CN102500365A - Preparation method of catalyst with core-shell structure for low-temperature fuel cell - Google Patents
Preparation method of catalyst with core-shell structure for low-temperature fuel cell Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 239000011258 core-shell material Substances 0.000 title abstract 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000000034 method Methods 0.000 claims abstract description 68
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 11
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000011135 tin Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 84
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000012018 catalyst precursor Substances 0.000 claims description 41
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
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- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical group [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 26
- 150000005846 sugar alcohols Polymers 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
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- 239000007864 aqueous solution Substances 0.000 claims description 8
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
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- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- 229940046892 lead acetate Drugs 0.000 claims description 2
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- 230000004044 response Effects 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
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- 150000002739 metals Chemical class 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
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- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000012792 core layer Substances 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
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- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229910002849 PtRu Inorganic materials 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 13
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- 229910021126 PdPt Inorganic materials 0.000 description 9
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- 239000013078 crystal Substances 0.000 description 6
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 3
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- 238000005303 weighing Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002669 PdNi Inorganic materials 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000011943 nanocatalyst Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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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- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a catalyst with a core-shell structure for a low-temperature fuel cell, belonging to the technical field of fuel cells. In the catalyst with the core-shell structure prepared with the preparation method, platinum is taken as a shell, a metal alloy consisting of more than one of metals including ruthenium, platinum, iron, cobalt, nickel, copper, tin, iridium, gold and silver is taken as an inner core, and the shell and the inner core are loaded on a carbon carrier. The preparation method comprises the following preparation steps of: reducing a metal chloride or a metal nitrate with a reducing agent, and forming a core on the carbon carrier with a large specific surface area; stabilizing the core; and precipitating Pt on a core layer with a impregnation reduction method, a high-pressure organic sol method, a microwave method or an electrodeposition process to form the catalyst with the core-shell structure. Due to the adoption of the preparation method, the utilization ratio of noble metal platinum is increased, the cost of an electro-catalyst is reduced effectively, and the methanol oxidizing capability and oxygen reducing activity of the obtained catalyst are increased by 10.8 times and 8.7 times in maximum respectively in comparison to the mass ratio and activity of a commercial JM4100Pt/C catalyst.
Description
Technical field
The present invention relates to fuel cell field, be specifically related to a kind of preparation method who is used for the catalyst with core-casing structure of low-temperature fuel cell.
Background technology
The environmental problem that causes along with fossil fuel such as energy problem and coal combustion severe day by day more and more obtains the great attention of countries in the world government and scientific circles about the research and development of hydrogen energy source and fuel cell.Fuel cell is rich and varied with its fuel source, energy conversion efficiency is high, to the little advantages such as (zero-emission or low emissions) of ambient influnence; Being considered to a kind of most possible extensive novel energy technology that substitutes the existing energy, is to solve future source of energy problem and because one of important technical of the burning serious problem of environmental pollution that fossil energy caused.In addition, the low-temperature fuel cell in the fuel cell is with advantages such as its cleaning, efficient, safe, removable, operating condition gentlenesses, and being described as is a types of fuel cells of the extensive industrialization prospect of tool.Low-temperature fuel cell comprises hydrogen-oxygen fuel cell, direct alcohol fuel battery and direct acid fuel battery etc.; These fuel-cell catalysts all use and cost an arm and a leg, the noble metal platinum of scarcity of resources is as main active component; The fuel cell that causes thus is with high costs, has become the key factor of restriction fuel cell commercialization process.Therefore, how on the basis that does not reduce catalyst catalytic performance, reducing the platinum carrying capacity and then reducing the catalyst price becomes a challenging problem.The fuel-cell catalyst of exploitation high-performance, low platinum carrying capacity has crucial meaning for the development and the commercialization process that promote fuel cell technology.
Reduce the platinum carrying capacity at present and mainly contain two approach: adopt Pt and other metals to form alloying; Adopt the Pt individual layer to modify the method that other metals perhaps form nucleocapsid structure.In catalyst with core-casing structure, precious metals pt is surperficial in nucleation material with the thin layer form high degree of dispersion, thereby has reduced noble metal dosage, can also bring into play the synergy between nucleation material and the noble metal simultaneously.
One Chinese patent application file CN101890368A discloses " carbon carries the preparation method of high activity gold or plation or golden core platinum-shell structural nano catalyst "; Promptly utilize the method for self assembly; Modifying the mercapto-functionalized carbon black of porous carbon acquisition with the pi-pi bond of modified chemical reagent is carrier; Again golden nanometer particle or a golden platinum alloy or golden core platinum-shell structural nano particle are deposited to the black carbon surface of coloured glaze base functionalization; Obtain having highly active gold or gold-platinum alloy or golden core platinum-shell structural nano carbon supported catalyst, but that the method prepares the required cycle of catalyst is long, the catalyst particle size of preparation is bigger.
One Chinese patent application file CN101664685A discloses " a kind of preparation method of catalyst with core-casing structure ", soon covers on the Metal Substrate kernel with platinum individual layer after the reducing agent reduction or bilayer and forms nucleocapsid structure.This preparation method is: adopt chloride or the nitrate with a kind of or two kinds of metals in zinc, iron, palladium, tin, cobalt, nickel, the copper such as sodium borohydride, formic acid, formaldehyde, ascorbic acid earlier, reduction makes catalyst precursor; On the catalyst precursor with preparation before platinum individual layer behind the reduction of ethylene glycol or double-deck the covering, promptly make catalyst with core-casing structure again.But this method is when the preparation catalyst precursor, and catalyst precursor is difficult for forming; Secondly the disclosed preparation method of this document lacks committed steps such as presoma stabilization processes, makes the poor stability of prepared catalyst with core-casing structure.
One Chinese patent application file 200810069271.7 discloses a kind of " preparation method of nucleocapsid structure gas perforated electrode catalyst "; Be to contain non-platinum family transition metal M ion (as: Cu; Co; Ni etc.) in the aqueous solution, earlier with the method for two pace pulse electro-deposition with the transition metal M electro-deposition with porous carbon electrodes that PEM contacts on, react through the chemical replacement between solubility platinum salt and the non-platinum family transition metal that deposited again; The surface of carrying non-platinum family transition metal at carbon forms the platinum monoatomic layer of displacement fully, forms the nucleocapsid structure gas perforated electrode catalyst.This method has overcome by serial problems such as Direct Electrochemistry deposition serious liberation of hydrogen effect, electrolyte hydrolysis deterioration and platinum grain that platinum caused are thick to a certain extent.But this method is not considered when deposition M examines on porous carbon electrodes; Because the influence that the porous carbon electrodes electric double layer capacitance discharges and recharges; Can not give full play to the high advantageous effect of instantaneous peak current in the pulse electrodeposition, thereby cause M nuclear crystal grain and MPt crystal grain is excessive, size is difficult to control.
After this; Patent application document CN101359744A has carried out further improvement to patent application document 200810069271.7 described methods; Specific as follows: as at first in the aqueous solution, to go on foot the transition metal M (as: Cu of electrodeposition processes with high degree of dispersion through four; Co. Ni etc.) nano particle is deposited on porous carbon electrodes and (on (PCE), then resulting M/PCE electrode is immersed in the platinum salting liquid of nitrogen protection the carbon supported ultra-low platinum catalytic electrode that obtains high dispersive through displacement reaction.This method has overcome in the two pace pulse electrodeposition process by electric double layer capacitance and has discharged and recharged the M nuclear crystal grain that is caused and MPt crystal grain is excessive, the unmanageable drawback of size when giving full play to the high advantage of the instantaneous peak current of pulse electrodeposition.But this prepares the method for catalyst with core-casing structure, and the process that still exists is loaded down with trivial details, and influence factor is too much, and nuclear is difficult to a series of problems such as control with the metal quality ratio of shell.
Summary of the invention
For solving defective and the deficiency that exists in the above-mentioned correlation technique, the purpose of this invention is to provide a kind of preparation method who is used for the catalyst with core-casing structure of low-temperature fuel cell, the catalyst of this nucleocapsid structure has the characteristic of high activity, low Pt carrying capacity.
Said catalyst with core-casing structure is to be shell with platinum, is kernel with more than one metal alloys in metal Ru, palladium, iron, cobalt, nickel, copper, tin, iridium, gold and the silver, and shell and kernel are carried on carbon carrier jointly, and its preparation process is following:
(1) preparation of nuclear
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds metal chloride or metal nitrate again; Ultrasonic, mix after; Add the carbon carrier of crossing through oxidation processes again, stir and ultrasonic to being uniformly dispersed, using mass concentration then is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again in the autoclave and react 4h～12h down in 100 ℃～160 ℃; Reaction treats that autoclave is cooled to room temperature after finishing, and the use mass concentration is rare HNO of 5%～10%
3The pH value that the aqueous solution is regulated reaction under high pressure pot systems reactant liquor is 4～6, washs and filtering reacting liquid with secondary water washing again, does not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst precursor 60 ℃～80 ℃ following vacuum drying; The carbon carrier quality is equivalent to 4～8 times of the total theoretical metal quality of metal chloride or metal nitrate reduction back; The mol ratio of total metal ion is 1:1～1:10 in polyalcohol reducing agent and metal chloride or the metal nitrate; The mol ratio of total metal ion is 2:1～2.5:1 in complexing agent and metal chloride or the metal nitrate; The mol ratio of metal chloride or metal nitrate and polyalcohol reducing agent is 1:0.3～1:3; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol;
(2) stabilization processes of nuclear
With catalyst precursor under inert atmosphere conditions, 100 ℃～150 ℃ following stabilization processes 1h～3h;
(3) preparation of shell
Catalyst precursor to handle through step (2) is a kernel, on kernel, prepares shell with immersion reduction method, high pressure organic sol method, microwave method or electrodeposition process, then kernel, shell is carried on the carbon carrier jointly, obtains catalyst with core-casing structure.
Said carbon carrier is Vulcan XC-72 carbon black or CNT.
The concrete steps of the said high pressure organic sol method of step (3) are:
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid to it again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, using mass concentration is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again in the autoclave and react 4h～12h down in 100 ℃～160 ℃; Reaction treats that autoclave is cooled to room temperature after finishing, and the use mass concentration is rare HNO of 5%～10%
3The pH value that the aqueous solution is regulated the reaction under high pressure pot systems is 4～6, washs reaction system with secondary water washing again and does not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst with core-casing structure 60 ℃～80 ℃ following vacuum drying; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate, and the mol ratio of itself and chloroplatinic acid is 2:1～2.5:1; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol, and the mol ratio of itself and chloroplatinic acid is 1:1～1:10.
The concrete steps of the said microwave method of step (3) are:
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid to it again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, using mass concentration is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again and react 1min～2min in the micro-wave oven; After reaction finished, the question response system was cooled to room temperature, washed reaction system with secondary water washing again and did not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst with core-casing structure 60 ℃～80 ℃ following vacuum drying; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate, and the mol ratio of complexing agent and chloroplatinic acid is 2:1～2.5:1; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol, and the mol ratio of polyalcohol reducing agent and chloroplatinic acid is 1:1～1:10.
The concrete steps of the said electrodeposition process of step (3) are:
Catalyst precursor is dispersed in the ethanolic solution of polytetrafluoroethylene (PTFE), stir into prepared Chinese ink shape solution after, prepared Chinese ink shape solution evenly is coated on the glass-carbon electrode, and dry under infrared lamp;
As electrolyte, adopt glass-carbon electrode that three-electrode system will be coated with prepared Chinese ink shape solution as working electrode with the electrolyte solution that contains the platinum presoma, platinum filament and Ag/AgCl electrode as to electrode and reference electrode, prepare catalyst with core-casing structure respectively; In the said platinum presoma quality of platinum be in the catalyst precursor catalyst gross mass 1%～15%.
Said platinum presoma is chloroplatinic acid or dichloro four ammino platinum; The pH of electrolyte solution is 3～6.
Can also add in polyethylene glycol, lead acetate, citric acid, natrium citricum or the softex kw more than one in the said electrolyte.
Said electrodeposition process comprises cyclic voltammetry, constant current pulsed deposition, constant potential pulsed deposition, constant current successive sedimentation method or batch (-type) electric current sedimentation.
The concrete steps of the said immersion reduction method of step (3) are:
Complexing agent is added in the mixed solution of ethanolic solution or ethanol and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, remove ethanol residual in the dereaction after resulting decorating film oven dry back grind; Again under hydrogen atmosphere in 100 ℃～180 ℃ following reductase 12 h～4h, promptly obtain catalyst with core-casing structure; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate.
Compared with prior art, the present invention has the following advantages:
1, the present invention is a kernel with simple substance such as ruthenium, palladium, iron, cobalt, nickel, copper, tin, iridium, gold, silver or its many metal alloys; Simple substance platinum behind the reducing agent is covered core surface through the mode that deposits; And be carried on the carbon carrier of high-specific surface area; Formation is shell with platinum, with simple substance such as metal Ru, palladium, iron, cobalt, nickel, copper, tin, iridium, gold, silver or its many metal alloys nucleocapsid structure that is kernel; Under low platinum carrying capacity, obtain high catalytic activity catalyst; Realized the low carrying capacity of platinum and the high activity of catalyst, effectively solved the cost of platinum based catalyst and the contradiction between the performance, had crucial meaning for solving the present problem that exists of fuel cell.
2, the present invention has carried out stabilization processes to catalyst precursor (nuclear), thereby the catalyst with core-casing structure of preparation has high stability.
3, electrodeposition process according to the invention prepares catalyst with core-casing structure, can when reducing the Pt carrying capacity greatly, activity of such catalysts significantly improved.
4, Preparation of catalysts of the present invention, technology is simple, and is with short production cycle, and easy control of reaction conditions is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 (a) is the TEM figure that embodiment 2 prepared Ru/C examine;
Fig. 1 (b) is the TEM figure of the prepared RuPt/C catalyst of embodiment 2;
Fig. 2 is the XRD figure of prepared Ru/C nuclear, RuPt/C catalyst and commercial JM4100 Pt/C catalyst of embodiment 2;
Fig. 3 is that the prepared homemade PtRu/C alloy catalyst of nucleocapsid structure RuPt/C catalyst and laboratory of PtRu/CE-TEK commercial catalysts, embodiment 2 is at 0.5MH
2S0
4Linear scan figure in the solution;
Fig. 4 is that the prepared homemade PtRu/C alloy catalyst of nucleocapsid structure RuPt/C catalyst and laboratory of PtRu/CE-TEK commercial catalysts, embodiment 2 is at 0.5MH
2S0
4+ 0.5MCH
3Linear scan figure in the OH solution;
Fig. 5 is that the prepared homemade PtRu/C alloy catalyst of nucleocapsid structure RuPt/C catalyst and laboratory of PtRu/CE-TEK commercial catalysts, embodiment 2 is at 0.5MH
2S0
4CO stripping voltammogram in the solution;
Fig. 6 is for being negative electrode with the JM4100Pt/C catalyst, does anode catalyst with the embodiment 2 prepared homemade PtRu/C catalyst in nucleocapsid structure RuPt/C catalyst, laboratory respectively and the membrane electrode for preparing, at H
2Electrode test figure in/air Proton Exchange Membrane Fuel Cells (PEMFC) monocell.
The specific embodiment
To combine specific embodiment and accompanying drawing that the present invention is further specified below, but be not limited thereto.
The catalyst that each embodiment is prepared, its XRD test is on day island proper Tianjin XD-3X of company x ray diffractometer x, to carry out, test voltage is 35kV; Electric current is 30mA, and sweep speed is 4
o/ min; Its active component size is to produce the JEM-100CXII transmission electron microscope through Japan to observe, and test voltage is 20～120KV; Its electro-chemical test carries out on electrochemical workstation (ZahnerIM6e, Germany), and the electrolyte that uses is 0.5mol/LH
2S0
4Solution or 0.5mol/LH
2S0
4+ 0.5mol/LCH
30H solution.
The homemade PtRu/C alloy catalyst in laboratory adopts the preparation of high pressure organic sol method.
Embodiment 1 PdPt/C Preparation of catalysts
The 180mg natrium citricum is added in 15mL ethylene glycol (EG) solution, and magnetic agitation dissolves it more than the ultrasonic 0.5h fully.In solution, drip 2.15mLPdCl then
2/ EG (PdCl
2Mass concentration be 20mg/ml) solution; Ultrasonic, mix after, add the good 100mgVulcanXC-72 carbon black of preliminary treatment again, ultrasonic, mix after; Use 5%KOH/EG solution; The pH value of regulator solution is 9, at last gained liquid is transferred in the autoclave, in 160 ℃ of reaction 8h; After reaction finishes, be cooled to room temperature, using mass concentration is that 5% diluted nitric acid aqueous solution is regulated after pH value is 5, washs to the solution detection less than Cl with secondary water washing
-Till, 70 ℃ of vacuum drying obtain catalyst precursor to weight, i.e. Pd/C nuclear;
With the aforementioned catalyst precursor for preparing (Pd/C nuclear) at N
2Under the gas condition, 120 ℃ of stabilization processes 1h;
Take by weighing the 24mg natrium citricum and add in the 10mLEG solution, stir, ultrasonicly dissolve fully until it; In solution, dropwise add 0.85mLH again
2PtCl
6/ EG (mass concentration is 20mg/ml) solution; Ultrasonic, mix after, add the catalyst precursor 50mg after the aforementioned stabilization processes, ultrasonic, mix after; Using the pH value of 5%KOH/EG solution regulator solution is 9.3; After stirring, ultrasonic being uniformly dispersed, change in the polytetrafluoroethylene (PTFE) autoclave 120 ℃ of reaction 6h over to; Reaction finishes, and is to be cooled to room temperature, with rare HNO of 5% mass concentration
3It is 4 that the aqueous solution is regulated the pH value, and secondary water washing is washed and the filtering reaction system again, and till the no Cl-of detection, the gained filter cake obtains nucleocapsid structure PdPt/C catalyst 80 ℃ of drying under vacuum overnight.
Through measuring, in the nucleocapsid structure PdPt/C catalyst, Pt accounts for 5% of catalyst gross mass; Pd accounts for 20% of catalyst gross mass.The average grain diameter size of active component is 3.4nm, compares hydrogen reduction half current potential of the PdPt/C catalyst 8mV that shuffled with commercial Pt/C (0.558V).
Embodiment 2 RuPt/C Preparation of catalysts
The 296mg natrium citricum is added in the mixed solution of 40 mL glycerine and water (volume ratio of glycerine and water is 3:1), magnetic agitation, ultrasonic each 0.5h dissolves natrium citricum fully; The RuCl that in solution, dropwise adds 5.3 mL then
3/ H
2O solution (RuCl
3Mass concentration 20mgmL
-1), ultrasonic, mix after, add the 300 mg Vulcan XC-72 carbon blacks of crossing through oxidation processes again, ultrasonic, stir mix after, use 5%KOH/H
2The pH value of O solution regulator solution is 9, gained liquid is transferred in the autoclave, in 160 ℃ of reaction 12h; Reaction finishes, and is to be cooled to room temperature, washs and the filtering reaction system with secondary water washing, to filtrating, detects less than Cl
-Till, the gained filter cake to weight, obtains catalyst precursor 80 ℃ of vacuum drying, i.e. Ru/C nuclear;
With the aforementioned catalyst precursor for preparing (Ru/C nuclear) at N
2Under the gas condition, 140 ℃ of stabilization processes 1h;
Take by weighing the 45mg natrium citricum and add in the 10mLEG solution, stir, ultrasonicly dissolve fully until it; In solution, dropwise add 1.6mLH again
2PtCl
6/ EG solution, ultrasonic, mix after, add the catalyst precursor 100mg after the aforementioned stabilization processes; Ultrasonic, mix after, with 5% KOH/EG solution, the pH value of regulator solution is 9.3; Place micro-wave oven at last, moderate heat reduction reaction 1min; After reaction finishes, to be cooled to room temperature, wash and filter the reactant liquor in the micro-wave oven with secondary water washing, to filtrating, detect less than Cl
-Till, the gained filter cake to weight, obtains nucleocapsid structure RuPt/C catalyst 80 ℃ of vacuum drying.
Through measuring, Pt accounts for 10.7% of catalyst gross mass in the RuPt/C catalyst with core-casing structure, and Ru accounts for 10.7% of catalyst gross mass.
Respectively Ru/C nuclear and nucleocapsid structure RuPt/C catalyst are carried out TEM scanning, shown in Fig. 1 (a) and Fig. 1 (b), as can be seen from the figure catalyst is more even in the carbon dust surface distributed.We carry out size statistics back to it and find that the average grain diameter size of Ru/C nuclear and RuPt/C catalyst is respectively 2nm and 2.5nm.
Simultaneously Ru/C nuclear and nucleocapsid structure RuPt/C catalyst are carried out XRD analysis, as shown in Figure 2, wide diffraction maximum shows that catalyst has smaller particle size among the figure.40.04 °, 44 ° of (111) crystal face and Ru (101) crystal faces of representing the Pt catalyst of face-centred cubic structure respectively.According to Scherre formula: Bee ,=size that 0.94 λ/rcos θ calculates active component is: Ru/C is 2.2nm, and RuPt/C is 2.6nm, and this is consistent with the result that TEM obtains.
Fig. 3 is that the homemade PtRu/C alloy catalyst of prepared nucleocapsid structure RuPt/C catalyst of PtRu/CE-TEK commercial catalysts, present embodiment and laboratory is at 0.5MH
2S0
4Linear scan figure in the solution, sweep speed: 20mV/s.Calculate: the electrochemically active specific surface area of RuPt/C (ECSA) is 116.6m
2g
-1Pt is respectively PtRu/CE-TEK (46.5m
2g
-1Pt) and PtRu/C (97.2m
2g
-1Pt) 2.5 times and 1.2 times.
Fig. 4 is that above-mentioned three kinds of catalyst are at 0.5MH
2S0
4+ 0.5MCH
3Linear scan figure in the OH solution, sweep speed: 20mV/s.As can be seen from the figure, the oxidation methyl alcohol peak current density of RuPt/C is 0.365 A mg
-1Pt is respectively PtRu/CE-TEK and PtRu/C 2.37 times and 1.61 times.
Fig. 5 is that above-mentioned three kinds of catalyst are at 0.5MH
2S0
4CO stripping voltammogram in the solution, sweep speed: 20mV/s.As can be seen from the figure, the order of anti-CO poisoning capability is RuPt/C>the homemade PtRu/C in laboratory>the PtRu/CE-TEK commercial catalysts.
With the JM4100Pt/C catalyst is cathod catalyst, respectively with the homemade PtRu/C alloy catalyst in present embodiment prepared nucleocapsid structure RuPt/C, laboratory do anode catalyst prepare membrane electrode, at H
2In/air Proton Exchange Membrane Fuel Cells (PEMFC) monocell two electrodes are tested.Battery temperature is that empty back pressure 30psi of 70 ℃, hydrogen and relative humidity are 100%, and test result is as shown in Figure 6.
When battery operated voltage is 0.7V, be that the monocell current density of anode catalyst reaches 712mAcm with RuPt/C
-2, be monocell current density (the 600 mA cm of anode catalyst than PtRu/C under the same terms
-2) exceed 16%; When 70 ℃ of battery temperatures, be that the monocell maximum power density of anode catalyst reaches 0.685Wcm with RuPt/C
– 2, be the monocell maximum power density (0.628Wcm of anode catalyst than PtRu/C under the same terms
– 2) exceed 10%.It is thus clear that the membrane electrode that the RuPt/C nucleocapsid catalyst for preparing with the present invention prepares has shown more performance.
Embodiment 3 RuPt/C Preparation of catalysts
With in the mixed solution of 296mg natrium citricum adding 40mL glycerine and water (volume ratio of glycerine and water is 3:1), magnetic agitation, ultrasonic each 0.5h dropwise adds 5.3mLRuCl again in solution
3/ H
2O solution (RuCl
3Mass concentration be 20mgmL
-1).Ultrasonic, mix after, add the 300mgVulcanXC-72 carbon black after oxidation processes, after ultrasonic the mixing, use 5%KOH/H
2O solution, the pH value of regulator solution is 9, then gained liquid is transferred in the autoclave, in 160 ℃ of reaction 12h; After reaction finished, the reactant liquor in the autoclave is washed and filtered to the room temperature that arrives to be cooled with secondary water washing, to filtrating, detects less than Cl
-Till, the gained filter cake to weight, obtains catalyst precursor (being Ru/C nuclear) in 70 ℃ of vacuum drying.
With the aforementioned catalyst precursor for preparing (Ru/C nuclear) at N
2Under the gas condition, 140 ℃ of stabilization processes 1h;
With the aforementioned stabilized catalyst processed presoma Ru/C of 3mg, (mass ratio Nafion:Ru/C=1:3) becomes the prepared Chinese ink shape in the solution, prepared Chinese ink is coated on the glass-carbon electrode uniformly, and infrared lamp is dry down to be dispersed in the 1mLNafion/ isopropyl alcohol; The glass-carbon electrode that will scribble Ru/C then is as working electrode; Pt silk and Ag/AgCl electrode are respectively electrode and reference electrode, as electrolyte, and add natrium citricum (mol ratio therein with the dichloro four ammino platinum solution of 0.1mol/L; Natrium citricum: Pt=2.5:1), the Na of 0.1mol/L
2SO
4Solution, the pH that regulates electrolyte is 4, adopts constant current pulse electrodeposition legal system to be equipped with nucleocapsid structure RuPt/C catalyst at last.
Through measuring, Pt accounts for 5% of whole catalyst in the catalyst, atomic ratio Ru:Pt=5:1.Through the electrochemically active specific surface area (ECSA) that calculates this catalyst up to 520.5m
2g
-1Pt, oxidation methyl alcohol peak current density is up to 3.78Amg
-1Pt is that commercial JM4100Pt/C (is 0.35Amg
-1Pt) 10.8 times.
Embodiment 4 PdFePt/C Preparation of catalysts
Claim to stir in the 50m1 round-bottomed flask that 294.3 mg natrium citricums join 25m1EG, more than the ultrasonic 0.5h it is dissolved fully; Add 106 mg iron chloride again, add 1mLPdCl simultaneously
2/ EG (containing Pd20mg/mL), ultrasonic, be stirred to fully dissolving after, add CNT 100mg again; Stir, ultrasonic it fully evenly mixed; The pH that uses 5%KOH/EG solution regulator solution then is 10, more above-mentioned solution is transferred in the autoclave, reacts 8h down in 160 ℃.After reaction finishes, to be cooled to room temperature, wash and filter the reactant liquor in the autoclave with secondary water washing, to filtrating, detect less than Cl
-Till, the gained filter cake to weight, gets catalyst precursor in 70 ℃ of vacuum drying, (being PdFe/C nuclear).
With the aforementioned catalyst precursor for preparing (PdFe/C nuclear) at N
2Under the gas condition, 120 ℃ of stabilization processes 1.5h;
With the stabilized catalyst processed presoma of 3mg (PdFe/C nuclear), (mass ratio, Nafion: isopropyl alcohol=1:3) become the prepared Chinese ink shape in the solution is coated in prepared Chinese ink on the glass-carbon electrode drying under the infrared lamp uniformly to be dispersed in the 1mLNafion/ isopropyl alcohol.The electrode that will scribble PdFe/C then is as working electrode; Pt silk and Ag/AgCl electrode are respectively electrode and reference electrode, as electrolyte, and add natrium citricum (mol ratio therein with the 0.1mol/L platinum acid chloride solution; Natrium citricum: Pt=2.5:1), the Na of 0.1mol/L
2SO
4Solution, the pH that regulates electrolyte is 4, adopts constant potential pulse electrodeposition legal system to be equipped with nucleocapsid structure PdFePt/C catalyst at last.
Through measuring, Pt accounts for 6.9% of whole catalyst in the PdFePt/C catalyst, and Pd accounts for 13% of catalyst gross mass, and Fe accounts for 11% of catalyst gross mass.The average grain diameter size of active component is 2.8nm, compares hydrogen reduction half current potential of the PdFePt/C catalyst 27mV that shuffled with commercial Pt/C (0.558 V).
Embodiment 5 PdCoPt/C Preparation of catalysts
The 232.0mg natrium citricum is joined in the 50mL beaker, adds 20mLEG again, stir, ultrasonic each make its all dissolving fully more than the 0.5h; Add 1.82mLPdCl simultaneously to it again
2/ EG solution and 32.3mg cobalt chloride; Stir, ultrasonic it is dissolved fully after; Add the VulcanXC-72 carbon black 100mg after oxidation processes again, ultrasonic, mix after, using the pH value of 5%KOH/EG solution regulator solution is 9; At last solution is transferred in the autoclave, reacted 8h down in 160 ℃.After reaction finishes, to be cooled to room temperature, with secondary water washing wash and the filtering reaction still in reactant liquor, to filtrating, detect less than Cl
-Till, the gained filter cake to weight, gets catalyst precursor (being PdCo/C nuclear) in 70 ℃ of vacuum drying;
With the aforementioned catalyst precursor for preparing (PdCo/C nuclear) at N
2Under the gas condition, 140 ℃ of stabilization processes 1h;
With 3mg through the catalyst precursor PdCo/C of stabilization processes, be dispersed in the 1mLNafion/ isopropyl alcohol (mass ratio, Nafion: isopropyl alcohol=1:3) become the prepared Chinese ink shape in the solution, prepared Chinese ink is coated on the glass-carbon electrode uniformly, infrared lamp is dry down; The electrode that will scribble PdCo/C then is as working electrode; Pt silk and Ag/AgCl electrode are respectively electrode and reference electrode, as electrolyte, and add citric acid (mol ratio therein with 0.1mol/L dichloro four ammino platinum solution; Citric acid: Pt=2.5:1), the Na of 0.1mol/L
2SO
4Solution, the pH that regulates electrolyte is 4, adopts constant current successive sedimentation legal system to be equipped with nucleocapsid structure PdCoPt/C catalyst.
Through measuring, Pt accounts for 3.8% of catalyst gross mass in the PdCoPt/C catalyst, and Pd accounts for 12% of catalyst gross mass, and Co accounts for 14% of catalyst gross mass.The average grain diameter of active component size 3nm compares with commercial Pt/C, hydrogen reduction half current potential of the PdCoPt/C catalyst 19mV that shuffled.
Embodiment 6 PdCuPt/C Preparation of catalysts
The 239.4mg natrium citricum is joined in the 50mL beaker, add 20 m1EG again, ultrasonic, stir each more than the 0.5h, make its all dissolving fully; Add 1.82mLPdCl simultaneously to it then
2/ EG solution and 34.7mg copper chloride stir, ultrasonic each 0.5h all after the dissolving, adds the CNT 100mg after oxidation processes again, and be ultrasonic, mix; The pH value of using 5%KOH/EG solution regulator solution again is 9, at last solution is transferred in the autoclave, and 160 ℃ are reacted 8h down.After reaction finishes, to be cooled to room temperature, with secondary water washing wash and the filtering reaction still in reactant liquor, to filtrating, detect less than Cl
-Till, the gained filter cake to weight, gets catalyst precursor (PdCu/C nuclear) in 70 ℃ of vacuum drying;
With the aforementioned catalyst precursor for preparing (PdCu/C nuclear) at N
2Under the gas condition, 140 ℃ of stabilization processes 1 h;
With the catalyst precursor PdCu/C of the stabilized processing of 3mg, be dispersed in the 1mLNafion/ isopropyl alcohol (mass ratio, Nafion: become the prepared Chinese ink shape in the solution of isopropyl alcohol=1:3), prepared Chinese ink is coated on the glass-carbon electrode uniformly, infrared lamp is dry down; The glass-carbon electrode that will scribble PdCu/C then is as working electrode; Pt silk and Ag/AgCl electrode are respectively electrode and reference electrode, as electrolyte, and add citric acid (mol ratio therein with 0.1mol/L dichloro four ammino platinum solution; Citric acid: Pt=2.5:1), the Na of 0.1mol/L
2SO
4Solution, the pH that regulates electrolyte is 4, adopts batch (-type) electric current multistage electrodeposition process to prepare nucleocapsid structure PdCuPt/C catalyst at last.
Through measuring, in the PdCuPt/C catalyst, Pt accounts for 4.5% of catalyst gross mass, and Pd accounts for 15% of catalyst gross mass, and Cu accounts for 11% of catalyst gross mass.The average grain diameter of active component size 3.2nm compares with commercial Pt/C, hydrogen reduction half current potential of the PdCuPt/C catalyst 18mV that shuffled.
Embodiment 7 PdNiPt/C Preparation of catalysts
The 243.1mg natrium citricum is joined in the 50 ml round-bottomed flasks, adds 20m1EG again, stir, ultrasonic each make its all dissolving fully more than the 0.5h, add 1.83mLPdCl simultaneously to it then
2/ EG solution and 45.9mg nickel chloride stir, ultrasonicly add the CNT 100mg that crosses through oxidation processes again to dissolving fully, ultrasonic, mix after, using the pH value of 5%KOH/EG solution regulator solution is 10; Above-mentioned solution is transferred in the autoclave, and 160 ℃ are reacted 7h down.After reaction finishes, to be cooled to room temperature, with secondary water washing wash and the filtering reaction still in reactant liquor, to filtrating, detect less than Cl
-Till, the gained filter cake to weight, gets catalyst precursor (PdNi/C nuclear) in 70 ℃ of vacuum drying;
With the aforementioned catalyst precursor for preparing (PdNi/C nuclear) at N
2Under the gas condition, 140 ℃ of stabilization processes 1h;
Take by weighing 12.3 mg natrium citricums and add 5mLH
2Among the O, stir, ultrasonicly dissolve fully until it.In solution, add 8.6mgH then
2PtCl
6H
2O, ultrasonic, be stirred to fully dissolving after, add above-mentioned stabilized catalyst processed presoma 50mg, ultrasonic, mix after, place 40 ℃ of water-baths dippings, evaporate to dryness, and then after the dry thing that will obtain grinds, place H
2In the stream, 200 ℃ of reductase 12 h get the PdNiPt/C catalyst with core-casing structure.
Through measuring, in the PdNiPt/C catalyst, Pt accounts for 4.4% of catalyst gross mass; Pd accounts for 15% of catalyst gross mass, and Ni accounts for 12% of catalyst gross mass.The average grain diameter of active component size 4.8nm compares with commercial Pt/C, hydrogen reduction half current potential of the PdPt/C catalyst 12mV that shuffled.
Embodiment 8 PdPtPt/C Preparation of catalysts
Claim that the 170mg natrium citricum joins in the 50m1 round-bottomed flask of 25m1EG, stir, more than the ultrasonic 0.5h it is dissolved fully; Add 0.8mLH more simultaneously
2PtCl
6/ EG solution (containing Pt20mg/mL) and 1.8mLPdCl
2/ EG solution (containing Pd20mg/mL); Ultrasonic, be stirred to mix fully after; Add the CNT 100mg that crosses through oxidation processes again, stir, ultrasonic it fully evenly mixed, the pH that uses 5%KOH/EG solution regulator solution then is 9; Again above-mentioned solution is transferred in the autoclave, reacted 6h down in 140 ℃.After reaction finishes, to be cooled to room temperature, with secondary water washing wash and the filtering reaction still in reactant liquor to filtrating in detect less than Cl
-Till, the gained filter cake to weight, gets catalyst precursor in 70 ℃ of vacuum drying, (being PdPt/C nuclear);
With the aforementioned catalyst precursor for preparing (PdPt/C nuclear) at N
2Under the gas condition, 120 ℃ of stabilization processes 1h;
With the stabilized catalyst processed presoma of 3mg (PdPt/C nuclear), (mass ratio, Nafion: isopropyl alcohol=1:3) become the prepared Chinese ink shape in the solution is coated in prepared Chinese ink on the glass-carbon electrode drying under the infrared lamp uniformly to be dispersed in the 1mLNafion/ isopropyl alcohol.The electrode that will scribble PdPt/C then is as working electrode; Pt silk and Ag/AgCl electrode are respectively electrode and reference electrode, as electrolyte, and add natrium citricum (mol ratio therein with the 0.1mol/L platinum acid chloride solution; Natrium citricum: Pt=2.5:1), the Na of 0.1 mol/L
2SO
4Solution, the pH that regulates electrolyte is 4, adopts cyclic voltammetry to prepare nucleocapsid structure PdPtPt/C catalyst at last.
Through measuring, Pt accounts for 9.5% of whole catalyst in the PdPtPt/C catalyst, and Pd accounts for 16% of catalyst gross mass; The average grain diameter size of active component is 2.5nm; Compare with commercial Pt/C, the methanol oxidation activity of PdPtPt/C catalyst has improved 50%, the hydrogen reduction half current potential 17mV that shuffles.
Claims (9)
1. preparation method who is used for the catalyst with core-casing structure of low-temperature fuel cell; Said catalyst with core-casing structure is shell with platinum; With more than one metal alloys in metal Ru, palladium, iron, cobalt, nickel, copper, tin, iridium, gold and the silver is kernel; Shell and kernel are carried on carbon carrier jointly, it is characterized in that preparation process is following:
(1) preparation of nuclear
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds metal chloride or metal nitrate again; Ultrasonic, mix after; Add the carbon carrier of crossing through oxidation processes again, stir and ultrasonic to being uniformly dispersed, using mass concentration then is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again in the autoclave and react 4h～12h down in 100 ℃～160 ℃; After reaction finishes, treat that autoclave is cooled to room temperature, using mass concentration is that the pH value that 5%～10% diluted nitric acid aqueous solution is regulated autoclave internal reaction liquid is 4～6; Wash and filtering reacting liquid with secondary water washing again, do not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst precursor 60 ℃～80 ℃ following vacuum drying; The carbon carrier quality is equivalent to 4～8 times of the total theoretical metal quality of metal chloride or metal nitrate reduction back; The mol ratio of total metal ion is 1:1～1:10 in polyalcohol reducing agent and metal chloride or the metal nitrate; The mol ratio of total metal ion is 2:1～2.5:1 in complexing agent and metal chloride or the metal nitrate; The mol ratio of metal chloride or metal nitrate and polyalcohol reducing agent is 1:0.3～1:3; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol;
(2) stabilization processes of nuclear
With catalyst precursor under inert atmosphere conditions, 100 ℃～150 ℃ following stabilization processes 1h～3h;
(3) preparation of shell
Catalyst precursor to handle through step (2) is a kernel, on kernel, prepares shell with immersion reduction method, high pressure organic sol method, microwave method or electrodeposition process, then kernel, shell is carried on the carbon carrier jointly, obtains catalyst with core-casing structure.
2. preparation method according to claim 1 is characterized in that said carbon carrier is Vulcan XC-72 carbon black or CNT.
3. preparation method according to claim 1 is characterized in that the concrete steps of the said high pressure organic sol method of step (3) are:
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid to it again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, using mass concentration is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again in the autoclave and react 4 h～12 h down in 100 ℃～160 ℃; Reaction treats that autoclave is cooled to room temperature after finishing, and the use mass concentration is rare HNO of 5%～10%
3The pH value that the aqueous solution is regulated the reaction under high pressure pot systems is 4～6, washs reaction system with secondary water washing again and does not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst with core-casing structure 60 ℃～80 ℃ following vacuum drying; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate, and the mol ratio of itself and chloroplatinic acid is 2:1～2.5:1; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol, and the mol ratio of itself and chloroplatinic acid is 1:1～1:10.
4. preparation method according to claim 1 is characterized in that the concrete steps of the said microwave method of step (3) are:
Complexing agent is added in the mixed solution of polyalcohol reductant solution or polyalcohol reducing agent and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid to it again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, using mass concentration is that to regulate pH value be 8～10 for 5%～10% alkaline solution; Be placed on again and react 1min～2min in the micro-wave oven; After reaction finished, the question response system was cooled to room temperature, washed reaction system with secondary water washing again and did not have Cl to detecting in the filtrating
-Till, the gained filter cake to weight, promptly obtains catalyst with core-casing structure 60 ℃～80 ℃ following vacuum drying; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate, and the mol ratio of complexing agent and chloroplatinic acid is 2:1～2.5:1; Said polyalcohol reducing agent is ethylene glycol, isopropyl alcohol, glycerine or n-butanol, and the mol ratio of polyalcohol reducing agent and chloroplatinic acid is 1:1～1:10.
5. preparation method according to claim 1 is characterized in that the concrete steps of the said electrodeposition process of step (3) are:
Catalyst precursor is dispersed in the ethanolic solution of polytetrafluoroethylene (PTFE), stir into prepared Chinese ink shape solution after, prepared Chinese ink shape solution evenly is coated on the glass-carbon electrode, and dry under infrared lamp;
As electrolyte, adopt glass-carbon electrode that three-electrode system will be coated with prepared Chinese ink shape solution as working electrode with the electrolyte solution that contains the platinum presoma, platinum filament and Ag/AgCl electrode as to electrode and reference electrode, prepare catalyst with core-casing structure respectively; In the said platinum presoma quality of platinum be in the catalyst precursor catalyst gross mass 1%～15%.
6. preparation method according to claim 5 is characterized in that said platinum presoma is chloroplatinic acid or dichloro four ammino platinum; The pH of electrolyte solution is 3～6.
7. preparation method according to claim 6 is characterized in that in said electrolyte, adding in polyethylene glycol, lead acetate, citric acid, natrium citricum or the softex kw more than one.
8. preparation method according to claim 7 is characterized in that said electrodeposition process comprises cyclic voltammetry, constant current pulsed deposition, constant potential pulsed deposition, constant current successive sedimentation method or batch (-type) electric current sedimentation.
9. according to the described preparation method of claim 1, it is characterized in that the concrete steps of the said immersion reduction method of step (3) are:
Complexing agent is added in the mixed solution of ethanolic solution or ethanol and water, after ultrasonic, stirring is dissolved complexing agent fully, adds chloroplatinic acid again; Ultrasonic, mix after; Add the resulting catalyst precursor of step (2) again, stir and ultrasonic after be uniformly dispersed, remove ethanol residual in the dereaction after resulting decorating film oven dry back grind; Again under hydrogen atmosphere in 100 ℃～180 ℃ following reductase 12 h～4h, promptly obtain catalyst with core-casing structure; Said complexing agent is natrium citricum, citric acid or sodium ethylene diamine tetracetate.
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