CN103721707A - Preparation of hollow pt and pt-alloy catalysts - Google Patents
Preparation of hollow pt and pt-alloy catalysts Download PDFInfo
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- CN103721707A CN103721707A CN201310582377.8A CN201310582377A CN103721707A CN 103721707 A CN103721707 A CN 103721707A CN 201310582377 A CN201310582377 A CN 201310582377A CN 103721707 A CN103721707 A CN 103721707A
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- core metal
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- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 238000005275 alloying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 25
- 230000006872 improvement Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- -1 methyl Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002837 PtCo Inorganic materials 0.000 description 3
- 229910002065 alloy metal Inorganic materials 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000003797 solvolysis reaction Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002844 PtNi Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
A method for preparing hollow platinum or platinum-alloy catalysts includes a step of forming a plurality of low-melting-point metal nanoparticles. A platinum or platinum-alloy coating is then deposited onto the low-melting-point metal nanoparticles to form platinum or platinum-alloy coated particles. The low-melting-point metal nanoparticles are then removed to form a plurality of hollow platinum or platinum-alloy particles.
Description
The cross reference of related application
The application requires the rights and interests of the U.S. Provisional Application that the sequence number of submission on October 15th, 2012 is 61/713,778, and its disclosed content is all introduced the application by reference at this.
Technical field
The present invention relates to the catalyst for fuel cells applications.
Background of invention
In the fuel cell of proton exchange film type, hydrogen is supplied to anode as fuel, and oxygen is supplied to negative electrode as oxidant.Oxygen can be pure oxygen (O
2) or air (O
2and N
2mixture).PEM (" PEM ") fuel cell has membrane electrode assembly (" MEA ") conventionally, and wherein solid polymer membrane has anode catalyst in one side, has cathod catalyst on opposing face.The anode of typical PEM fuel cell and cathode layer are by porous conductive material, as woven graphite, graphitization sheet material or carbon paper form so that fuel can be dispersed on the film surface of fuel supplying electrode.Typically, ionic-conductive polymer film comprises perfluorinated sulfonic acid (PFSA) ionomer.
Each catalyst layer has the catalyst granules in small, broken bits (for example platinum grain) that loads on carbon granule to promote hydrogen reduction at negative electrode place at the oxidation at anode place and oxygen.Proton flows to negative electrode from anode through ionic conductive polymer membrane, and at this, they are combined with oxygen and form water, and water is discharged from battery.
MEA is clipped between a pair of porous gas diffusion layer (" GDL "), and this is clipped in again between pair of conductive flow field element or plate GDL.This plate serves as the colelctor electrode of anode and negative electrode, and contain therein form for the gaseous reactant of this fuel cell being distributed in to anode and the lip-deep suitable passage of cathod catalyst and opening separately.For effective generating, the polymer dielectric film of PEM fuel cell must be thin, chemically stable, can transmit proton, non-conductive and airtight.In typical use, fuel cell provides a large amount of electric power with many individual fuel cell groups in heaps.
In many fuel cells applications, electrode (catalyst) layer is formed by ink composite, and described ink composite comprises noble metal and perfluorinated sulfonic acid polymer (PFSA).For example, in the electrode layer of Proton Exchange Membrane Fuel Cells is manufactured, generally PFSA is joined in Pt/C catalyst ink, the bonding of proton conduction and porous carbon network is provided with the Pt nanoparticle catalyst to disperseing.Traditional fuel-cell catalyst by carbon black platinum deposit and the ionomer on described carbon surface be combined.Carbon black provides (part) high surface conductive substrates.Described platinum deposit provides catalytic performance, and ionomer provides proton conductive component.This electrode is by comprising carbon black catalyst and ionomeric ink forms, and its drying is in conjunction with to form electrode layer.
Although it is fairly good to manufacture the prior art of the electrode ink that is used for fuel cells applications, but still there is the problem that needs solution.For example, the catalyst layer that formed by such ink is mechanical equivalent of light fragility often, and has the redox ability of suboptimal.
Therefore, the invention provides the improved preparation method of catalyst useful in fuel cells applications.
Brief summary of the invention
The method that hollow platinum and hollow platinum-alloy catalyst are provided by providing at least one embodiment in the present invention has solved one or more problem of the prior art.The method comprises the step that forms a plurality of low melting point core metal nanoparticles.Then platinum or platinum-alloy coat are deposited on low-melting-point metal nano particle, to form platinum or the platinum-alloy shell that applies described core metal nanoparticle.Then remove low-melting-point metal nano particle, to have formed a plurality of hollow platinum or platinum-alloying pellet.When platinum or platinum-alloy deposition are annealed to (annealing) when improving its catalytic activity during low melting point core metal nanoparticle or to described shell on described core metal nanoparticle time or described in melting, use ionic liquid at room temperature as medium.Advantageously, due to its high oxygen reducing ability, the hollow platinum catalyst being formed by the method for present embodiment is expected to become the candidate of fuel-cell catalyst of future generation.In addition, the platinum catalyst of hollow does not comprise base metal (base-metal), has avoided thus dissolving relevant endurance issues to base metal.
The present invention also comprises following aspect:
1. the method for preparing hollow platinum or platinum-alloy catalyst, described method comprises:
In oxygen-free nonaqueous solvents, form a plurality of low melting point core metal nanoparticles;
By platinum or platinum-alloy deposition to described low-melting-point metal nano particle, to form platinum or the platinum-alloy shell that applies described core metal nanoparticle; And
From the particle of described platinum or platinum-alloy-coated, remove described low-melting-point metal nano particle, to form a plurality of hollow platinum or platinum-alloying pellet, wherein when on described core metal nanoparticle time or described in melting during low melting point core metal nanoparticle or when described shell is annealed to improve its catalytic activity, using ionic liquid at room temperature as medium platinum or platinum-alloy deposition.
2. according to the method described in aspect 1, wherein said core metal nanoparticle comprises fusing point lower than the metal of approximately 400 ℃.
3. according to the method described in aspect 1, wherein said core metal nanoparticle comprises the low-melting-point metal that is selected from In, Ga, Ge, Sn, Sb, Tl, Pb, Bi, Zn, Cd, Hg and combination thereof.
4. according to the method described in aspect 1, wherein said core metal nanoparticle by forming metal sputtering in described nonaqueous solvents.
5. according to the method described in aspect 1, wherein said non-aqueous solution comprises ionic liquid at room temperature (RTIL).
6. according to the method described in aspect 1, wherein said core metal nanoparticle has the average diameter up to 500 nanometers.
7. according to the method described in aspect 1, wherein said core metal nanoparticle has from approximately 0.5 average diameter to approximately 500 nanometers.
8. according to the method described in aspect 1, wherein said core metal nanoparticle has from approximately 1 average diameter to approximately 100 nanometers.
9. according to the method described in aspect 1, wherein said nonaqueous solvents is the ionic liquid at room temperature with cation and anion.
10. according to the method described in aspect 9, wherein said cation is selected from
R wherein
1, R
2and R
3c independently of one another
1-20alkyl or C
2-20alkyl ether.
11. according to the method described in aspect 10, wherein R
1, R
2and R
3methyl, ethyl independently of one another, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-hexyl, n-octyl, positive decyl, n-C
16h
33, CH
3oCH
2-and CH
3oC
2h
4-.
12. according to the method described in aspect 9, and wherein said anion is selected from BF
4]
-, [B (CN)
4]
-, [CF
3bF
3]
-, [C
2f
5bF
3]
-, [n-C
3f
7bF
3]
-, [n-C
4f
9bF
3]
-, [(C
2f
5)
3pF
3]
-, [CF
3cO
2]
-, [CF
3sO
3]
-, [N (COCF
3) (SO
2cF
3)]-, [N (SO
2f)
2]
-, [EtOSO
3]-, [N (CN)
2]-, [C (CN)
3]-, [SCN]-, [SeCN]-, [CuCl
2]-, [AlCl
4]
-, [ZnCl
4]
2-, or[F (HF)
23]-.
13. according to the method described in aspect 9, the effect of wherein said ionic liquid at room temperature be prevent coalescent.
14. according to the method described in aspect 1, and wherein said hollow platinum or platinum-alloying pellet and solvent, ionomer and optional filler are combined to form ink.
15. according to the method described in aspect 14, wherein described ink composite is applied to the surface in fuel cell module, and then dry.
16. according to the method described in aspect 14, and wherein said fuel cell module is ionic conduction layer or gas diffusion layers.
17. according to the method described in aspect 1, wherein by described nano particle is contacted with platinum or platinum-alloy precursor by platinum or platinum-alloy deposition to described low-melting-point metal nano particle.
18. according to the method described in aspect 17, and wherein said platinum-alloy precursor is selected from K
2ptCl
6, K
2ptCl
4, H
2ptBr
4, Pt (NO
3)
2, acetylacetone,2,4-pentanedione Pt and combination thereof.
19. according to the method described in aspect 18, wherein with chemical reducing agent or by solvolysis, described platinum-alloy precursor is reduced into metal.
20. according to the method described in aspect 1, wherein by replace the metal in described low melting point core metal nanoparticle with platinum Galvanic, by platinum or platinum-alloy deposition to described low-melting-point metal nano particle.
21. according to the method described in aspect 1, and wherein said hollow platinum or platinum-alloying pellet have approximately 7 atomic layers to the average thickness of about 1.5nm.
Accompanying drawing explanation
From detailed explanation and relevant drawings, can understand more fully illustrative embodiments of the present invention, wherein:
Fig. 1 provides the schematic diagram of introducing the fuel cell of hollow platinum catalyst at least one electrode; With
Fig. 2 is the indicative flowchart that shows prepared by hollow platinum and/or platinum-alloying pellet.
Detailed Description Of The Invention
To at length touch upon now at present preferred composition of the present invention, embodiment and method, it forms at present for known for inventor puts into practice best mode of the present invention.Accompanying drawing is not must be pro rata.However, it should be understood that disclosed embodiment is only example of the present invention, the present invention can be contained different and optional form.Therefore, details disclosed herein should not be construed as restrictive, but only as the representative basis of either side of the present invention, and/or diversely use representative basis of the present invention as instruction those skilled in the art.
Except in an embodiment or other side is clear indicate, all numerical quantities in this description of indication material quantity or reaction and/or service condition are interpreted as being modified by wording " approximately ", describe wide region of the present invention.Practice in described number range is normally preferred.In addition, unless clearly demonstrated on the contrary: percentage, " umber " and rate value are by weight; As the explanation about the suitable of the given object of the present invention or preferred combination of materials or kind represent part suitable or preferably combination or kind comparably any two or more; The molecular weight form registration average molecular weight providing for any polymer; The component when explanation of component represents to add in any combination illustrating in description in the technical terms of chemistry, once and not certain chemical interaction of getting rid of between each component of mixing rear mixture; The first definition of acronym or other abbreviation is applied to the use of all follow-up identical abbreviations, and changes in addition necessary change for the universal grammar of the abbreviation of original definition; Unless with clearly demonstrate on the contrary, by for identical performance previously or the constructed measurement performance of touching upon subsequently.
Specific components and/or condition it is to be further understood that the present invention is not limited to the specific embodiment of the following stated and method, because certainly can change.In addition, term is only for describing particular of the present invention as used herein, but not is used for being limited by any way.
Be also pointed out that singulative " ", " a kind of " and " being somebody's turn to do " comprise plural object, unless clearly indicated in addition in context as used in description and claims.For example, the parts of singulative intention comprises a plurality of parts.
Run through the application, when quoting publication, at this, disclosure of these publications is all introduced to the application as a reference, to describe more fully the prior art under the present invention.With reference to figure 1, provide the cross sectional representation of introducing the fuel cell of catalyst or film.PEM (PEM) fuel cell 10 comprises the polymerization plasma conductive membranes 12 being arranged between cathode catalyst layer 14 and anode catalyst layer 16.Fuel cell 10 also comprises flow- field plate 18,20, gas passage 22 and 24, and gas diffusion layers 26 and 28.Advantageously, cathode catalyst layer 14 and/or anode catalyst layer 16 comprise hollow platinum or the platinum-alloying pellet being formed by following method.In the operating process of fuel cell, fuel is supplied to the flow-field plate 20 of anode-side as hydrogen, and oxidant is as the flow-field plate 18 of oxygen supply to cathode side.The hydrogen ion being produced by anode catalyst layer 16 is by 12 migrations of polymerization plasma conductive membranes, and wherein they react to form water at cathode catalyst layer 14 places.This electrochemical process is by being connected (load connects) generation current with 20 load to flow-field plate 18.
In one embodiment, provide the method for preparing hollow platinum and hollow platinum-alloy catalyst.With reference to Fig. 2, the method comprises as formed the step of a plurality of low-melting-point metals (LMPM) nanoparticle core 30 by low-melting-point metal in step described in a).Usually, the fusing point of low-melting-point metal that is used to form LMPM particle is lower than approximately 400 ℃.In an improvement, be used to form the fusing point of low-melting-point metal of LMPM particle lower than approximately 300 ℃.In another improves, be used to form the fusing point of low-melting-point metal of LMPM particle lower than approximately 200 ℃.In another improvement, the fusing point that is used to form the low-melting-point metal of LMPM particle is greater than approximately 100 ℃.Low melting glass is not in the situation that used acid or other oxidant of the integrality that can lose Pt shell to remove core.The example that forms the suitable metal of LMPM particle includes, but not limited to In, Ga, Ge, Sn, Sb, Tl, Pb, Bi, Zn, Cd, Hg etc.In an improvement, LMPM particle is by being used ionic liquid at room temperature (RTIL) and low-melting-point metal to form.Especially, by LMPM particle deposition in ionic liquid.Usually, RTIL is oxygen-free.Article " Room-Temperature Ionic Liquid.A New Medium for Material Production and Analyses under Vacuum Conditions by S.Kuwabataet al.; J.Phys.Chem.Lett.2010; 1; 3177-3188 " has been described metallic particles has been deposited to the method in RTIL, and whole disclosures of this article are incorporated herein.As described in S.Kuwabata etc., metal nanoparticle can form by sputter, plasma-deposited or electron beam and gamma-radiation irradiation.In sputtering method, under reduced pressure use Ar
+and N2
+ions Bombardment low-melting-point metal target, and deposited in RTIL.Plasma-deposited metal ion is guided into RTIL and required RTIL to have low-vapor pressure.The solution that electron beam and gamma-radiation irradiation technique irradiation contain slaine, thus induction is reduced to metallic particles.
Low-melting-point metal nano particle is characterised in that their bulk.In an improvement, low-melting-point metal nano particle has the average diameter up to 500 nanometers.In another improves, low-melting-point metal nano particle has approximately 0.5 average diameter to approximately 500 nanometers.In another improvement, low-melting-point metal nano particle has from approximately 1 average diameter to approximately 100 nanometers.
Step b), in, platinum or platinum-alloy coat 32 are deposited on low-melting-point metal nano particle, to form the particle of platinum or platinum-alloy-coated.In an improvement, by nano particle is contacted with platinum precursor or platinum-alloy precursor by platinum or platinum-alloy deposition to low-melting-point metal nano particle.The example of applicable platinum precursor includes, but not limited to K
2ptCl
6, K
2ptCl
4, H
2ptBr
4, Pt (NO
3)
2, acetylacetone,2,4-pentanedione Pt and combination thereof.Usually, with chemical reducing agent or by solvolysis, the precursor of platinum or platinum-alloy is reduced into metal.This reduction is by selecting suitable reducing agent and reaction temperature to realize.In this respect, the wide operating temperature window of RTIL is favourable aspect optimizing process.For example, after platinum and/or platinum-alloy-metal precursor add in the RTIL solution of LMPM-nano particle, use the metal on hydrogen, CO gas, boron hydride or other reducing agent reduction nucleus.
In another kind of modification, by replace the metal in described low melting point core metal nanoparticle with platinum Galvanic, by platinum or platinum-alloy deposition to described low-melting-point metal nano particle.Galvanic displacement has utilized the difference of the reduction potential of various metals.Especially, can use the metal of more easily oxidation as copper reduction platinum precursor.Consequently, the reduction of platinum is that to take copper dissolution (oxidation) be cost, and this is a cell reaction in itself.For example, due to most metals, comprise that Pt, Co and Ni (noticing that PtCo and PtNi are considered to one of the most promising platinum-alloy catalyst) compare, In has more negative reduction potential, therefore can use In by these metallic reducings to low melting point core metal nanoparticle.This is to realize by under agitation platinum and alloy-metal precursor being joined in the RTIL solution of degassed LMPM-nano particle.Counter ion counterionsl gegenions by RTIL are by the In of any dissolving
2+solvation stabilisation.
In another modification, use the chemical property of the stablize/solvated electron of RTIL uniqueness that the precursor induction of platinum or platinum-alloy is reverted on low melting point nuclear particle, described electronics is to be applied by electron beam or other RADIATION DECOMPOSITION that produces the electronics of solvation.Use this character, can direct-reduction platinum and alloy-metal precursor, and without using the reducing agent adding.
Step c), in, remove low-melting-point metal nano particle to form platinum or the platinum-alloying pellet 34 of a plurality of hollows.Usually, by the solution containing particle is heated to slightly higher than the temperature of RTIL center melting point metal LMPM core is removed.In an improvement, core metal can be overflowed by the aperture (pin hole) in platinum or platinum-alloy coat.Finally, the hollow particle can heat treatment in inert atmosphere (for example, approximately 400 ℃) obtaining, to improve the oxygen reducing ability of catalyst by reducing the amount of low ligancy surface atom (i.e. atom in edge and kink (kink)).In an improvement, hollow platinum or platinum-alloying pellet have average approximately 7 atomic layers to the thickness of about 1.5nm.
Discovery is the heat treatment at approximately 400 ℃ in inert atmosphere, by reducing the amount of low ligancy surface atom (atom in edge and kink), has improved the oxygen reducing ability of catalyst.
The use of RTIL provides wide operating temperature range, can deposit at low temperatures like this Pt shell (more uniform Pt shell generally can be provided) and molten substrate metal at higher temperature.In the article of S.Kuwabata, provided the example of suitable RTIL.Especially, this liquid is to be formed by the ionic compound with cation and anion.The example of suitable cationic components comprises:
R wherein
1, R
2and R
3c independently of one another
1-20alkyl, C
2-20alkyl ether etc.Especially, R
1, R
2and R
3methyl, ethyl independently of one another, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-hexyl, n-octyl, positive decyl, n-C
16h
33, CH
3oCH
2-, CH
3oC
2h
4-etc.The example of suitable anionic group comprises [BF
4]
-, [B (CN)
4]
-, [CF
3bF
3]
-, [C
2f
5bF
3]
-, [n-C
3f
7bF
3]
-, [n-C
4f
9bF
3]
-, [(C
2f
5)
3pF
3]
-, [CF
3cO
2]
-, [CF
3sO
3]-, [N (COCF
3) (SO
2cF
3)]-, [N (SO
2f)
2]
-, [EtOSO
3]-, [N (CN)
2]-, [C (CN)
3]-, [SCN]-, [SeCN]-, [CuCl
2]-, [A1Cl
4]
-, [ZnCl
4]
2-, [F (HF) 2
3]-etc.In an improvement, RTIL is coalescent to prevent as the stabilizing agent of nano particle.Notice having shown that RTIL can be easily separated from product, to form active conventional Pt/C.
In another improves, hollow platinum or platinum-alloying pellet can be loaded on carbon black pellet, to improve its dispersiveness.Then for example, by the beaded catalyst of load and solvent and optional ionomer (, NAFION
tM-perfluorinated sulfonic acid polymer) combination.This ink composite is applied to the surface (for example, ionic conduction layer or gas diffusion layers) in fuel cell module, then dry.In this latter's improvement, applicable solvent comprises alcohols (for example, methyl alcohol, ethanol, propyl alcohol etc.) and water.The combination of finding alcohol and water is useful especially.Hollow platinum or platinum-alloying pellet that typical negative electrode ink formulations comprises 1 to 6 % by weight, the water of 8 to 16 % by weight, the ethanol of 60% to 80 % by weight, the ionomer of 4 to 15 % by weight.In an improvement, ink composite and filler close as zirconium oxide bead burl.The experience of the fuel cell of the catalyst based on employing prior art, platinum disperses should be at least～30m
2/ g
pt.
the preparation of LMPM nano particle
The preparation of LMPM nano particle is by with about 20mA/cm
2speed indium (In) is splashed to and is completed on RTIL, described RTIL at room temperature under argon gas atmosphere (approximately 2 Pascal) be dispersed on glass surface.RTIL has tetrafluoro boric acid (BF
4) imidazoles-class ionic liquid of anion.Find, granular size depends primarily on the viscosity of RTIL.This method provides and has had good uniformity the nano particle of (diameter is generally 6 to 10nm), and without any stabilizing agent.In addition, also find that these nano particles have formed colloidal solution, that is, they keep being suspended in solution for a long time.
platinum and platinum-alloy deposition are to LMPM core
By by K
2ptCl
6or K
2ptCl
6+ Co (NO
3)
26H
2o joins has tetrafluoro boric acid (BF
4) realize the deposition of Pt or PtCo layer in imidazoles-class ionic liquid of anion.Then in Ar gas, at 80 ℃, with 5% hydrogen, purge and within 1 hour, reduce resulting solution, so that Pt or PtCo are deposited on LMPM particle.
the removal of LMPM core
By prepared solution being heated to slightly higher than the temperature of indium core melting point metal (157 ℃), remove LMPM core.Discovery the heat treatment of approximately 400 ℃, by reducing the amount of low ligancy surface atom, can improve the oxygen reducing ability of catalyst in inert atmosphere.Note, when using galvanic to replace to deposit Pt or Pt-alloy-layer, In core oxidation dissolution, so LMPM core removal step does not need.
Although have illustrated and described embodiments of the invention, yet these embodiment not illustrate and have described all possible forms of the invention.On the contrary, the word using is in this manual to describe rather than restriction, is to be understood that without departing from the spirit and scope of the present invention, can make various changes.
Claims (10)
1. the method for preparing hollow platinum or platinum-alloy catalyst, described method comprises:
In oxygen-free nonaqueous solvents, form a plurality of low melting point core metal nanoparticles;
By platinum or platinum-alloy deposition to described low-melting-point metal nano particle, to form platinum or the platinum-alloy shell that applies described core metal nanoparticle; And
From the particle of described platinum or platinum-alloy-coated, remove described low-melting-point metal nano particle, to form a plurality of hollow platinum or platinum-alloying pellet, wherein when on described core metal nanoparticle time or described in melting during low melting point core metal nanoparticle or when described shell is annealed to improve its catalytic activity, using ionic liquid at room temperature as medium platinum or platinum-alloy deposition.
2. method according to claim 1, wherein said core metal nanoparticle comprises fusing point lower than the metal of approximately 400 ℃.
3. method according to claim 1, wherein said core metal nanoparticle comprises the low-melting-point metal that is selected from In, Ga, Ge, Sn, Sb, Tl, Pb, Bi, Zn, Cd, Hg and combination thereof.
4. method according to claim 1, wherein said core metal nanoparticle by forming metal sputtering in described nonaqueous solvents.
5. method according to claim 1, wherein said non-aqueous solution comprises ionic liquid at room temperature (RTIL).
6. method according to claim 1, wherein said nonaqueous solvents is the ionic liquid at room temperature with cation and anion.
7. method according to claim 6, wherein said cation is selected from
R wherein
1, R
2and R
3c independently of one another
1-20alkyl or C
2-20alkyl ether.
8. method according to claim 6, wherein said anion is selected from [BF
4]
-, [B (CN)
4]
-, [CF
3bF
3]
-, [C
2f
5bF
3]
-, [n-C
3f
7bF
3]
-, [n-C
4f
9bF
3]
-, [(C
2f
5)
3pF
3]
-, [CF
3cO
2]
-, [CF
3sO
3]
-, [N (COCF
3) (SO
2cF
3)]-, [N (SO
2f)
2]
-, [EtOSO
3]-, [N (CN)
2]-, [C (CN)
3]-, [SCN]-, [SeCN]-, [CuCl
2]-, [AlCl
4]
-, [ZnCl
4]
2-, or[F (HF)
23]-.
9. method according to claim 1, wherein by described nano particle is contacted with platinum or platinum-alloy precursor by platinum or platinum-alloy deposition to described low-melting-point metal nano particle.
10. method according to claim 17, wherein said platinum-alloy precursor is selected from K
2ptCl
6, K
2ptCl
4, H
2ptBr
4, Pt (NO
3) 2, acetylacetone,2,4-pentanedione Pt and combination thereof.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261713778P | 2012-10-15 | 2012-10-15 | |
| US61/713778 | 2012-10-15 | ||
| US61/713,778 | 2012-10-15 | ||
| US14/044,165 US9425462B2 (en) | 2012-10-15 | 2013-10-02 | Preparation of hollow Pt and Pt-alloy catalysts |
| US14/044,165 | 2013-10-02 | ||
| US14/044165 | 2013-10-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103721707A true CN103721707A (en) | 2014-04-16 |
| CN103721707B CN103721707B (en) | 2016-11-30 |
Family
ID=
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| CN108410001A (en) * | 2018-03-22 | 2018-08-17 | 河南科技学院 | Application of the low-melting point metal alloy in preparing organic polymer sponge and foam |
| CN108774336A (en) * | 2018-03-22 | 2018-11-09 | 河南科技学院 | Application of the liquid metal microballoon as pore-foaming agent in preparing solid-phase extraction column |
| CN112473691A (en) * | 2020-11-28 | 2021-03-12 | 海南大学 | Preparation method of low-platinum hollow polyhedral nano-structured catalyst |
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Cited By (5)
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| CN108410001A (en) * | 2018-03-22 | 2018-08-17 | 河南科技学院 | Application of the low-melting point metal alloy in preparing organic polymer sponge and foam |
| CN108774336A (en) * | 2018-03-22 | 2018-11-09 | 河南科技学院 | Application of the liquid metal microballoon as pore-foaming agent in preparing solid-phase extraction column |
| CN108410001B (en) * | 2018-03-22 | 2020-10-30 | 河南科技学院 | Application of low-melting-point metal alloy in preparation of organic polymer sponge and foam |
| CN108774336B (en) * | 2018-03-22 | 2021-01-08 | 河南科技学院 | Application of liquid metal microspheres as pore-forming agent in preparation of solid-phase extraction column |
| CN112473691A (en) * | 2020-11-28 | 2021-03-12 | 海南大学 | Preparation method of low-platinum hollow polyhedral nano-structured catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102013220270A1 (en) | 2014-04-17 |
| DE102013220270B4 (en) | 2016-10-06 |
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