CN104475126A - Carbon-supported core-shell type platinum cobalt-platinum catalyst for fuel cells and preparation method for carbon-supported core-shell type platinum cobalt-platinum catalyst - Google Patents
Carbon-supported core-shell type platinum cobalt-platinum catalyst for fuel cells and preparation method for carbon-supported core-shell type platinum cobalt-platinum catalyst Download PDFInfo
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Abstract
The invention relates to a carbon-supported core-shell type platinum cobalt-platinum catalyst for fuel cells and a preparation method for the carbon-supported core-shell type platinum cobalt-platinum catalyst, belonging to the field of electrochemistry. The catalyst comprises the following components in percentage by weight: 60%-90% of a carrier, 1%-20% of cobalt, and 9%-20% of platinum. According to the invention, a mixed solution of ethylene glycol and sodium borohydride acts as a reducing agent, the core-shell type platinum cobalt-platinum catalyst Pt-Co@Pt/C with an ordered structure is prepared by high-temperature annealing treatment. The catalyst with the ordered structure, which is prepared by the invention, has the advantages of low Pt carrying capacity, high catalysis activity, high stability and the like, and the development of fuel cells can be promoted further.
Description
Technical field
The present invention relates to a kind of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst and preparation method thereof, this catalyst is that a kind of carbon carries the orderly hud typed platinum cobalt-platinum catalyst (Pt-Co Pt/C) of nuclear atom arrangement, belongs to electrochemical field.
Technical background
In the face of current global energy crisis, environmental pollution and climate warming problem; be directly that energy conversion efficiency is high, environmental friendliness, energy density advantages of higher because it has for the fuel cell of electric energy by chemical energy, be considered to be expected to alternative regenerative resource most.At present, fuel-cell catalyst is still best with the platinum or its alloy nano catalyst with good resistance to corrosion, excellent electrocatalysis characteristic and chemical property.But, platinum scarcity of resources, expensive, reduce the cost of catalyst, prepare low carrying capacity, high catalytic activity, high stability platinum based catalyst be the key realizing commercializing fuel cells.With relatively inexpensive and aboundresources transition metal or alloy as core, at hud typed platinum nano catalyst prepared by core surface coverage skim Pt (or even monoatomic layer), reduce the use of platinum while increasing substantially catalyst utilization in a large number, effectively reduce fuel cell and widely use catalyst cost.During the shell of Pt as catalyst with core-casing structure, what lattice paprmeter was relatively little check shell Pt produces compression strain effect, and its d center of being with moves down the absorption and the activation that reduce to be conducive to oxygen with surface strain power, therefore improves its work to oxygen reduction reaction.
CN103084175A describes a kind of deficient electromotive force deposition-displacement and prepares carbon load hud typed Pt-Au@Pt catalyst method.The method first uses sodium borohydride reduction gold compound, and obtained load is at the Au/C of carbon surface.Then by Au/C ultrasonic disperse in platinum compound aqueous solution, obtain loaded Pt-Au alloy nanoparticle.By deficient electromotive force deposition, Co atomic deposition is surperficial to Pt-Au alloy nanoparticle, finally with platinum compounds, the Co atom be deposited on Pt-Au alloy is replaced, obtained carbon supported core-shell Pt-Au@Pt nanocatalyst.Catalyst activity prepared by the method is high and stable, and preparation is simple, but cost is higher, and prepared catalyst metallic particle diameter is wayward, wider range.
Sun seminar utilizes liquid phase chemical pyrolysismethod and the high temperature anneal to prepare FePt nanocatalyst orderly in structure.First by pyrolysis iron pentacarbonyl (Fe (CO)
5) and reduction acetylacetone,2,4-pentanedione platinum obtain the FePt nano particle of face-centered cubic (fcc) structure, then at the thermodynamically stable MgO of its surface coverage, the FePt of fcc structure is made to be converted into the structurally ordered hud typed FePt nano particle of face centered tetragonal (fct) by high annealing, finally dissolve MgO at hydrochloric hexadecanethiol (HDT) and oleic acid hexane solution, obtained structurally ordered FePt nanocatalyst.Comparatively business platinum catalyst Pt/C is high for the structure ordering nucleocapsid FePt nanocatalyst catalytic activity that this legal system is standby and stability, good dispersion, but its pt utilization is low, and catalytic activity is still less, and is not suitable at HClO
4catalytic oxidation-reduction.
Summary of the invention
Main purpose of the present invention is to provide one to prepare simply, and cost is lower, and platinum specific area is large, utilization rate is high, the fuel-cell catalyst of high catalytic activity and good stability.
In order to realize above-mentioned purpose of the present invention, by the following technical solutions:
A kind of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst, be specially a kind of fuel cell carbon and carry the orderly hud typed platinum cobalt-platinum alloy catalyst of nuclear atom arrangement, be made up of carrier and active component, its mass percent consists of: carrier carbon: 60% ~ 90%, cobalt: 1 ~ 20%, platinum: 9 ~ 20%.
In above-mentioned catalyst, described carrier carbon is XC-72 carbon black; Active component is structurally ordered platinum cobalt-platinum alloy, and wherein structurally ordered cobalt-platinum alloy is core, and platinum layer is shell.
Another order of the present invention is to provide the preparation method of the orderly platinum cobalt-platinum alloy catalyst of a kind of new structure.
A preparation method for fuel cell carbon supported core-shell platinum cobalt-platinum catalyst, comprises the steps:
(1) in powdered carbon, add ethylene glycol (EG), carry out ultrasonic disperse, then the ethylene glycol solution of soluble cobalt and the ethylene glycol solution of chloroplatinic acid is under agitation added respectively, make the mass ratio of carbon in mixed solution, cobalt ions and platinum ion for (60 ~ 90): (1 ~ 20): (9 ~ 20), magnetic agitation;
(2) with the ethylene glycol solution of potassium hydroxide, the pH of above-mentioned mixed solution is adjusted to 9 ~ 11, after stable, 80 DEG C ~ 120 DEG C are heated under nitrogen atmosphere protection, stirring condition, dropwise add the ethylene glycol solution of sodium borohydride, keep whole course of reaction pH constant, after reaction, obtain carbon and carry cobalt-platinum alloy slurries;
(3) step (2) gained reactant liquor is carried out centrifugation by ethanol, deionized water as washing agent successively wash to neutrality and without chlorion, obtain carbon and carry cobalt-platinum alloy particle Pt-Co/C;
(4) carbon that step (3) obtains is carried the vacuum drying of cobalt-platinum alloy particle, then at oven drying;
(5) carbon that step (4) obtains is carried cobalt-platinum alloy particle under a nitrogen atmosphere, utilize tube furnace to carry out the high temperature anneal, obtain structurally ordered hud typed carbon and carry platinum cobalt-platinum catalyst Pt-Co@Pt/C.
In step (1), described soluble cobalt is cobalt chloride, cobalt nitrate or cobaltous sulfate, and described carbon dust is XC-72 conductive black.
In the ethylene glycol solution of described chloroplatinic acid, Pt ion concentration is 0.01 ~ 0.1 mol/L.
Described ultrasonic disperse at room temperature carries out, and the ultrasonic disperse time is 0.5 ~ 2h; The magnetic agitation time is 2 ~ 4h.
Preferably, in 60 ~ 90mg powdered carbon, add 30 ~ 50 milliliters of ethylene glycol (EG).
In step (2), the ethylene glycol solution of sodium borohydride is the sodium borohydride mixture (NaBH being dissolved in ethylene glycol
4/ EG), be the reducing agent of reaction, its concentration is 1 ~ 3 mol/L, and the reaction time is 2 ~ 4h.The volume ratio of the ethylene glycol solution of sodium borohydride and step (1) gained mixed solution is 1:(2 ~ 5).
Preferably, in above-mentioned mixed solution, the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol is dropwise added
4, 2M) and solution.
In step (4), described vacuum drying is vacuum drying 24 ~ 35h at condensation temperature-60 DEG C ~-40 DEG C.Oven drying temperature is 80 DEG C, and drying time is 22 ~ 26h.
In step (5), the temperature of described high annealing is 600 DEG C ~ 1000 DEG C, and the time is 2 ~ 6h.
By carrying out structural characterization to prepared product, proving that it is is carrier with carbon, and active metal is carried on carbon surface, wherein active metal be with structure ordering platinum cobalt alloy be core, the platinum core-shell type nano material that is shell, particle diameter is 5 ~ 10nm, and electron microscopic observation finds distribution uniform.
Advantage of the present invention:
The present invention take ethylene glycol as solvent, and the mixed liquor of ethylene glycol and sodium borohydride is reducing agent, is synthesized the Pt-Co/C alloy of different atomic ratio by the amount controlling to add Pt and Co presoma, regulates the pH of course of reaction to control alloy particle diameter.Ethylene glycol can generate a kind of Na with mixing of sodium borohydride
+b
-(OCH
2cH
2oH)
4, its reducing power is stronger than ethylene glycol, platinum and cobalt atom can be restored jointly, obtain Pt-Co alloy.Meanwhile, the ethylene glycol that viscosity is larger can be used as stabilizing agent, effectively can control grain growth in course of reaction, obtained more short grained nanocatalyst.By above-mentioned Pt-Co/C alloy under inert gas conditions, control calcining heat, time by tube furnace, suitable the high temperature anneal is carried out to it, obtained coreshell type structure ordering Pt-Co@Pt/C catalyst.
The present invention adopts ethylene glycol and sodium borohydride mixed liquor to be reducing agent, effectively obtained certain atomic ratio and the less Pt-Co/C Nanoalloy material of particle diameter; At N
2under protection; utilize temperature-programmed technique; the high temperature anneal is carried out to produced Nanoalloy; obtain the super crystal lattice material of Pt and Co ordered arrangement on atomic level; gained nano particle take Pt as shell; structure ordering Pt-Co alloy is core, greatly can improve utilization rate and the stability of precious metals pt.And calcination process uses N
2as protective gas, significantly reduce preparation cost, will further developing of ordering structure catalyst be promoted.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the XRD figure of Pt-Co/C prepared by the present invention.
Fig. 2 be the fcc structure Pt-Co@Pt/C for preparing of the present invention under inert gas conditions, after 750 DEG C of high-temperature process 2h, obtain the XRD figure of face centered tetragonal (fct) configuration Pt-Co@Pt/C-750 alloy.
Fig. 3-1 and Fig. 3-2 is high resolution electron microscopy figure of Pt-Co/C.
Fig. 4-1 and Fig. 4-2 is high resolution electron microscopy figure of Pt-Co/C gained Pt-Co@Pt/C-750 after 750 DEG C of high-temperature process.
Detailed description of the invention
The hud typed platinum cobalt-platinum catalyst of fuel cell of the present invention is made up of carrier and active component, carrier is XC-72 carbon black, active component is structurally ordered platinum cobalt-platinum alloy, wherein structurally ordered cobalt-platinum alloy is core, platinum layer is shell, its material quality percentage consists of: carrier: 60% ~ 90%, cobalt: 1 ~ 20%, platinum: 9 ~ 20%.
The fuel cell of the present invention preparation method of hud typed platinum cobalt-platinum catalyst comprises two large steps, first utilizes co-reducing process, the concentration of being reacted by control, pH, reaction temperature and time, and synthesis carbon carries type cobalt-platinum alloy Pt-Co/C catalyst; Then, the catalyst upper step obtained is at N
2lower high annealing prepares structurally ordered hud typed platinum cobalt-platinum catalyst.Concrete steps are as follows:
(1) take 60 ~ 90mg charcoal ball and be placed in tripod bottle, add 30 ~ 50 milliliters of ethylene glycol (EG), ultrasonic disperse 0.5 ~ 1h at ambient temperature, then the ethylene glycol solution of soluble cobalt and the ethylene glycol solution of chloroplatinic acid is under agitation added respectively, the mass ratio of carbon in mixed solution, cobalt ions and platinum ion is made to be 6 ~ 9:1.5:3, magnetic agitation 3h;
(2) with the potassium hydroxide solution being dissolved in ethylene glycol, the pH of above-mentioned mixed solution is adjusted to 9 ~ 11; after a period of stabilisation; under nitrogen atmosphere protection, strong agitation, be heated to 80 DEG C ~ 120 DEG C, dropwise add the sodium borohydride (NaBH that 15 ~ 20ml is dissolved in ethylene glycol
4, 2M) and solution, keep whole course of reaction pH constant, the reaction time is 3h, obtains carbon and carries cobalt-platinum alloy slurries;
(3) step (2) gained reactant liquor is carried out centrifugation with ethanol, ultra-pure water as washing agent according to this wash to neutrality and without chlorion, obtain carbon and carry cobalt-platinum alloy particle;
(4) carbon that step (3) obtains is carried cobalt-platinum alloy particle vacuum drying 24h, then at 180 DEG C of dry 1h, obtain the irregular Pt-Co/C of Atomic Arrangement;
(5) carbon that step (4) obtains is carried cobalt-platinum alloy particle under logical condition of nitrogen gas, utilize tube furnace to carry out the high temperature anneal, obtain the hud typed carbon of structure ordering and carry platinum cobalt-platinum catalyst Pt-Co@Pt/C.
Embodiment 1
(1) take 80mg carbon dust (XC-72 carbon black, as follows) in triangular flask, add 40ml ethylene glycol, at ambient temperature ultrasonic 1 ~ 2h, make carbon dust be dispersed in ethylene glycol;
(2) by 7.39mg CoCL2 6H2O (CoCl
26H
2and 48.27mg chloroplatinic acid (H O)
2ptCl
6h
2o) ethylene glycol is dissolved in and ultrasonic 1h makes it even.Then, under room temperature and strong agitation, dropwise add the presoma of above-mentioned Pt and Co, stir 3h;
(3) under room temperature and magnetic agitation, regulate the pH to 10 of above-mentioned reacting slurry with 1M KOH/EG solution, and stablize 0.5h;
(4) under nitrogen atmosphere protection, magnetic agitation, utilize oil bath pan to heat above-mentioned reactant liquor, make its temperature reach 80 DEG C, then slowly dropwise add the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol
4/ EG, 2M) solution, make it react 3h;
(5) reaction makes it be down to room temperature after terminating, and utilizes ethanol and deionized water to carry out centrifugation washing to gained slurries respectively, until without chlorion (Cl
-) and neutrality till.Again gained solid is carried out suction filtration, vacuum drying 24h at temperature-60 DEG C; Then at 80 DEG C of oven drying 24h, Pt-Co/C is obtained;
(6) the above-mentioned alloy material of 50mg is taken in porcelain boat, at N
2under condition, utilize tube furnace to its high-temperature process 2 hours at 750 DEG C, obtain the Pt-Co/C@Pt/C catalyst that structure ordering is hud typed.
Embodiment 2
(1) take 90mg carbon dust in triangular flask, add 40ml ethylene glycol, at ambient temperature ultrasonic 1 ~ 2h, make carbon dust be dispersed in ethylene glycol;
(2) by 3.70mg CoCL2 6H2O (CoCl
26H
2and 23.14mg chloroplatinic acid (H O)
2ptCl
6h
2o) ethylene glycol is dissolved in and ultrasonic 1h makes it even.Then, under room temperature and strong agitation, dropwise add the presoma of above-mentioned Pt and Co, stir 3h;
(3) under room temperature and magnetic agitation, regulate the pH to 10 of above-mentioned reacting slurry with 1M KOH/EG, and stablize 0.5h;
(4) under nitrogen atmosphere protection, magnetic agitation, utilize oil bath pan to heat above-mentioned reactant liquor, make its temperature reach 80 DEG C, then slowly dropwise add the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol
4/ EG, 2M) solution, make it react 3h;
(5) reaction makes it be down to room temperature after terminating, and utilizes ethanol and deionized water to carry out centrifugation washing to gained slurries, until without Cl respectively
-till and neutral.Again gained solid is carried out suction filtration, vacuum drying 25h at condensation temperature-45 DEG C, 80 DEG C of oven drying 24h, obtain Pt-Co/C;
(6) take in the above-mentioned alloy material of 50mg and porcelain boat, then N
2under condition, utilize tube furnace to its high-temperature process 2 hours at 750 DEG C, obtain the Pt-Co@Pt/C catalyst that structure ordering is hud typed.
Embodiment 3
(1) take 60mg carbon dust in triangular flask, add 40ml ethylene glycol, at ambient temperature ultrasonic 1 ~ 2h, make carbon dust be dispersed in ethylene glycol;
(2) by 14.78mg CoCL2 6H2O (CoCl
26H
2and 96.54mg chloroplatinic acid (H O)
2ptCl
6h
2o) ethylene glycol is dissolved in and ultrasonic 1h makes it even.Then, under room temperature and strong agitation, dropwise add the presoma of above-mentioned Pt and Co, stir 3h;
(3) under room temperature and magnetic agitation, regulate the pH to 10 of above-mentioned reacting slurry with 1M KOH/EG, and stablize 0.5h;
(4) under nitrogen atmosphere protection, magnetic agitation, utilize oil bath pan to heat above-mentioned reactant liquor, make its temperature reach 80 DEG C, then slowly dropwise add the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol
4/ EG, 2M) solution, make it react 3h;
(5) reaction makes it be down to room temperature after terminating, and utilizes ethanol and deionized water to carry out centrifugation washing to gained slurries, until without Cl respectively
-till and neutral.Again gained solid is carried out suction filtration, vacuum drying 28h at condensation temperature-50 DEG C, 80 DEG C of oven drying 24h, obtain Pt-Co/C;
(6) take in the above-mentioned alloy material of 50mg and porcelain boat, then N
2under condition, utilize tube furnace to its high-temperature process 2 hours at 700 DEG C, obtain the Pt-Co@Pt/C catalyst that structure ordering is hud typed.
Embodiment 4
(1) take 80mg carbon dust in triangular flask, add 40ml ethylene glycol, at ambient temperature ultrasonic 1 ~ 2h, make carbon dust be dispersed in ethylene glycol;
(2) by 14.78mg CoCL2 6H2O (CoCl
26H
2and 48.27mg chloroplatinic acid (H O)
2ptCl
6h
2o) ethylene glycol is dissolved in and ultrasonic 1h makes it even.Then, under room temperature and strong agitation, dropwise add the presoma of above-mentioned Pt and Co, stir 3h;
(3) under room temperature and magnetic agitation, regulate the pH to 10 of above-mentioned reacting slurry with 1M KOH/EG, and stablize 0.5h;
(4) under nitrogen atmosphere protection, magnetic agitation, utilize oil bath pan to heat above-mentioned reactant liquor, make its temperature reach 80 DEG C, then slowly dropwise add the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol
4/ EG, 2M) solution, make it react 3h;
(5) reaction makes it be down to room temperature after terminating, and utilizes ethanol and deionized water to carry out centrifugation washing to gained slurries respectively, until without chlorion (Cl
-) and neutrality till.Again gained solid is carried out suction filtration, vacuum drying 35h at condensation temperature-40 DEG C, 80 DEG C of oven drying 24h, obtain Pt-Co/C;
(6) take in the above-mentioned alloy material of 50mg and porcelain boat, then N
2under condition, utilize tube furnace to its high-temperature process 2 hours at 800 DEG C, obtain the Pt-Co@Pt/C catalyst that structure ordering is hud typed.
Structural characterization is carried out to product prepared by embodiment 1-4, proving that it is is carrier with carbon, and active metal is carried on carbon surface, wherein active metal be with structure ordering platinum cobalt alloy be core, the platinum core-shell type nano material that is shell, particle diameter is 5 ~ 10nm, and electron microscopic observation finds to be evenly distributed.
(1) X-ray diffraction analysis
X-ray diffraction is carried out to Pt-Co/C and Pt-Co@Pt/C prepared by the present invention, analyzes its diffracting spectrum.
The XRD figure of Pt-Co/C sample, has the diffraction maximum that wider, belongs to carbon carrier (200) crystallographic plane diffraction peak about 2 θ=25 °.It is 39.8 ° at 2 θ, 46.2 °, 67.5 ° and the neighbouring peak occurred, 82.4 ° of places, belong to (111) of Pt face-centered cubic (fcc) crystal formation, (200) (220) and (311) crystal face diffractive features peak respectively.Observe the feature peak-to-peak finding Pt strong more weak, show that sample particle particle diameter is very little and crystal formation is imperfect.As shown in Figure 1, be the XRD figure of the Pt-Co/C of embodiment 1 preparation.
The XRD figure of Pt-Co@Pt/C sample, has the diffraction maximum of four obvious Pt face-centred cubic structures.Compared with the characteristic peak of standard P t/C, its diffraction maximum is shuffled, and shows that less Co enters Pt face-centered cubic type lattice, produces Lattice Contraction, forms Pt-Co alloy phase.Especially, we find at 2 θ is 23 °, 32.8 °, 53.1 °, there is special diffraction maximum to occur near 58.6 °, belong to respectively (100) of characterisation of structures ordering and intermetallic compound, (110), (210) and (211) crystallographic plane diffraction peak, show that Pt-Co/C structure changes fct into by fcc after high-temperature process.In the collection of illustrative plates of Pt-Co@Pt/C-750, peak is sharply and very strong, does not find other assorted peaks, shows that Pt or Co does not have oxidized, and Pt and Co alloying completely in sample.Experiment prove, by unordered Pt-Co/C in inert gas shielding and uniform temperature process a period of time, the complete alloying of Pt-Co can be made, and form the intermetallic compound of structure ordering.As shown in Figure 2, the fcc structure Pt-Co@Pt/C being embodiment 1 preparation under inert gas conditions, obtains the XRD figure of face centered tetragonal (fct) configuration Pt-Co@Pt/C-750 alloy after 750 DEG C of high-temperature process 2h.
(2) electronic microscope photos
Electronic microscope photos is carried out to Pt-Co/C and Pt-Co@Pt/C prepared by the present invention.
By finding the high resolution electron microscopy photo analysis of Pt-Co/C sample, catalyst particle is carried on carbon support, and is evenly distributed, particle size close (about 3nm), and shows to define Pt-Co alloy phase.As shown in figure 3-1, be the high resolution electron microscopy figure of Pt-Co/C prepared by embodiment 1, can see, a large amount of catalyst particle is carried on carbon support, and is evenly distributed, particle size close (about 3nm); Fig. 3-2 is enlarged drawings of Fig. 3-1, can see and amplify particle lattice fringe after several times, fringe spacing through measurement discovery arrow points is 0.195nm, close with (200) interplanar distance (0.19616nm) of Pt, shows to define Pt-Co alloy phase.
By finding the high resolution electron microscopy photo analysis of Pt-Co@Pt/C sample, the alloying pellet particle diameter after high-temperature calcination increases, and have good dispersion, particle diameter is approximately 7nm; And show the intermetallic compound defining structure ordering.As the high resolution electron microscopy figure that Fig. 4-1 is Pt-Co/C gained Pt-Co@Pt/C-750 after 750 DEG C of high-temperature process prepared by embodiment 1, contrast with Fig. 3-1 and Fig. 3-2 and find, alloying pellet particle diameter after calcining increases, but still show good dispersion, only have small part agglomeration, its particle diameter is approximately 7nm.Fig. 4-2 is enlarged drawings of a zonule in Fig. 4-1, through measuring each interplanar distance, finds that there is Pt (200) crystal face, shows that particle surface is one deck Pt.In addition the superlattices crystal face (100) found by survey calculation and (110), show the intermetallic compound defining structure ordering, this is consistent with XRD Measurement results.
The present invention adopts the mixed liquor of ethylene glycol and sodium borohydride to be reducing agent, and prepare structurally ordered hud typed platinum cobalt-platinum catalyst Pt-Co@Pt/C by the high temperature anneal, its quality group becomes charcoal: 60%-90%, Co:1-20%, platinum: 9-20%.Structure ordering catalyst prepared by the present invention has that Pt carrying capacity is low, catalytic activity is high and chemical stability advantages of higher, is further developed by promotion fuel cell.
Claims (10)
1. fuel cell carbon supported core-shell platinum cobalt-platinum catalyst, is characterized in that: its mass percent consists of carrier carbon: 60% ~ 90%, cobalt: 1 ~ 20%, platinum: 9 ~ 20%.
2. fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 1, is characterized in that: described carrier is XC-72 carbon black.
3. fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 1, is characterized in that: the active component of described catalyst is structurally ordered platinum cobalt-platinum alloy, and wherein structurally ordered cobalt-platinum alloy is core, and platinum layer is shell.
4. a fuel cell preparation method for carbon supported core-shell platinum cobalt-platinum catalyst, comprises the steps:
(1) in powdered carbon, ethylene glycol is added, carry out ultrasonic disperse, then the ethylene glycol solution of soluble cobalt and the ethylene glycol solution of chloroplatinic acid is under agitation added respectively, make the mass ratio of carbon in mixed solution, cobalt ions and platinum ion for (60 ~ 90): (1 ~ 20): (9 ~ 20), magnetic agitation;
(2) with the ethylene glycol solution of potassium hydroxide, the pH of above-mentioned mixed solution is adjusted to 9 ~ 11, after stable, 80 DEG C ~ 120 DEG C are heated under nitrogen atmosphere protection, stirring condition, dropwise add the ethylene glycol solution of sodium borohydride, keep whole course of reaction pH constant, after reaction, obtain carbon and carry cobalt-platinum alloy slurries;
(3) gained reactant liquor is carried out centrifugation by ethanol, deionized water as washing agent successively wash to neutrality and without chlorion, obtain carbon and carry cobalt-platinum alloy particle;
(4) carbon obtained is carried the vacuum drying of cobalt-platinum alloy particle, then at oven drying;
(5) carbon obtained is carried cobalt-platinum alloy particle under a nitrogen atmosphere, utilize tube furnace to carry out the high temperature anneal, obtain structurally ordered hud typed carbon and carry platinum cobalt-platinum catalyst.
5. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, it is characterized in that: described soluble cobalt is cobalt chloride, cobalt nitrate or cobaltous sulfate, described carbon dust is XC-72 carbon black.
6. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, it is characterized in that: in the ethylene glycol solution of described chloroplatinic acid, Pt ion concentration is 0.01 ~ 0.1 mol/L.
7. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, is characterized in that: the concentration of the ethylene glycol solution of sodium borohydride is 1 ~ 3 mol/L.
8. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, is characterized in that: the ethylene glycol solution of sodium borohydride is 1:(2 ~ 5 with the volume ratio of the mixed solution added).
9. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, it is characterized in that: described vacuum drying temperature is-60 DEG C ~-40 DEG C, the vacuum drying time is 24 ~ 35h.
10. the preparation method of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst according to claim 4, is characterized in that: the temperature of described high annealing is 600 DEG C ~ 1000 DEG C, and the time is 2 ~ 6h.
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