as a cathode material of a hydrogen fuel cell. By adopting the mode, the problems of easy aggregation of nano particles, low catalyst activity and the like existing in the preparation of the catalyst in the prior art are effectively solved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the Pt-supported ZIF-67-based hydrogen fuel cell catalyst is characterized by comprising the following steps of:
s1, respectively dissolving cobalt nitrate and 2-methylimidazole in a first organic solution to obtain a cobalt nitrate solution and a 2-methylimidazole solution, slowly pouring the 2-methylimidazole solution into the cobalt nitrate solution, and performing hydrothermal reaction for 10-24 hours in an environment with the temperature of 120-150 ℃; washing the product obtained by the reaction with a second organic solution, centrifuging, and drying at 50-80 ℃ for 3-5 hours to obtain ZIF-67 powder; under the protection of inert gas, carrying out heat treatment on ZIF-67 powder for 2-5h in an environment with the temperature of 300-700 ℃, grinding a product after calcining, mixing the ground powder with an oxidizing solution, magnetically stirring for 1-3h, filtering, washing, and freeze-drying to obtain a pretreated carrier;
s2, adding the carrier prepared in the step S1 into a chloroplatinic acid solution, and carrying out ultrasonic treatment for 1-3 hours to ensure that the carrier is completely dispersed in the solution; then slowly adding the first reducing solution, magnetically stirring for 1-3h to convert platinum ions in the chloroplatinic acid solution into a platinum salt compound capable of being thermally reduced and decomposed, and then slowly dropwise adding a mixed solution of the second reducing solution and a dispersing agent into a reaction system for 2-30min; after the reaction is finished, freeze-drying and grinding the collected solid product, and performing heat treatment for 2-5 hours in an environment with the temperature of 300-700 ℃ under the protection of inert gas, so that the platinum salt compound is thermally reduced and decomposed into simple substance Pt, and the ZIF-67-based hydrogen fuel cell catalyst for loading Pt is prepared, wherein the particle size of Pt particles in the catalyst is 3.0-5.0nm.
2. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S1, the oxidizing solution is one or more of hydrogen peroxide, peracetic acid and ammonium persulfate, and the mass percentage of the oxidizing solution is 10-30%.
3. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst as recited in claim 1, wherein in step S1, the amount of the ZIF-67 powder added during the mixing of the ZIF-67 powder with the oxidizing solution is 5-10mg/mL.
4. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S2, the concentrations of the first reducing solution and the second reducing solution are 1.5-5.0mg/mL; the first reducing solution and the second reducing solution are one or more of ascorbic acid, ascorbate, formaldehyde, hydrazine hydrate, metal borohydride and ammonium chloride, and the content of substances which play a role in reduction in the added first reducing solution and the added second reducing solution is 1.0-1.2 times of the theoretical use amount.
5. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S2, the dispersant is one or more of gelatin, polyethylene glycol, polyvinyl alcohol, PVP, PVA, citrate and quaternary ammonium salt, and the concentration of the dispersant is 1.5-2.5mg/mL.
6. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S1, the concentration of the 2-methylimidazole solution is 0.005-50mg/mL and the concentration of the cobalt nitrate solution is 0.5-30mg/mL.
7. The method for preparing a Pt-supported ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S1, the first organic solution is one or more of methanol, ethanol, propanol, ethylene glycol, isopropanol and N, N-dimethylformamide, N-dimethylacetamide and diethylformamide.
8. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst as claimed in claim 1, wherein the inert gas is one or more of argon, nitrogen and helium.
9. The method for preparing a Pt-loaded ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein the heat treatment is performed by: heating from 25 ℃ to 300 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h at 300 ℃; then heating from 300 ℃ to 500 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 0.5-1.0h; finally, the temperature is increased from 500 ℃ to 700 ℃ at a heating rate of 5-30 ℃/min, and the temperature is kept for 1.0-3.0h.
10. The method for preparing a Pt-supported ZIF-67-based hydrogen fuel cell catalyst according to claim 1, wherein in step S1, the second organic solution is one or more of N, N-dimethylformamide, N-dimethylacetamide, and diethylformamide.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266770A (en) * | 2011-06-28 | 2011-12-07 | 南京大学 | Preparation method of platinum/graphene nanometer electro-catalyst used for proton exchange membrane fuel cell |
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| WO2017161980A1 (en) * | 2016-03-24 | 2017-09-28 | 武汉凯迪工程技术研究总院有限公司 | Ultra-dispersed cobalt/platinum-based catalyst for fischer-tropsch synthesis and manufacturing method thereof |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
| CN110931805A (en) * | 2019-11-19 | 2020-03-27 | 一汽解放汽车有限公司 | Platinum alloy catalyst, preparation method thereof and application thereof in fuel cell cathode catalyst |
| CN113422073A (en) * | 2021-06-23 | 2021-09-21 | 长春黄金研究院有限公司 | Preparation method of cobalt-modified carbon-supported superfine platinum nano-alloy catalyst |
| CN115133050A (en) * | 2022-07-06 | 2022-09-30 | 北京化工大学 | Platinum-cobalt alloy catalyst, preparation method and application thereof |
-
2023
- 2023-06-14 CN CN202310703981.5A patent/CN116435528B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266770A (en) * | 2011-06-28 | 2011-12-07 | 南京大学 | Preparation method of platinum/graphene nanometer electro-catalyst used for proton exchange membrane fuel cell |
| WO2017161980A1 (en) * | 2016-03-24 | 2017-09-28 | 武汉凯迪工程技术研究总院有限公司 | Ultra-dispersed cobalt/platinum-based catalyst for fischer-tropsch synthesis and manufacturing method thereof |
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
| CN110931805A (en) * | 2019-11-19 | 2020-03-27 | 一汽解放汽车有限公司 | Platinum alloy catalyst, preparation method thereof and application thereof in fuel cell cathode catalyst |
| CN113422073A (en) * | 2021-06-23 | 2021-09-21 | 长春黄金研究院有限公司 | Preparation method of cobalt-modified carbon-supported superfine platinum nano-alloy catalyst |
| CN115133050A (en) * | 2022-07-06 | 2022-09-30 | 北京化工大学 | Platinum-cobalt alloy catalyst, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| X.SHI: "Pt-Co@NCNTs cathode catalyst using ZIF-67 for porton exchange membrane fuel cell", 《INTERNATIONAL JOUNAL OF HYDROGEN ENERGY》 * |
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