CN1979930A - Preparing method for noble metal catalyst for proton exchanging film fuel cell - Google Patents
Preparing method for noble metal catalyst for proton exchanging film fuel cell Download PDFInfo
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- CN1979930A CN1979930A CNA2005101261160A CN200510126116A CN1979930A CN 1979930 A CN1979930 A CN 1979930A CN A2005101261160 A CNA2005101261160 A CN A2005101261160A CN 200510126116 A CN200510126116 A CN 200510126116A CN 1979930 A CN1979930 A CN 1979930A
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- catalyst
- noble metal
- aqueous solution
- platinum
- inverse micellar
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 35
- 239000000446 fuel Substances 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 66
- 239000000693 micelle Substances 0.000 claims description 39
- 230000002441 reversible effect Effects 0.000 claims description 36
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000010970 precious metal Substances 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 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 4
- OSOSMTZOKLTVFS-UHFFFAOYSA-N S(=O)(=O)(O)C(C(=O)O)CC(=O)O.C(C)C(C[Na])CCCC Chemical group S(=O)(=O)(O)C(C(=O)O)CC(=O)O.C(C)C(C[Na])CCCC OSOSMTZOKLTVFS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- -1 chloroplatinate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- YNXWJQUOWPUKIF-UHFFFAOYSA-N [Na].[Pt].S(O)(O)=O Chemical compound [Na].[Pt].S(O)(O)=O YNXWJQUOWPUKIF-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000366 colloid method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 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
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- Catalysts (AREA)
Abstract
The method includes steps: (1) adding water solution of noble metal compounds, and water solution of reducing agent to non aqueous solution of surface active agent respectively, and then stirring them evenly so as to obtain two inverse micellar solutions; (2) mixing the obtained two inverse micellar solutions, making the mixed solution contact with carrier of catalyst, and stirring them to make grains of noble metal be loaded to carrier of catalyst, obtaining catalyst grains of noble metal. Controlling size of fluid drop i.e. water content, the method can control size of grain of noble metal catalyst. Thus, the invention can obtain catalyst with high catalytic activity and smaller grain size so as to raise use ratio of noble metal, lower cost. Features are: simple method, controllable technical condition, and no pollution of reducing agent on environment.
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 noble metal catalyst of Proton Exchange Membrane Fuel Cells about a kind of.
Background technology
Fuel cell is a kind of chemical energy directly to be changed into the device of electric energy, 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, in the fuel cell of middle low temperature, being widely used of loaded noble metal platinum nanocatalyst is with the reduction reaction that improves anode and cathode and the speed of oxidation reaction.The preparation method that this class catalyst is commonly used is an infusion process, ion-exchange, B nnemann method, intercalation compound reaction method, colloid method, deposition-precipitation method, microemulsion method.
CN1577928A discloses a kind of fuel cell platinum based noble metal Catalysts and its preparation method of high electrocatalytic active.Described platinum based noble metal catalyst as the platinum precursor, is an additive precursor with the mixture of a kind of slaine or several slaines with the mixture of a kind of platinum salt or several platinum salt, when being loaded, but is carrier with conducting medium; Being heating source with the microwave radiation in preparation, is reducing agent and protective agent with the polyalcohol, under microwave radiation, can obtain fast that particle diameter is controlled, high dispersive one, two, ternary and polynary supporting and non-supported platinum based noble metal catalyst.This Preparation of catalysts method comprises: the platinum polybasic salt alcoholic solution of (1) configuration solubility or the mixed solution of slaine polyalcohol and water, metal salt solution concentration is 1.0 * 10
-5-10mol/L; (2) the additive precursor metal salts polyhydric alcohol solutions of configuration solubility or the mixed solution of slaine polyalcohol and water, metal salt solution concentration is 1.0 * 10
-5-10mol/L; (3) carrier is scattered in the mixed solution or water of polyhydric alcohol solutions or polyalcohol and water ultrasonic dispersion, carrier suspension concentration 0.1-1000g/L; (4) solution in step (1) and (2) is mixed; (5) add alkaline solution, the pH value of the solution of gained in the regulating step (4); (6) carrier of gained solution in the step (5) with the middle gained of step (3) fully mixed, with the carry out microwave radiation heating reduction, the solution of gained in the perhaps first carry out microwave radiation heating reduction step (5), the carrier with the middle gained of step (3) fully mixes again; (7) add setting accelerator, filter, washing, vacuumize.The metallic of the catalyst for preparing according to this method is between 0.5-10nm, and additive is closely adjacent with platinum particles or form alloy.But this kind method step is various, the preparation process complexity, (3), wayward the putting in place of reaction condition of (5), (6) step, therefore make the particle size of the catalyst granules for preparing be not easy control, and short heavy agent all is acid, environment is had certain pollution.
US5068161 discloses the method that a kind of immersion reduction method prepares supported metal catalyst, this method comprises compound loaded to a kind of carbon carrier of conduction with the aqueous slkali of platinum and one or more alloying elements, the amount that loads on the platinum on the carrier is 20-60 weight %, then by adding a kind of reducing agent in formaldehyde, formic acid, the hydrazine etc.; Perhaps feed N after the Direct Filtration drying
2/ H
2Gaseous mixture heating reduction and the alloy that load is had the carrier of this compound to heat-treat to obtain platinum and another element at least, the specific area of this alloy is greater than 35 meters
2/ gram platinum.Thereby make loaded Pt/C catalyst.This method adopts conducts such as formaldehyde, formic acid, hydrazine to change former dose, and toxicity is big, contaminated environment, and adopt the hydrogen heating reduction, and metallic is grown up, thereby reduce activity of such catalysts, and easily make catalyst generation spontaneous combustion, have certain risk.
US3992331 discloses a kind of method for preparing the active carbon supported platinum catalyst of high dispersive, and this method comprises makes sulfurous acid platinum sodium (Na with chloroplatinic acid earlier
6[Pt (SO
3)
4]), make the sodium ion in the sulfurous acid platinum sodium be exchanged into hydrogen ion by ion-exchange then, in air, be heated to boiling, discharge unnecessary sulfite ion, dry at a certain temperature at last prepared black platinum colloid, this colloid can be distributed in water or other solvent once more, thereby is easy to support on all kinds of carriers.Adopt this method can make the platinum catalyst that granular size is the 1.5-2.5 nanometer, therefore this method, can effectively be avoided because the catalytic activity that trace chlorine causes reduces owing to utilize inferior sulfate radical that chloride ions displace is fallen simultaneously.
But in sum, the preparation method of existing supported metal catalyst and some technological process complexity, process conditions are not easy control, make that the Preparation of catalysts cycle is long, the preparation cost height.In addition, some poisonous reducing agents that adopted also can pollute environment.
Summary of the invention
The objective of the invention is in order to overcome preparation method's complexity of existing fuel-cell catalyst, technical process is wayward, manufacturing cycle is long, the shortcoming that preparation cost is high, and provide a kind of new, simple and can control the preparation method of the fuel cell noble metal catalysts of gained catalyst particle size easily.
Preparation of catalysts method provided by the invention may further comprise the steps: (1) joins the aqueous solution of precious metal chemical complex and the aqueous solution of reducing agent in the non-aqueous solution of surfactant respectively, and stirs, and obtains two kinds of inverse micellar solutions; (2) two kinds of inverse micellar solutions that obtain in the step (1) are mixed and contact with catalyst carrier, stir, noble metal granule is loaded on the catalyst carrier, filtration obtains containing the catalyst granules of described noble metal.
This new Preparation of catalysts method provided by the invention is to utilize the reverse micelle drop in the inverse micellar solution or be called " pond " as a kind of special nanometer space, prepares the method for nanoparticle as reacting field.The preparation method of this new noble metal catalyst provided by the invention and used instrument and equipment are simple, process conditions are controlled, preparation flow is short, adopt preparation method provided by the invention can pass through the size of the reacting field of control reverse micelle drop, it is the particle size that the size of water content is accurately controlled required noble metal catalyst, can be by the catalyst that particle diameter is less and catalytic activity is high that how much prepares of control water content, improved utilance, thereby reduced cost, and the reducing agent that preparation method of the present invention adopted can not pollute all to environment.
Embodiment
Described reverse micelle is meant that surfactant aligns and a kind of aggregation of spontaneous formation in non-aqueous solution.Inverse micellar solution is to be decentralized medium with water-fast organic solvent, is the dispersion of decentralized photo with the aqueous solution, because the existence of surfactant, this system is even, transparent, the isotropic thermodynamic stable system of a kind of dispersed phase distribution." pond " in the reverse micelle microreactor, reverse micelle drop just, its controlled amount is within a few to tens of nanometers, and yardstick is little and separated from one another.
After the inverse micellar solution that contains two kinds of differential responses thing A, B mixes, because processes such as the collision between the micella, fusion, separation, reorganization, make the aqueous phase reactions thing intercourse, mix in " pond ", and react, the product of generation can be limited in the micella by strictness.The micella that contains the product molecule forms the supersaturated solution of product in " pond " after colliding many times, reach certain degree of super saturation and will produce the nucleus particle.Because the nucleus particle size that generates is inhomogeneous, the solubility of small-particle is big, and the solubility of macroparticle is little, thereby slaking (be the small-particle dissolving, macroparticle is grown up) takes place and nucleus is grown up gradually, is stored in the reverse micelle " pond ", finally forms nanoparticle.
It is the size of drop that water content in the reverse micelle influences reverse micelle microreactor " pond ", i.e. the size of the noble metal granule that influence is generated.Water content=the water of reverse micelle and the mol ratio of surfactant, the water content linear correlation of droplet radius and reverse micelle, droplet radius increases with the increase of reverse micelle water content.The value of water content by the control reverse micelle is controlled the size of drop, thereby controls the particle size of resulting noble metal granule.
Generally speaking, when reverse micelle water content＜7, the micella of formation is spherical, and in micella, water is mainly to exist in conjunction with attitude; When 7＜reverse micelle water content＜20, the spherical micelle of formation can be the increase of reverse micelle water content and swelling along with the increase of water, and in micella, water is except to exist in conjunction with attitude, and some exists with free state and intermediate state; When reverse micelle water content＞20, water mainly exists with free state; When reverse micelle water content＞30, then can not form micella but be divided into two-phase.
According to Preparation of catalysts method provided by the invention, the water in the described reverse micelle system is mainly from the water in the precious metal chemical complex aqueous solution and the reducing agent aqueous solution.In order to be controlled at the size of the noble metal that generates in the reverse micelle, according to method provided by the invention, the amount of the amount of the precious metal chemical complex aqueous solution that is added, the amount of the reducing agent aqueous solution and surfactant non-aqueous solution makes the mol ratio of water and surfactant in the final reverse micelle system that forms, the value that is the reverse micelle water content is controlled between the 1-20, and preferably the value with the reverse micelle water content is controlled between the 1-10.
Surfactant is a kind of amphiphile, amphiphilic molecule, i.e. a part of possess hydrophilic property in the molecule, and another part has lipophile.When the surfactant of capacity was dissolved in the organic solvent, surfactant existed with the form of micelle, and the hydrophily polar head of surfactant flocks together, and the outside is nonpolar alkyl afterbody, aligned in organic solvent and formed reverse micelle.The number and the surfactant concentrations of the contained surfactant molecule of each micelle have direct relation.Therefore, the concentration of surfactant in organic solvent can influence the size of the drop of final formation, also will influence the particle size of the nano particle that forms in reverse micelle and the stability of particle.When surfactant concentrations increased, the reverse micelle size increased but decreased number, thereby the particle diameter of the nanoparticle that generates increases.
Therefore, according to method provided by the invention, described be used for two kinds of inverse micellar solution surfactant concentrations described in the preparation steps (1) can be identical also can be inequality, under the preferable case, the described surfactant concentrations that is used for two kinds of inverse micellar solutions described in the preparation steps (1) is identical, and concentration is 1.0 * 10
-5-10 mol are preferably the 0.1-1.0 mol.
The kind that is used to form the surfactant of reverse micelle of the present invention comprises anion surfactant, cationic surfactant and non-ionic surface active agent.For example, anion surfactant can be 2-ethylhexyl sodium sulfosuccinate (AOT), neopelex (DBS), lauryl sodium sulfate (SDS); Cationic surfactant can be softex kw (CTAB); Non-ionic surface active agent can be Triton X-100 Triton X-100, and lauryl alcohol APEO C12E5, and the surfactant that contains APEO are as the surfactant of NP series.
Preferred surfactants of the present invention is a 2-ethylhexyl sodium sulfosuccinate (AOT).Because AOT is a kind of anion surfactant, the mean molecule aggregation number of its formed reverse micelle is bigger than other surfactant, and solubilizing amount is big, be uniformly dispersed, stablize, do not need cosurfactant, therefore, the preferred surfactant of the present invention is a 2-ethylhexyl sodium sulfosuccinate (AOT).
The solvent of described surfactant is preferably organic solvent, and for example C6-C8 straight-chain hydrocarbons or cycloalkane are preferably in cyclohexane, normal heptane, the isooctane one or more.
According to Preparation of catalysts method provided by the invention, the noble metal in the described precious metal chemical complex is preferably platinum; Described precious metal chemical complex be can be water-soluble precious metal chemical complex in one or more, be preferably in the complex compound of nitrate, platinum of chloride, the platinum of chloroplatinic acid soluble in water, chloroplatinate, platinum one or more.
Utilizing inverse micellar solution to prepare in the process of noble metal catalyst, concentration of reactants can influence the size and the particle size distribution of noble metal granule equally, therefore, the Cmin of the described precious metal chemical complex aqueous solution is for reacting with described reducing agent at least, Cmax is the saturated concentration in the aqueous solution, is preferably the 0.1-1.0 mol; The Cmin of the described reducing agent aqueous solution is for reacting with precious metal chemical complex at least, Cmax is the saturated concentration in the aqueous solution, be preferably the 1.0-5.0 mol, more preferably under the situation, the concentration of the described reducing agent aqueous solution is greater than the concentration of the precious metal chemical complex aqueous solution.
The amount of described reducing agent is at least 1 times of noble metal molal quantity in the precious metal chemical complex, is preferably 1-20 doubly, and described reducing agent be the reducing agent that described precious metal chemical complex can be reduced, as in formic acid, sodium thiosulfate, the sodium borohydride one or more.
The kind of described catalyst carrier is conventionally known to one of skill in the art, for example can adopt carbon nano-tube and/or acetylene black, preferably adopts acetylene black; Be 0.5-15 hour the time of contact of the mixed inverse micellar solution that described catalyst carrier and step (2) obtain, and is preferably 2-6 hour; The temperature of contact is preferably room temperature.In the described precious metal chemical complex weight of noble metal be catalyst carrier weight 0.1-5 doubly; Be preferably 0.1-2 doubly.
Can adsorb the noble metal granule that is reduced out more fully in order to make catalyst carrier, to improve the utilance of noble metal, cut the waste, reduce cost, with described mixed inverse micellar solution with after catalyst carrier contacts, described Preparation of catalysts method also comprises and adds demulsifier and fully stir, to destroy the step (3) of inverse micellar solution, described demulsifier destroys reverse micelle, and utilizes catalyst carrier such as acetylene black to adsorb the noble metal granule that is reduced out more fully.
Described demulsifier is selected from one or more in ethanol, propyl alcohol, butanols, ethylene glycol, the glycerol.
The volume ratio of the cumulative volume of described inverse micellar solution and the demulsifier of adding is 1-50: 1, be preferably 2-10: 1.
The mixing time of described step (3) is 2-5 hour, is preferably 2-3 hour; Whipping temp is preferably room temperature.
According to Preparation of catalysts method provided by the invention, also be included in the washing step that adds after demulsifier fully adsorbs carrier to obtain load the catalyst that noble metal granule is arranged, described washing comprise adopt organic solvent washing with the nonaqueous solvents of removing unnecessary surfactant and surfactant and with the distilled water washing to remove foreign ion.
According to Preparation of catalysts method provided by the invention, also comprise the drying steps after the washing, the method of described drying can adopt the method for well known to a person skilled in the art, as vacuumize, air dry, forced air drying, under the preferable case, described drying is to carry out in the inert gas atmosphere of argon gas or nitrogen or in the atmosphere of hydrogen or oxygen.The temperature of described drying can be a room temperature to 120 ℃, is preferably 40-100 ℃; The dry time is 2-20 hour, is preferably 6-10 hour.
Containing in the catalyst for preparing according to method provided by the invention, is benchmark with the catalyst total amount, in platinum, and the platinum of 30-50 weight %.The mean radius of described noble metal catalyst particle is the 2.5-10 nanometer, is preferably the 2.5-6 nanometer.
Below will further describe the present invention by specific embodiment.
Embodiment 1
Present embodiment illustrates Preparation of catalysts method provided by the invention
(1) with 0.2 ml concn is the H of 0.2 mol
2PtCl
6The aqueous solution and 1.85 ml concns are the NaBH of 2.0 mol
4The aqueous solution join respectively 25 milliliters in cyclohexane concentration be in the AOT solution of 0.2 mol.
(2) AOT/H that step (1) is obtained
2PtCl
6The aqueous solution/cyclohexane and AOT/NaBH
4The aqueous solution/cyclohexane mixes, and at room temperature stirs 30 minutes colors up to system continuously fast from Huang blackening gradually.Total moisture content in the reaction system is about 2 milliliters.The mol ratio of water and AOT in reverse micelle system, promptly the value of reverse micelle water content is 10.Add 0.5 gram Vulcan XC-72 acetylene black then, add 10 milliliters of ethanol after 2 hours, stirred 2 hours, filter, then successively with cyclohexane and ethanol washing; It is colourless being washed with distilled water to solid product at last, and drying obtained catalyst metal particles in 8 hours in 100 ℃ of baking ovens.The mean radius of the catalyst platinum grain that obtains is 3.6 nanometers, and the content of platinum is 45 weight %.
Embodiment 2
Present embodiment illustrates Preparation of catalysts method provided by the invention
(1) with 0.45 ml concn is the H of 0.5 mol
2PtCl
6The aqueous solution and 3.6 ml concns are the NaBH of 4.0 mol
4The aqueous solution join respectively 25 milliliters in cyclohexane concentration be in the AOT solution of 0.3 mol.
(2) AOT/H that step (1) is obtained
2PtCl
6The aqueous solution/cyclohexane and AOT/NaBH
4The aqueous solution/cyclohexane mixes, and at room temperature stirs 20 minutes colors up to system continuously fast from Huang blackening gradually.Total moisture content in the reaction system is about 4 milliliters.The mol ratio of water and AOT in reverse micelle system, promptly the value of reverse micelle water content is 15.Add 0.7 gram Vulcan XC-72 acetylene black then, add 20 milliliters of ethanol after 5 hours, stir after 2.5 hours, filter, then successively with cyclohexane and ethanol washing; It is colourless being washed with distilled water to solid product at last, and drying obtained catalyst metal particles in 6 hours in 100 ℃ of baking ovens.The mean radius of the catalyst platinum grain that obtains is 6 nanometers, and the content of platinum is 35 weight %.
Embodiment 3
Present embodiment illustrates Preparation of catalysts method provided by the invention
(1) with 0.07 ml concn is the H of 0.8 mol
2PtCl
6The aqueous solution and 1 ml concn are the NaBH of 1.0 mol
4The aqueous solution join respectively 25 milliliters in cyclohexane concentration be in the AOT solution of 0.2 mol.
(2) AOT/H that step (1) is obtained
2PtCl
6The aqueous solution/cyclohexane and AOT/NaBH
4The aqueous solution/cyclohexane mixes, and at room temperature stirs 30 minutes colors up to system continuously fast from Huang blackening gradually.Total moisture content in the reaction system is about 1 milliliter.The concentration ratio of the material of water and AOT in reverse micelle system, promptly the value of reverse micelle water content is 5.Add 0.3 gram Vulcan XC-72 acetylene black then, add 10 milliliters of ethanol after 3 hours, stirred 3 hours, filter, then successively with cyclohexane and ethanol washing; It is colourless being washed with distilled water to solid product at last, and drying obtained the catalyst platinum grain in 10 hours in 100 ℃ of baking ovens.The mean radius of the catalyst platinum grain that obtains is 2.8 nanometers, and the content of platinum is 40 weight %.
Claims (17)
1, a kind of preparation method who is used for the noble metal catalyst of Proton Exchange Membrane Fuel Cells, it is characterized in that, this method may further comprise the steps: (1) joins the aqueous solution of precious metal chemical complex and the aqueous solution of reducing agent in the non-aqueous solution of surfactant respectively, stir, obtain two kinds of inverse micellar solutions;
(2) two kinds of inverse micellar solutions that obtain in the step (1) are mixed and contact with catalyst carrier, stir, noble metal granule is loaded on the catalyst carrier, filtration obtains containing the catalyst granules of described noble metal.
2, method according to claim 1, wherein, the concentration of the described precious metal chemical complex aqueous solution is the 0.1-1.0 mol, the concentration of the described reducing agent aqueous solution is the 1.0-5.0 mol.
3, method according to claim 2, wherein, the concentration of the described reducing agent aqueous solution is greater than the concentration of the precious metal chemical complex aqueous solution.
4, method according to claim 1, wherein, described precious metal chemical complex is selected from one or more in the complex compound of nitrate, platinum of chloride, the platinum of chloroplatinic acid, chloroplatinate, platinum.
5, method according to claim 1, wherein, described reducing agent is selected from one or more in formic acid, sodium thiosulfate, the sodium borohydride.
6, method according to claim 1, wherein, the concentration of described surfactant non-aqueous solution is 1.0 * 10
-5-10 mol.
7, method according to claim 1, wherein, described surfactant is a 2-ethylhexyl sodium sulfosuccinate.
8, method according to claim 1, wherein, the mol ratio of water and surfactant in the mixed inverse micellar solution that described step (2) obtains, promptly the value of the water content of reverse micelle is 1-20.
9, method according to claim 8, wherein, the mol ratio of water and surfactant in the mixed inverse micellar solution that described step (2) obtains, promptly the value of the water content of reverse micelle is 1-10.
10, method according to claim 1, wherein, when two kinds of inverse micellar solutions that in step (2) step (1) obtained mixed, the molal quantity of described reducing agent was at least 1 times of noble metal molal quantity in the precious metal chemical complex.
11, method according to claim 1, wherein, when mixed two kinds of inverse micellar solutions that will obtain in the step (2) contact with catalyst carrier, in the described precious metal chemical complex weight of noble metal be catalyst carrier weight 0.1-5 doubly; Be 0.5-15 hour time of contact; The temperature of contact is a room temperature.
12, method according to claim 1, wherein, this method also is included in and mixed two kinds of inverse micellar solutions are contacted the back adds demulsifier and stir to destroy the step (3) of inverse micellar solution with catalyst carrier.
13, method according to claim 12, wherein, the cumulative volume of described inverse micellar solution is 2-10 with the volume ratio of the demulsifier that is added: 1.
14, method according to claim 12, wherein, the mixing time of described step (3) is 2-5 hour, whipping temp is a room temperature.
15, method according to claim 1, wherein, the particle mean radius of described catalyst granules is the 2.5-10 nanometer.
16, method according to claim 15, wherein, the particle mean radius of described catalyst granules is the 2.5-6 nanometer.
17, method according to claim 1 wherein, contains in the catalyst that obtains, and is benchmark with the catalyst total amount, in platinum, and the platinum of 30-50 weight %.
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| CN101937999A (en) * | 2010-09-09 | 2011-01-05 | 哈尔滨工业大学 | Preparation method of supported binary alloy direct alcohol fuel cell catalyst with porous hollow sphere structure |
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| JP3373135B2 (en) * | 1997-06-13 | 2003-02-04 | 長一 古屋 | Method for producing reaction layer of gas diffusion electrode |
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| CN101937999B (en) * | 2010-09-09 | 2013-06-05 | 哈尔滨工业大学 | Preparation method of supported binary alloy direct alcohol fuel cell catalyst with porous hollow sphere structure |
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| CN116230961B (en) * | 2023-05-10 | 2023-07-18 | 上海韵量新能源科技有限公司 | Fuel cell alloy catalyst and preparation method and application thereof |
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