CN1805192A - Preparation method of electro-catalyst for fuel cells - Google Patents
Preparation method of electro-catalyst for fuel cells Download PDFInfo
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- CN1805192A CN1805192A CNA2005100005805A CN200510000580A CN1805192A CN 1805192 A CN1805192 A CN 1805192A CN A2005100005805 A CNA2005100005805 A CN A2005100005805A CN 200510000580 A CN200510000580 A CN 200510000580A CN 1805192 A CN1805192 A CN 1805192A
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- catalyst
- platinum
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- organic solvent
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- 238000002360 preparation method Methods 0.000 title claims description 36
- 239000000446 fuel Substances 0.000 title abstract description 12
- 239000010411 electrocatalyst Substances 0.000 title description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 6
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 18
- 229940045985 antineoplastic platinum compound Drugs 0.000 claims description 15
- 150000003058 platinum compounds Chemical class 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000001291 vacuum drying Methods 0.000 abstract description 6
- 239000011806 microball Substances 0.000 abstract 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 239000004971 Cross linker Substances 0.000 abstract 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000013019 agitation Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 chloroplatinate Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- 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 relates to a method for preparing catalyst, which comprises: adding platinum into the catalyst carrier which is a micro ball. The producing method comprises: (1) reacting the monomer, cross linker, initiator and the hole maker in the protection of inert gas and one emulsion to be eccentrically deposited and vacuum dried to attain one solid polymer micro ball; (2) in the protection of inert gas and the hydrogen dioxide or ammonium peroxodisulfate, reacting the mixture of polymer micro ball and the carbowax or polyacrylic acid with the pyrrole to be filtered and using the distilled water to wash the solid product to remove color, and vacuum drying to attain the catalyst carrier micro ball. The inventive catalyst has high catalytic activity, high specific power, and the fuel battery with said invention has better discharge property.
Description
Technical field
The present invention relates to a kind of preparation method of fuel-cell catalyst, more particularly, is the preparation method who is used for the eelctro-catalyst of fuel cell about a kind of.
Background technology
Fuel cell is a kind of device that chemical energy is directly changed into electric energy.It has advantages such as energy conversion efficiency height, work noiselessness, non-environmental-pollution.In recent years, especially with the fastest developing speed with Proton Exchange Membrane Fuel Cells, because it has advantages such as volume is little, working temperature is low, be easy to carry, be fit to be applied to the portable power source field, have development prospect widely, obtained the generally attention of countries in the world.But Proton Exchange Membrane Fuel Cells still faces problems, and especially the performance of eelctro-catalyst does not still reach desirable requirement.
At present, the eelctro-catalyst that fuel cell adopts all is carrier with carbon, a kind of used in proton exchange membrane fuel cell platinum/carbon electrode Preparation of catalysts method is disclosed as Chinese invention patent CN1267922A, this method comprises: (1) carries out activation processing to carbon carrier: carbon carrier is placed tube furnace, feed carbon dioxide, heating, heating-up temperature is 400-600 ℃, be 2-6 hour heating time; (2) preparation Na
6Pt (SO
3)
4Intermediate: chloroplatinate is suspended in the deionized water, adds NaHSO
3Saturated solution reacts, and solution colour is thin out gradually until water white transparency by Huang, and making pH value is 2-4, adds Na then
2CO
3, until precipitation occurring, accent PH is 6-8, standing over night, after filtration, washing, 90-120 ℃ dry Na
6Pt (SO
3)
4Intermediate; (3) with the Na of above-mentioned preparation
6Pt (SO
3)
4Intermediate adds in the deionized water, drips sulfuric acid and makes it dissolving, and transferring pH value with NaOH is 3, adds the carbon carrier that the first step obtains, its addition and Na
6Pt (SO
3)
4The weight ratio of intermediate is 1: 0.2-2 then, drips H
2O
2Carry out precipitation reaction, ebuillition of heated 1 hour, cooling, more after filtration, washing, 90-120 ℃ oven dry promptly obtain the platinum/carbon electrode catalyst of this method preparation.This method adopts carbon black as carrier, and carbon black support is easy to reunite, and makes to be carried in platinum on the carbon black by the carbon black embedding, can not effectively participate in catalytic reaction, makes catalytic activity lower.In addition, because the profile irregularity of carbon black, when being used in the preparation pole catalyze layer, form closely knit Catalytic Layer easily, cause the porosity of Catalytic Layer to descend, specific area reduces, make the gaseous diffusion difficulty, this also is as the lower reason of the catalyst activity of carrier with carbon black.Eelctro-catalyst catalytic activity with this method preparation is lower, shows that the power of battery of this catalyst of use is less.
Summary of the invention
To the objective of the invention is the not high defective of fuel cell electro-catalyst catalytic activity of utilizing prior preparation method preparation in order overcoming, a kind of preparation method with fuel cell electro-catalyst of higher catalytic activity to be provided.
Preparation of catalysts method provided by the invention comprises to be introduced platinum in a kind of catalyst carrier, wherein, described catalyst carrier is a kind of microballoon, its preparation method comprises that (1) is under inert gas shielding and in a kind of emulsion, with monomer, crosslinking agent, initator and perforating agent reaction, centrifugation, vacuumize obtains a kind of solid polymer microballoon; Described emulsion is to contain the organic solvent of 0.1-5 weight % emulsifying agent and the mixed liquor of water, and the weight ratio of organic solvent and water is 0.2-5; Crosslinking agent: monomer: initator: perforating agent: the weight ratio that contains the mixed liquor of the organic solvent of 0.1-5 weight % emulsifying agent and water is 1: 2.5-400: 0.02-40: 0.01-100: 40-3000; Described monomer is selected from styrene, methyl methacrylate or butyl methacrylate; Described crosslinking agent is selected from divinylbenzene or phthalic acid double methacrylate; Described initator is selected from one or more in benzoyl peroxide, azodiisobutyronitrile or the potassium peroxydisulfate; Described perforating agent is selected from one or more in toluene, dibutyl phthalate and the dioctyl phthalate; Described emulsifying agent is selected from neopelex and/or lauryl sodium sulfate; Described organic solvent is selected from one or more in absolute ethyl alcohol, butanols and the ethylene glycol; Reaction temperature is 30-120 ℃, and the reaction time is 1-50 hour; (2) under inert gas shielding, in the presence of hydrogen peroxide or ammonium persulfate, the pH value that step (1) is made is mixture and pyrroles's reaction of polymer microballoon and the polyethylene glycol or the polyacrylic aqueous solution of 1-5, filter, extremely colourless with distilled water washing solid product, and vacuumize, obtain the catalyst carrier microballoon; Pyrroles: porous polymer microsphere: polyethylene glycol or polyacrylic acid: hydrogen peroxide or ammonium persulfate: the weight ratio of water is 1: 0.1-7.5: 0.005-0.75: 0.15-45: 15-500; Reaction temperature is 0-50 ℃, and the reaction time is 5-50 hour.
The catalyst carrier microballoon that adopts method provided by the invention to prepare is a kind of porous polymer of neat appearance, agglomeration can not take place, and when the preparation pole catalyze layer, also can not form closely knit Catalytic Layer, and voidage is descended.Therefore, adopt the catalyst of method preparation provided by the invention to have advantages of high catalytic activity, the battery specific power is improved, and adopt the fuel cell of the catalyst of method preparation provided by the invention to have good discharge performance.
Description of drawings
Fig. 1 is the voltage-to-current curve chart of battery
Embodiment
According to method provided by the invention, described emulsion is preferably the organic solvent that contains 0.15-3 weight % emulsifying agent and the mixed liquor of water, and the weight ratio of organic solvent and water is preferably 0.2-3.5.
Crosslinking agent: monomer: initator: perforating agent: the weight ratio that contains the mixed liquor of the organic solvent of 0.1-5 weight % emulsifying agent and water is preferably 1: 2.5-200: 0.3-2: 0.05-100: 45-2000.
The reaction temperature of described step (1) is preferably 50-100 ℃, and the reaction time is preferably 10-30 hour.
Described pyrroles: porous polymer microsphere: polyethylene glycol or polyacrylic acid: hydrogen peroxide or ammonium persulfate: the weight ratio of water is preferably 1: 0.5-2: 0.01-0.2: 0.3-10: 50-160.
The reaction temperature of described step (2) is preferably 0-30 ℃, and the reaction time is preferably 10-30 hour.
The pH value of regulating the mixture of described polymer microballoon and polyethylene glycol or the polyacrylic aqueous solution can adopt various acid or aqueous acid, as in sulfuric acid, hydrochloric acid, nitric acid and their aqueous solution one or more.The pH value of the mixture of described polymer microballoon and polyethylene glycol or the polyacrylic aqueous solution is preferably 1-3.
Step (1) and the described inert gas of step (2) refer to not any one gas or the admixture of gas with reactant and product generation chemical reaction, as in nitrogen, the periodic table of elements zero group gas one or more, are preferably nitrogen.
Step (1) and the described vacuum drying temperature of step (2) all can be room temperatures to 120 ℃, are preferably 40-80 ℃.
The particle diameter of the catalyst carrier microballoon for preparing according to method provided by the invention is the 50-1000 nanometer, is preferably the 100-500 nanometer.
According to method provided by the invention, the method that platinum is introduced on the described porous carrier can adopt existing the whole bag of tricks, realizes as infusion process.For example, with the described porous carrier of a kind of solution impregnation of platinum compounds.The solution of described platinum compounds can be the organic solution or the aqueous solution of platinum compounds.Described platinum compounds can be to be dissolved in the platinum compounds of organic solvent and in the platinum compounds that can be water-soluble one or more, be preferably can be water-soluble platinum compounds in one or more, a kind of as in the complex compound of the nitrate of the chloride of chloroplatinic acid soluble in water, chloroplatinate, platinum, platinum, platinum.
Described infusion process can adopt conventional dipping method, as the method for saturated infusion process or immersion.
Under the preferable case, describedly platinum is introduced method on the porous carrier comprise described porous carrier is evenly spread in a kind of organic solvent, and with the aqueous solution of platinum compounds, vacuumize then, the addition of the platinum compounds aqueous solution makes in the catalyst that finally obtains and contains, and is benchmark with the catalyst total amount, in platinum, 20-50 weight % is preferably the platinum of 30-40 weight %.Described organic solvent is selected from one or more in liquid unary alcohol, the polyalcohols, is preferably in ethanol, propyl alcohol, the glycerol one or more.
Described platinum can be with the compound of metal platinum and/or platinum, exists as the form of the oxide of platinum.
When platinum exists with metallic state, method provided by the invention also comprises a reduction step, this reduction step comprises has the porous carrier of platinum compounds to contact with a kind of solution that contains reducing agent load, filter, washing and vacuumize obtain solid product, and the consumption of reducing agent is at least 1 times of platinum molal quantity in the platinum compounds, are preferably 1-20 doubly, the temperature of reduction is 30-100 ℃, is preferably 40-90 ℃; Recovery time is 0.5-20 hour; Be preferably 1-16 hour.Described reducing agent is selected from one or more in formic acid, sodium thiosulfate, the sodium borohydride.
The following examples will the present invention will be further described.
Embodiment 1
This example illustrates method provided by the invention.
(1) preparation of polymer microballoon.
Take by weighing 15 gram absolute ethyl alcohols, 75 gram distilled water, 2 gram neopelexes place four-hole boiling flask, feed nitrogen protection, under agitation are warming up to 80 ℃ with water-bath, stir.Take by weighing 5 gram styrene again, 2 gram divinylbenzenes, 0.9 gram benzoyl peroxide, 0.1 gram toluene after mixing, joins in the four-hole boiling flask, and reaction is 12 hours under 80 ℃.Centrifugation after the emulsion that obtains is cooled to 30 ℃ obtained the solid polymer microballoon with solid product in 10 hours 60 ℃ of vacuumizes.
(2) preparation of catalyst carrier microballoon.
The solution that dried microballoons of 1.5 grams and 0.15 gram polyethylene glycol and 100 ml distilled waters are prepared mix, and are uniformly dispersed with ultrasonic wave, then, with the hydrochloric acid of 5 mol the pH value of system are adjusted to 1, feed nitrogen protection again.Under agitation adding 9 gram concentration is the aqueous hydrogen peroxide solution of 30% weight %, slowly add 2 monomer pyrroles then, 30 ℃ down reaction filter after 12 hours, it is colourless to be washed with distilled water to filtrate, and the product that obtains is obtained the catalyst carrier microballoon 70 ℃ of following vacuumizes.The particle diameter of catalyst carrier microballoon is 400 nanometers.
(3) introducing of platinum
20 gram glycerol are heated to 90 ℃, under agitation mix with the mixture (ethanol: the weight ratio of catalyst carrier microballoon is 200) that step (2) obtains catalyst carrier microballoon and ethanol, be uniformly dispersed with ultrasonic wave, be that the chloroplatinic acid aqueous solution of 0.2 mol mixes with concentration then, the consumption of chloroplatinic acid aqueous solution makes in the catalyst and contains, with the catalyst total amount is benchmark, in platinum, and the platinum of 50% weight %.With concentration is that the pH value that the aqueous hydrochloric acid solution of 5 mol is regulated mixed liquor is 5, add the formic acid reducing agent that is equivalent to 10 times of platinum molal quantitys, 50 ℃ and stir under reduction 1 hour, filter, be washed with distilled water to no acid ion, the dry catalyst C1 that obtains method preparation provided by the invention in 130 ℃ of vacuum drying chambers.
Embodiment 2
This example illustrates method provided by the invention.
(1) preparation of polymer microballoon.
Take by weighing 65 gram butanols, 20 gram distilled water, 0.15 gram lauryl sodium sulfate places four-hole boiling flask, feeds nitrogen protection, under agitation is warming up to 60 ℃ with water-bath, stirs.Take by weighing 9.75 gram methyl methacrylates again, 0.05 gram faces the phthalic acid double methacrylate, 0.05 gram azodiisobutyronitrile, and 5 gram dibutyl phthalates after mixing, join in the four-hole boiling flask, and reaction is 24 hours under 60 ℃.Centrifugation after the emulsion that obtains is cooled to 20 ℃ obtained the solid polymer microballoon with solid product in 24 hours 40 ℃ of vacuumizes.
(2) preparation of catalyst carrier microballoon.
The solution that dried microballoon of 0.2 gram and 0.01 gram polyacrylic acid and 30 ml distilled waters are prepared mixes, and is uniformly dispersed with ultrasonic wave, then, with the sulfuric acid of 5 mol the pH value of system is adjusted to 3, feeds nitrogen protection again.Under agitation adding 0.3 gram concentration is the ammonium persulfate of 30% weight %, the monomer pyrroles who slowly adds 0.2 gram then, filters after 24 hours in reaction under 0 ℃, it is colourless to be washed with distilled water to filtrate, and the product that obtains is obtained the catalyst carrier microballoon 40 ℃ of following vacuumizes.The particle diameter of catalyst carrier microballoon is 300 nanometers.
(3) introducing of platinum
22 gram glycerol are heated to 50 ℃, under agitation mix with the mixture (ethanol: the weight ratio of catalyst carrier microballoon is 50) that step (2) obtains catalyst carrier microballoon and ethanol, be uniformly dispersed with ultrasonic wave, be that the chloroplatinic acid aqueous solution of 0.05 mol mixes with concentration then, the consumption of chloroplatinic acid aqueous solution makes in the catalyst and contains, with the catalyst total amount is benchmark, in platinum, and the platinum of 20% weight %.With concentration is that the pH value that the aqueous hydrochloric acid solution of 5 mol is regulated mixed liquor is 3, add the sodium borohydride reduction agent that is equivalent to 3 times of platinum molal quantitys, 70 ℃ and stir under reduction 15 hours, filter, be washed with distilled water to no acid ion, the dry catalyst C2 that obtains method preparation provided by the invention in 80 ℃ of vacuum drying chambers.
Embodiment 3
This example illustrates method provided by the invention.
(1) preparation of polymer microballoon.
Take by weighing 31 gram ethylene glycol, 40 gram distilled water, 1.5 gram neopelexes place four-hole boiling flask, feed nitrogen protection, under agitation are warming up to 70 ℃ with water-bath, stir.Take by weighing 20 gram butyl methacrylates again, 1.5 gram divinylbenzenes, 2 gram potassium peroxydisulfates, 4 gram dioctyl phthalates after mixing, join in the four-hole boiling flask, and reaction is 20 hours under 70 ℃.Centrifugation after the emulsion that obtains is cooled to 25 ℃ obtained the solid polymer microballoon with solid product in 16 hours 50 ℃ of vacuumizes.
(2) preparation of catalyst carrier microballoon.
The solution that the dried microballoon of 1 gram and 0.1 gram polypropylene acid and 70 ml distilled waters are prepared mixes, and is uniformly dispersed with ultrasonic wave, then, with the hydrochloric acid of 5 mol the pH value of system is adjusted to 2, feeds nitrogen protection again.Under agitation adding 4 gram concentration is the aqueous hydrogen peroxide solution of 30% weight %, the monomer pyrroles who slowly adds 1 gram then, filters after 20 hours in reaction under 25 ℃, it is colourless to be washed with distilled water to filtrate, and the product that obtains is obtained the catalyst carrier microballoon 60 ℃ of following vacuumizes.The particle diameter of catalyst carrier microballoon is 200 nanometers.
(3) introducing of platinum
30 gram glycerol are heated to 80 ℃, under agitation mix with the mixture (ethanol: the weight ratio of catalyst carrier microballoon is 100) that step (2) obtains catalyst carrier microballoon and ethanol, be uniformly dispersed with ultrasonic wave, be that the chloroplatinic acid aqueous solution of 0.1 mol mixes with concentration then, the consumption of chloroplatinic acid aqueous solution makes in the catalyst and contains, with the catalyst total amount is benchmark, in platinum, and the platinum of 40% weight %.With concentration is that the pH value that the aqueous hydrochloric acid solution of 5 mol is regulated mixed liquor is 4, add the sodium borohydride reduction agent that is equivalent to 5 times of platinum molal quantitys, 80 ℃ and stir under reduction 10 hours, filter, be washed with distilled water to no acid ion, the dry catalyst C3 that obtains method preparation provided by the invention in 100 ℃ of vacuum drying chambers.
Embodiment 4
This example illustrates method provided by the invention.
(1) preparation of polymer microballoon.
Take by weighing 60 gram absolute ethyl alcohols, 20 gram distilled water, 2 gram lauryl sodium sulfate place four-hole boiling flask, feed nitrogen protection, under agitation are warming up to 75 ℃ with water-bath, stir.Take by weighing 13 gram styrene again, 1 gram second dialkylene benzene, 1 gram azodiisobutyronitrile, 3 gram dibutyl phthalates after mixing, join in the four-hole boiling flask, and reaction is 22 hours under 75 ℃.Centrifugation after the emulsion that obtains is cooled to 23 ℃ obtained the solid polymer microballoon with solid product in 20 hours 55 ℃ of vacuumizes.
(2) preparation of catalyst carrier microballoon.
The solution that dried microballoon of 0.8 gram and 0.1 gram polyethylene glycol and 80 ml distilled waters are prepared mixes, and is uniformly dispersed with ultrasonic wave, then, with the hydrochloric acid of 5 mol the pH value of system is adjusted to 1, feeds nitrogen protection again.Under agitation adding 6 gram concentration is the aqueous hydrogen peroxide solution of 30% weight %, the monomer pyrroles who slowly adds 1.6 grams then, filters after 22 hours in reaction under 0 ℃, it is colourless to be washed with distilled water to filtrate, and the product that obtains is obtained the catalyst carrier microballoon 65 ℃ of following vacuumizes.The particle diameter of catalyst carrier microballoon is 250 nanometers.
(3) introducing of platinum
25 gram glycerol are heated to 70 ℃, under agitation mix with the mixture (ethanol: the weight ratio of catalyst carrier microballoon is 150) that step (2) obtains catalyst carrier microballoon and ethanol, be uniformly dispersed with ultrasonic wave, be that the chloroplatinic acid aqueous solution of 0.15 mol mixes with concentration then, the consumption of chloroplatinic acid aqueous solution makes in the catalyst and contains, with the catalyst total amount is benchmark, in platinum, and the platinum of 45% weight %.With concentration is that the pH value that the aqueous hydrochloric acid solution of 5 mol is regulated mixed liquor is 5, add the sodium borohydride reduction agent that is equivalent to 6 times of platinum molal quantitys, 60 ℃ and stir under reduction 12 hours, filter, be washed with distilled water to no acid ion, the dry catalyst C4 that obtains method preparation provided by the invention in 110 ℃ of vacuum drying chambers.
Embodiment 5-8
Following embodiment illustrates the performance of the catalyst that the present invention prepares.
Apply one deck in carbon paper one side and be the slurry that the 60%PTFE emulsion mixes with carbon black and solid content, mixing back PTFE content is 15 weight % of mixed slurry total weight, with this mixed slurry carbon paper is carried out smooth processing.The catalyst of the embodiment 2 preparation Nafion solution with the 5 weight % that are equivalent to 10 times heavy of catalyst of E.I.Du Pont Company production is mixed, and the ultrasonic then slurry that is separated into is coated in smooth black carbon surface with this slurry.To be attached with the carbon paper oven dry of the catalyst of embodiment 2, hot pressing is in the same place with proton exchange membrane Nafion115 then, forms membrane electrode.Membrane electrode is assemblied in the monocell testing apparatus, and recording voltage-current curve is estimated the catalyst performance of embodiment 2.The battery testing condition is: 70 ℃ of battery temperatures, and the pressure of anode hydrogen gas and negative electrode oxygen is 0.1 MPa, 75 ℃ of gas humidification temperature, the platinum carrying capacity of electrode is 0.8 milligram/centimetre
2Evaluation result is shown among Fig. 11.
Comparative Examples 1
The performance of activated carbon as the catalyst of carrier adopted in following Comparative Examples explanation.
According to the method for embodiment 5, the activated carbon of Cabot company is estimated as the performance of the E-TEK catalyst (platinum content is 20 weight %) of carrier, the result is shown among Fig. 12.
As can be seen from Figure 1, under identical discharging current, the voltage of the battery of the catalyst of use the inventive method preparation is apparently higher than the voltage that uses activated carbon as the battery of the E-TEK catalyst of carrier, the power of battery of catalyst that promptly uses the inventive method preparation is apparently higher than the E-TEK catalyst that uses activated carbon as carrier, and this catalyst activity that method preparation provided by the invention is described is higher.
Claims (11)
1, a kind of Preparation of catalysts method comprises platinum is introduced in a kind of catalyst carrier, it is characterized in that, described catalyst carrier is a kind of microballoon, its preparation method comprises that (1) is under inert gas shielding and in a kind of emulsion, with monomer, crosslinking agent, initator and perforating agent reaction, centrifugation obtains a kind of solid polymer microballoon, vacuumize; Described emulsion is to contain the organic solvent of 0.1-5 weight % emulsifying agent and the mixed liquor of water, and the weight ratio of organic solvent and water is 0.2-5; Crosslinking agent: monomer: initator: perforating agent: the weight ratio that contains the mixed liquor of the organic solvent of 0.1-5 weight % emulsifying agent and water is 1: 2.5-400: 0.02-40: 0.01-100: 40-3000; Described monomer is selected from styrene, methyl methacrylate or butyl methacrylate; Described crosslinking agent is selected from divinylbenzene or phthalic acid double methacrylate; Described initator is selected from one or more in benzoyl peroxide, azodiisobutyronitrile or the potassium peroxydisulfate; Described perforating agent is selected from one or more in toluene, dibutyl phthalate and the dioctyl phthalate; Described emulsifying agent is selected from neopelex and/or lauryl sodium sulfate; Described organic solvent is selected from one or more in absolute ethyl alcohol, butanols and the ethylene glycol; Reaction temperature is 30-120 ℃, and the reaction time is 1-50 hour; (2) under inert gas shielding, in the presence of hydrogen peroxide or ammonium persulfate, polymer microballoon that step (1) is made and polyethylene glycol or polyacrylic mixture and pyrroles's reaction, filter, extremely colourless with distilled water washing solid product, and vacuumize, the catalyst carrier microballoon obtained; Pyrroles: porous polymer microsphere: polyethylene glycol or polyacrylic acid: hydrogen peroxide or ammonium persulfate: the weight ratio of water is 1: 0.1-7.5: 0.005-0.75: 0.15-45: 15-500; Reaction temperature is 0-50 ℃, and the reaction time is 5-50 hour.
2, method according to claim 1 is characterized in that, described emulsion is to contain the organic solvent of 0.15-3 weight % emulsifying agent and the mixed liquor of water, and the weight ratio of described organic solvent and water is 0.2-3.5.
3, method according to claim 1, it is characterized in that described crosslinking agent: monomer: initator: perforating agent: the weight ratio that contains the mixed liquor of the organic solvent of 0.1-5 weight % emulsifying agent and water is 1: 2.5-200: 0.3-2: 0.05-100: 45-2000.
4, method according to claim 1 is characterized in that, the reaction temperature of described step (1) is 50-100 ℃, and the reaction time is 10-30 hour.
5, method according to claim 1 is characterized in that, the reaction temperature of described step (2) is 0-30 ℃, and the reaction time is 10-30 hour.
6, method according to claim 1 is characterized in that, described pyrroles: porous polymer microsphere: polyethylene glycol or polyacrylic acid: hydrogen peroxide or ammonium persulfate: the weight ratio of water is 1: 0.5-2: 0.01-0.2: 0.3-10: 50-160.
7, method according to claim 1 is characterized in that, described inert gas is selected from one or more in nitrogen, the periodic table of elements zero group gas.
8, method according to claim 1 is characterized in that, the particle diameter of described catalyst carrier microballoon is the 50-1000 nanometer.
9, method according to claim 1, it is characterized in that, platinum is introduced method on the described porous carrier to be comprised porous carrier is evenly spread in a kind of organic solvent, and mix with the solution of platinum compounds, vacuumize then, the addition of platinum compounds solution make in the catalyst that finally obtains and contain, and are benchmark with the catalyst total amount, in platinum, the platinum of 20-50 weight %.
10, method according to claim 1, it is characterized in that, this method also comprises a reduction step, this reduction step comprises has the porous carrier of platinum compounds to contact with a kind of solution that contains reducing agent load, filter, washing and vacuumize obtain solid product, and the consumption of reducing agent is at least 1 times of platinum molal quantity in the platinum compounds, and reduction temperature is 30-100 ℃; Recovery time is 0.5-20 hour.
11, method according to claim 9 is characterized in that, described reducing agent is selected from one or more in formic acid, sodium thiosulfate, the sodium borohydride.
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| CN100543052C (en) * | 2007-09-24 | 2009-09-23 | 南京大学 | The preparation method of nano-level crosslinked polystyrene hollow microsphere |
| CN114665111A (en) * | 2022-04-15 | 2022-06-24 | 湖南清牛新材料科技有限公司 | Fuel cell anode catalyst and preparation method thereof |
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| US6254978B1 (en) * | 1994-11-14 | 2001-07-03 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
| JP3883956B2 (en) * | 2002-11-29 | 2007-02-21 | 三洋電機株式会社 | Solid polymer electrolyte membrane and fuel cell using the same. |
| KR100464322B1 (en) * | 2002-12-30 | 2005-01-03 | 삼성에스디아이 주식회사 | Method for manufacturing fuel cell electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100543052C (en) * | 2007-09-24 | 2009-09-23 | 南京大学 | The preparation method of nano-level crosslinked polystyrene hollow microsphere |
| CN114665111A (en) * | 2022-04-15 | 2022-06-24 | 湖南清牛新材料科技有限公司 | Fuel cell anode catalyst and preparation method thereof |
| CN114665111B (en) * | 2022-04-15 | 2024-02-09 | 湖南清牛新材料科技有限公司 | Fuel cell anode catalyst and preparation method thereof |
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