CN115036522A - Method for preparing alloy catalyst for fuel cell in limited area - Google Patents
Method for preparing alloy catalyst for fuel cell in limited area Download PDFInfo
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- CN115036522A CN115036522A CN202210538139.6A CN202210538139A CN115036522A CN 115036522 A CN115036522 A CN 115036522A CN 202210538139 A CN202210538139 A CN 202210538139A CN 115036522 A CN115036522 A CN 115036522A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 40
- 239000000956 alloy Substances 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 29
- 239000002923 metal particle Substances 0.000 claims abstract description 15
- 238000005275 alloying Methods 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 73
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
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- 238000011068 loading method Methods 0.000 claims description 4
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
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- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910000531 Co alloy Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 229910001339 C alloy Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910021069 Pd—Co Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
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- 238000004821 distillation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing an alloy catalyst for a fuel cell by utilizing a confinement effect, which is characterized by depositing a metal salt precursor around and on the surface of noble metal particles of carbon-supported noble metal, utilizing the confinement effect of the metal precursor on the noble metal particles to limit the agglomeration and growth of the noble metal particles, and enabling part of metal to enter the crystal lattices of the noble metal particles to form an alloy through high-temperature calcination, thereby obtaining the alloy catalyst with uniform dispersion and 2-4 nm of alloy particle size. The method realizes alloying through the confinement effect of the metal precursor, can inhibit the migration and growth of noble metal particles in the high-temperature calcination process, is beneficial to keeping small size and high dispersion of the alloy particles, can realize the confinement effect on different types of metal particles, and has strong universality.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of an alloy catalyst for a fuel cell with high stability and high performance.
Background
The Membrane Electrode Assembly (MEA) of a fuel cell is a key component of the fuel cell, and the catalytic layer on the MEA is a place where reaction occurs, and the performance of the MEA directly determines the power density of the fuel cell. Fuel cell cathode catalysts are always subject to a key problem of slow kinetic reactions, and therefore large amounts of Pt metal are often required in fuel cell stacks, resulting in increased costs. Meanwhile, the fuel cell has problems of insufficient durability, etc., which seriously affects the commercialization progress of the fuel cell. The durability of the membrane electrode is insufficient mainly because the Pt particles on the surface of the catalyst are easy to migrate, agglomerate, fall off and dissolve on the carrier in the operating state of the fuel cell, which reduces the active area of the catalyst, and further reduces the catalytic performance of the catalyst, resulting in the performance reduction of the fuel cell. Therefore, on the premise of not reducing or even improving the performance of the platinum-based catalyst, the emphasis on improving the utilization rate of the noble metal platinum and reducing the cost is the current research.
Alloying noble metal Pt with lower-priced transition metals and main group metals is an effective way to improve catalytic activity of the catalyst, enhance stability, and improve Pt utilization rate and thus reduce Pt usage. The Pt-based alloy has better catalytic performance and better application prospect, and mainly comes from the following sources: (1) the addition of the transition metal can adjust the electronic structure of Pt, reduce the d-band center of Pt, further improve the adsorption property of Pt on the oxygen reduction oxygen-containing intermediate and improve the catalytic performance of the catalyst; (2) transition metal enters into crystal lattices of Pt to cause obvious tensile crystal lattice strain on a surface Pt layer, so that the catalytic performance of the catalyst is further adjusted; (3) the Pt alloy can be prepared, so that the use amount of Pt can be reduced, and the cost of the membrane electrode is reduced. However, the preparation of Pt-based alloys often requires high temperature conditions to promote alloying, which results in difficult control of particle size, and disordered movement of the transition metal during heat treatment also results in difficult uniform distribution of particles on the carbon support. Therefore, how to prepare a Pt-based alloy with uniformly distributed particles and a small size still presents a great challenge.
Chinese patent CN 113161563a discloses a platinum-cobalt alloy catalyst for fuel cells and a preparation method thereof, wherein a polyol reduction method is adopted to prepare the platinum-cobalt alloy catalyst, and the method mainly comprises the steps of adding a platinum precursor, a cobalt precursor, a carbon carrier and a reducing agent into polyol, and directly reacting in the polyol to obtain the carbon-supported alloy catalyst. However, in this method, the size control of the alloy particles, the uniformity of the particle distribution, and the control of the alloy composition need to be optimized.
Disclosure of Invention
Based on the preparation defects of the alloy catalyst used by the conventional proton exchange membrane fuel cell, the invention provides a method for preparing the alloy catalyst for the fuel cell in a limited domain manner.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon-supported noble metal is added into a metal precursor solution, the solution is uniformly dispersed and then stirred and evaporated to dryness, so that the metal precursor covers the surfaces of noble metal particles and fills gaps among the noble metal particles, then high-temperature alloying is carried out in a reducing atmosphere, and the alloy catalyst suitable for a fuel cell is obtained after acid washing and drying.
Furthermore, the loading amount of noble metal in the carbon-supported noble metal is 5-80%; the carbon carrier is any one of carbon powder, carbon nanotubes, nitrogen-doped carbon nanotubes, graphene oxide and graphene, and the noble metal is any one of Pt, Ir, Pd, Ru and Rh.
Further, the metal precursor solution is prepared by dissolving a metal precursor in water and/or a volatile organic solvent (such as methanol, ethanol, acetone, n-hexane, cyclohexane, etc.); the metal precursor is a hydrochloride, a carbonate, a nitrate, a sulfate, an acetate, an oxalate, a phosphate, an amino complex, a carbonyl complex or an acetylacetone complex of at least one of metal elements scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium and tin; the concentration of the metal element contained in the metal precursor solution is 0.1mmol/L-3 mol/L.
Further, the amount of the metal precursor is converted according to the mass ratio of the noble metal to the metal element in the metal precursor of 1:1-1: 7.
Further, the reducing atmosphere is hydrogen or a mixed gas of hydrogen and inert gas, wherein the volume content of the hydrogen is 1-100%;
further, the high-temperature alloying is carried out for 0.5 to 6 hours at the temperature of between 300 and 1000 ℃.
Further, the size of alloy particles in the obtained alloy catalyst is 2-4 nm.
Compared with the current situation, the invention has the following beneficial effects:
1. according to the invention, a metal precursor is deposited around and on the surface of the noble metal particles, in the high-temperature calcination process, part of the metal precursor is firstly generated into a metal simple substance in a high-temperature reducing atmosphere, and then enters the crystal lattice of the noble metal through migration to form an alloy, so that the performance of the catalyst can be promoted to be improved; meanwhile, the metal precursor deposited around the noble metal particles has a confinement effect on the noble metal particles, and can prevent the noble metal particles from agglomerating and growing up in the high-temperature calcination process, so that alloy particles with smaller size and uniform distribution are formed, the reduction of the electrochemical active area is avoided, and the catalytic efficiency is further improved.
2. The invention provides metal elements required for forming the alloy by depositing the metal precursor around and on the surface of the noble metal particles and provides a confinement effect as a protective layer, and the oxygen reduction performance and the fuel cell efficiency of the alloy can be obviously optimized by accurately regulating and controlling the proportion of the metal precursor and the noble metal in the process.
Drawings
FIG. 1 is an SEM image of catalyst samples obtained in examples 1 to 3 and comparative examples 1 to 3;
FIG. 2 is an SEM image of catalyst samples obtained in example 4 and example 5;
FIG. 3 is an X-ray diffraction pattern of example 2 and comparative example 1;
FIG. 4 is a graph showing oxygen reduction performance of samples of the catalysts obtained in examples 1 to 3 and comparative examples 1 to 3;
fig. 5 shows the results of performance tests of single cells prepared using the catalyst samples obtained in example 2 and comparative example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene glycol chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and the heating was stopped after 2 hours of reflux by condensation at 200 ℃. After cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and placing in a 60 ℃ drying oven for drying for 12 hours to obtain carbon-supported platinum black powder.
2) Firstly weighing 200mg of carbon-supported platinum for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 1:1, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, adding weighed carbon-supported platinum, performing ultrasonic stirring until the cobalt chloride is uniformly dispersed, performing immersion drying at 70 ℃, drying for 12 hours in a vacuum drying oven at 70 ℃ after the cobalt chloride is completely dried, then placing in a tubular furnace maintaining flowing hydrogen, performing heat treatment at 500 ℃ for 2 hours for alloying, switching to nitrogen after the tubular furnace is reduced to room temperature, continuing to place for one hour, and taking out.
3) Weighing 100mg of the heat-treated sample, adding the sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed transition metal cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the mixture in a vacuum drying oven at 60 ℃ to dry for 12 hours to prepare the uniformly dispersed ultra-small Pt-Co/C alloy catalyst.
Example 2
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and after 2 hours of reflux by condensation at 200 ℃, the heating was stopped. And after cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and drying in an oven at 60 ℃ for 12 hours to obtain carbon-supported platinum black powder.
2) Firstly weighing 200mg of carbon-supported platinum for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 1:3, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, then adding weighed carbon-supported platinum, ultrasonically stirring until the cobalt chloride hexahydrate is uniformly dispersed, then carrying out immersion evaporation at 70 ℃, drying by distillation completely, then placing in a vacuum drying oven at 70 ℃ for 12 hours, then placing in a tubular furnace keeping flowing hydrogen, carrying out heat treatment at 500 ℃ for 2 hours for alloying, switching to nitrogen after the tubular furnace is reduced to room temperature, and continuing to place for one hour and then taking out.
3) Weighing 100mg of the heat-treated sample, adding the sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed metallic cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the beaker in a vacuum drying oven at 60 ℃ for drying for 12 hours to prepare the uniformly dispersed ultra-small Pt-Co/C alloy catalyst.
Example 3
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and after 2 hours of reflux by condensation at 200 ℃, the heating was stopped. And after cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and drying in an oven at 60 ℃ for 12 hours to obtain carbon-supported platinum black powder.
2) Firstly weighing 200mg of carbon-supported platinum for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 1:7, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, adding weighed carbon-supported platinum, performing ultrasonic stirring until the cobalt chloride is uniformly dispersed, performing immersion drying at 70 ℃, drying for 12 hours in a vacuum drying oven at 70 ℃ after the cobalt chloride is completely dried by distillation, then placing in a tubular furnace maintaining flowing hydrogen, performing heat treatment at 500 ℃ for 2 hours for alloying, switching to nitrogen after the tubular furnace is reduced to room temperature, and continuing to place for one hour and then taking out.
3) Weighing 100mg of the heat-treated sample, adding the sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed metallic cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the beaker in a vacuum drying oven at 60 ℃ for drying for 12 hours to prepare the uniformly dispersed ultra-small Pt-Co/C alloy catalyst.
Example 4
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon nanotubes and 13.5mL of an 8mg/mL ethylene chloroplatinate solution were mixed in a 500mL flask and subsequently placed in an oil bath and the heating was stopped after 2h of reflux by condensation at 200 ℃. And after cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and drying in an oven at 60 ℃ for 12 hours to obtain black powder of the carbon nano tube supported platinum.
2) Firstly weighing 200mg of carbon nano tube platinum-carrying for standby; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 1:3, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, then adding weighed platinum-carrying carbon nano tubes, carrying out ultrasonic stirring until the cobalt chloride is uniformly dispersed, then carrying out immersion evaporation to dryness at 70 ℃, after complete evaporation to dryness, placing the obtained product in a vacuum drying oven at 70 ℃ for drying for 12 hours, then placing the obtained product in a tubular furnace keeping flowing hydrogen, carrying out heat treatment at 500 ℃ for 2 hours for alloying, after the temperature of the tubular furnace is reduced to room temperature, switching to nitrogen, continuing to place for one hour, and then taking out the obtained product.
3) Weighing 100mg of the heat-treated sample, adding the sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed transition metal cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the mixture in a vacuum drying oven at 60 ℃ to dry for 12 hours to prepare the uniformly dispersed ultra-small Pt-Co/CNT alloy catalyst.
Example 5
1) Firstly weighing 200mg of commercial Pd/C catalyst (produced by Aldrich chemical Co., Ltd., Pd loading amount of 30 wt%) for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pd element to the Co element of 1:3, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, then adding a weighed Pd/C catalyst, carrying out ultrasonic stirring until the cobalt chloride hexahydrate is uniformly dispersed, then carrying out immersion drying at 70 ℃, after complete drying, placing the obtained product in a vacuum drying oven at 70 ℃ for drying for 12 hours, then placing the obtained product in a tubular furnace keeping flowing hydrogen, carrying out heat treatment at 500 ℃ for 2 hours for alloying, after the temperature of the tubular furnace is reduced to the room temperature, switching to nitrogen, continuing to place for one hour, and then taking out the obtained product.
2) Weighing 100mg of the heat-treated sample, adding the sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed transition metal cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the mixture in a vacuum drying oven at 60 ℃ to dry for 12 hours to prepare the uniformly dispersed ultra-small Pd-Co/C alloy catalyst.
Comparative example 1
0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene glycol chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and the heating was stopped after 2 hours of reflux by condensation at 200 ℃. And after cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and drying in an oven at 60 ℃ for 12 hours to obtain carbon-supported platinum black powder.
Comparative example 2
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene glycol chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and the heating was stopped after 2 hours of reflux by condensation at 200 ℃. After cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and placing in a 60 ℃ drying oven for drying for 12 hours to obtain carbon-supported platinum black powder.
2) Firstly weighing 200mg of carbon-supported platinum for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 2:1, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, adding weighed carbon-supported platinum, performing ultrasonic stirring until the cobalt chloride is uniformly dispersed, performing immersion drying at 70 ℃, drying for 12 hours in a vacuum drying oven at 70 ℃ after the cobalt chloride is completely dried, placing the dried cobalt chloride in a tubular furnace maintaining flowing hydrogen, performing heat treatment at 500 ℃ for 2 hours, switching to nitrogen after the tubular furnace is reduced to room temperature, continuing to stand for one hour, and taking out.
3) Weighing 100mg of the heat-treated sample, adding the heat-treated sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed transition metal cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the mixture in a vacuum drying oven at 60 ℃ to dry for 12 hours to prepare the Pt-Co/C alloy catalyst.
Comparative example 3
1) 0.4g of sodium hydroxide, 200mL of ethylene glycol, 200mg of carbon powder, and 13.5mL of an 8mg/mL ethylene glycol chloroplatinate solution were mixed in a 500mL flask, and then placed in an oil bath, and the heating was stopped after 2 hours of reflux by condensation at 200 ℃. And after cooling to room temperature, adjusting the pH value of the solution to acidity by using 1M hydrochloric acid, then performing suction filtration, washing for 3 times by using deionized water, and drying in an oven at 60 ℃ for 12 hours to obtain carbon-supported platinum black powder.
2) Firstly weighing 200mg of carbon-supported platinum for later use; weighing a proper amount of cobalt chloride hexahydrate according to the mass ratio of the Pt element to the Co element of 1:9, dispersing the cobalt chloride hexahydrate in 100mL of aqueous solution, then adding weighed carbon-supported platinum, carrying out ultrasonic stirring until the cobalt chloride hexahydrate is uniformly dispersed, then carrying out immersion evaporation at 70 ℃, drying the cobalt chloride hexahydrate till dryness completely, then placing the cobalt chloride hexahydrate in a vacuum drying oven at 70 ℃ for 12 hours, then placing the cobalt chloride in a tubular furnace keeping flowing hydrogen, carrying out heat treatment at 500 ℃ for 2 hours, switching to nitrogen after the tubular furnace is reduced to the room temperature, and continuously placing the cobalt chloride for one hour and then taking out the cobalt chloride.
3) Weighing 100mg of the heat-treated sample, adding the heat-treated sample into a beaker filled with 200mL of 1M hydrochloric acid, stirring for 2h at room temperature to remove part of incompletely alloyed transition metal cobalt, performing suction filtration and washing for 3 times by using deionized water, and then placing the mixture in a vacuum drying oven at 60 ℃ to dry for 12 hours to prepare the Pt-Co/C alloy catalyst.
FIG. 1 is an SEM photograph of catalyst samples obtained in examples 1 to 3 and comparative examples 1 to 3. The results in the figure show that the Pt particles on the carbon-supported platinum prepared in comparative example 1 were uniformly distributed on the carbon support, and the particle size thereof was 2.1nm on average. The Pt alloy particles on the catalysts prepared in examples 1-3 were uniformly distributed, and the average particle diameters of the particles were 3.8nm, 2.8nm, and 4.7nm, respectively. This is due to the transition metal entering into the lattice of Pt, causing a slight increase in particle size, but still maintaining a smaller size. The average size of the Pt alloy particles in the comparative example 2 is 7.6nm, because the amount of the metal precursor used is small (the mass ratio of the Pt element to the Co element is 2: 1), the confinement effect is small, the growth of the particles in the high-temperature process is not limited enough, the particle size of the prepared alloy particles is obviously increased, and the condition of uneven distribution occurs. The proportion of the deposited metal precursor in comparative example 3 is higher (the mass ratio of the Pt element to the Co element is 1: 9), the particle size of the alloy particles is larger due to uneven deposition, the particle size reaches 5.2nm, but the particle size is still obviously smaller than that of comparative example 2 with too little metal precursor. Therefore, the mass ratio of the Pt element to the metal element in the metal precursor is 1:1-1:7, and the phenomenon of particle growth caused by migration in the high-temperature heat treatment process can be effectively limited.
FIG. 2 is an SEM image of catalyst samples obtained in examples 4 and 5. The results in the figures show that when carbon nanotubes are used as the carrier, the confinement of the metal precursor and the defect sites on the carbon nanotubes can act together, so that the prepared alloy has smaller particle size (the alloy particle size is 2.5 nm) and more uniform distribution. And when the Pt particles are replaced by the Pd particles, the effective confinement effect can be realized, and the ultra-small Pd-Co alloy particles with uniform distribution and the size of 3.5nm are prepared.
Fig. 3 is an X-ray diffraction pattern of example 2 and comparative example 1. The results in the graph show that the Pt peak is significantly shifted after the addition of a second metal Co other than Pt, demonstrating that the particles formed are Pt — Co alloy particles.
FIG. 4 is a graph showing oxygen reduction performance of the catalyst samples obtained in examples 1 to 3 and comparative examples 1 to 3. The results in the figure show that the performances of the examples 1-3 and the comparative examples 2 and 3 are superior to that of the comparative example 1, and the catalyst sample formed by alloying is proved to have obviously improved catalytic performance compared with a single Pt catalyst. The performances of the examples 1-3 are superior to those of the comparative examples 2 and 3, and the results prove that when the mass ratio of the Pt element to the Co element is 1:1-1:7, the proper confinement effect can ensure a better particle distribution state and a smaller particle size, so that the oxygen reduction catalysis is facilitated. Among them, example 2 in which the mass ratio of the Pt element to the Co element was 1:3 showed the best catalytic activity.
Mixing a catalyst sample with a nafion solution in a volume ratio of 7:3, adding a proper amount of ethanol for dispersion to prepare catalyst slurry, and then respectively spraying the catalyst slurry on two sides of a proton membrane to prepare a catalyst membrane (the spraying amount is 0.25mg/cm according to the double-sided Pt loading capacity) -2 ) Cutting small catalyst films with the area of 5 multiplied by 5 cm to assemble a single cell, and testing a polarization curve and an energy density curve according to the American energy department testing standard. Fig. 5 is a result of performance test of a single cell prepared using the catalyst samples obtained in example 2 and comparative example 1. From the figureIt can be seen that the uniformly dispersed, smaller particle size Pt-Co/C catalyst has superior fuel cell performance over the carbon-supported platinum catalyst.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A method for preparing an alloy catalyst for a fuel cell in a limited domain mode is characterized in that carbon-supported noble metal is added into a metal precursor solution, the mixture is uniformly dispersed and then stirred and evaporated to dryness, so that a metal precursor covers the surfaces of noble metal particles and fills gaps among the noble metal particles, then high-temperature alloying is carried out in a reducing atmosphere, and the alloy catalyst suitable for the fuel cell is obtained after acid pickling and drying.
2. The method for preparing the alloy catalyst for the fuel cell in a limited domain mode according to claim 1, wherein the loading amount of the noble metal in the carbon-supported noble metal is 5-80%; the carbon carrier is any one of carbon powder, carbon nanotubes, nitrogen-doped carbon nanotubes, graphene oxide and graphene, and the noble metal is any one of Pt, Ir, Pd, Ru and Rh.
3. The method for preparing the alloy catalyst for the fuel cell in a limited domain manner according to claim 1, wherein the metal precursor solution is prepared by dissolving a metal precursor in water and/or a volatile organic solvent;
the metal precursor is a hydrochloride, a carbonate, a nitrate, a sulfate, an acetate, an oxalate, a phosphate, an amino complex, a carbonyl complex or an acetylacetone complex of at least one of metal elements scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium, magnesium and tin;
the concentration of the metal element contained in the metal precursor solution is 0.1mmol/L-3 mol/L.
4. The method for limited-range preparation of an alloy catalyst for fuel cells according to claim 1, wherein the amount of the metal precursor used is converted in such a manner that the mass ratio of the noble metal to the metal element in the metal precursor is from 1:1 to 1: 7.
5. The method for preparing the alloy catalyst for the fuel cell in a limited domain mode according to claim 1, wherein the reducing atmosphere is hydrogen or a mixed gas of hydrogen and an inert gas, and the volume content of the hydrogen is 1-100%.
6. The method for preparing the alloy catalyst for the fuel cell in the limited domain mode according to claim 1, wherein the high-temperature alloying is carried out for 0.5-6 hours at 300-1000 ℃.
7. The method for preparing the alloy catalyst for the fuel cell in a limited domain manner according to claim 1, wherein the size of alloy particles in the obtained alloy catalyst is 2-4 nm.
8. An alloy catalyst for fuel cells prepared by the method of any one of claims 1 to 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646508A (en) * | 2022-10-13 | 2023-01-31 | 厦门大学 | Supported Ni-Ru catalyst, preparation method and application |
| CN115966719A (en) * | 2023-03-16 | 2023-04-14 | 国家电投集团氢能科技发展有限公司 | Anode catalyst, preparation method thereof and proton exchange membrane fuel cell |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326262A1 (en) * | 2008-05-01 | 2009-12-31 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
| CN105126828A (en) * | 2015-08-31 | 2015-12-09 | 武汉理工大学 | Porous carbon load noble metal catalyst and preparation method thereof |
| CN106944044A (en) * | 2017-03-27 | 2017-07-14 | 中国科学院深圳先进技术研究院 | Palladium-based catalyst and preparation method and application |
| CN110931806A (en) * | 2019-11-19 | 2020-03-27 | 一汽解放汽车有限公司 | Carbon-supported noble metal alloy catalyst, and preparation method and application thereof |
| CN111146453A (en) * | 2019-12-27 | 2020-05-12 | 大连理工大学 | Carbon-supported noble metal-transition metal oxide composite electrocatalyst and preparation method and application thereof |
| CN112563523A (en) * | 2020-12-11 | 2021-03-26 | 航天氢能(上海)科技有限公司 | Multi-element platinum alloy catalyst with graphitized carbon layer confinement and preparation method thereof |
| WO2022012072A1 (en) * | 2021-03-01 | 2022-01-20 | 中国科学院广州能源研究所 | Preparation method for and use of self-assembly-based nitrogen-doped ordered porous precious metal nanomaterial |
-
2022
- 2022-05-18 CN CN202210538139.6A patent/CN115036522A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090326262A1 (en) * | 2008-05-01 | 2009-12-31 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
| CN105126828A (en) * | 2015-08-31 | 2015-12-09 | 武汉理工大学 | Porous carbon load noble metal catalyst and preparation method thereof |
| CN106944044A (en) * | 2017-03-27 | 2017-07-14 | 中国科学院深圳先进技术研究院 | Palladium-based catalyst and preparation method and application |
| CN110931806A (en) * | 2019-11-19 | 2020-03-27 | 一汽解放汽车有限公司 | Carbon-supported noble metal alloy catalyst, and preparation method and application thereof |
| CN111146453A (en) * | 2019-12-27 | 2020-05-12 | 大连理工大学 | Carbon-supported noble metal-transition metal oxide composite electrocatalyst and preparation method and application thereof |
| CN112563523A (en) * | 2020-12-11 | 2021-03-26 | 航天氢能(上海)科技有限公司 | Multi-element platinum alloy catalyst with graphitized carbon layer confinement and preparation method thereof |
| WO2022012072A1 (en) * | 2021-03-01 | 2022-01-20 | 中国科学院广州能源研究所 | Preparation method for and use of self-assembly-based nitrogen-doped ordered porous precious metal nanomaterial |
Non-Patent Citations (2)
| Title |
|---|
| WEI WU ET AL: "《Encapsulating Pt Nanoparticles inside a Derived Two-Dimensional Metal−Organic Frameworks for the Enhancement of Catalytic Activity》", 《ACS APPLED MATERIALS INTERFACES》, pages 10359 - 10368 * |
| 胡冶州等: "《限域型贵金属氧还原反应电催化剂研究进展》", 《储能科学与技术》, vol. 11, no. 4, pages 1264 - 1277 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646508A (en) * | 2022-10-13 | 2023-01-31 | 厦门大学 | Supported Ni-Ru catalyst, preparation method and application |
| CN115966719A (en) * | 2023-03-16 | 2023-04-14 | 国家电投集团氢能科技发展有限公司 | Anode catalyst, preparation method thereof and proton exchange membrane fuel cell |
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