CN104475126B - Fuel cell carbon supported core-shell platinum cobalt platinum catalyst and preparation method thereof - Google Patents
Fuel cell carbon supported core-shell platinum cobalt platinum catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fuel cell carbon supported core-shell platinum cobalt platinum catalyst and preparation method thereof, belong to electrochemical field.The mass percent of the catalyst is constituted：Carrier：60%~90%, cobalt：1~20%, platinum：9~20%.The mixed liquor that the present invention uses ethylene glycol and sodium borohydride prepares structurally ordered hud typed platinum cobalt platinum catalyst Pt Co@Pt/C for reducing agent by the high temperature anneal.Structure ordering catalyst prepared by the present invention has the advantages that Pt carrying capacity is low, catalytic activity is high and chemical stability is high, and fuel cell will be promoted further to develop.
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, the catalyst
Nuclear atom arrangement hud typed platinum cobalt-platinum catalyst (Pt-Co Pt/C) in order is carried for a kind of carbon, belongs to electrochemical field.
Technical background
In face of current global energy crisis, environmental pollution and climate warming problem, chemical energy is directly converted into electric energy
Fuel cell have the advantages that energy conversion efficiency is high, environment-friendly, energy density is high because of it, it is considered to be most expected to replace
The regenerative resource in generation.At present, fuel-cell catalyst is still with good resistance to corrosion, excellent electrocatalysis characteristic and electrification
The platinum or its alloy nano catalyst for learning performance are optimal.However, platinum scarcity of resources, expensive, the cost of reduction catalyst, system
Standby low carrying capacity, high catalytic activity, the platinum based catalyst of high stability are the keys for realizing commercializing fuel cells.With relatively inexpensive
And aboundresources transition metal or alloy cover nucleocapsid prepared by a thin layer Pt (even monoatomic layer) on core surface as core
Type platinum nano catalyst, can increase substantially a large amount of uses for reducing platinum while catalyst utilization, be effectively reduced limitation
Fuel cell widely uses catalyst cost.Pt as catalyst with core-casing structure shell when, the relatively small verification of lattice constant
Shell Pt produces compression strain effect, and its d is moved down with center reduces the absorption and activation that are conducive to oxygen with surface strain power, therefore
Improve its work to oxygen reduction reaction.
CN103084175A describes a kind of deficient potential deposition-displacement and prepares the hud typed Pt-Au@Pt catalyst sides of carbon load
Method.This method first uses sodium borohydride reduction gold compound, and the Au/C for being supported on carbon surface is made.Then Au/C ultrasonic disperses are existed
In platinum compound aqueous solution, loaded Pt-Au alloy nanoparticles are obtained.By owing potential deposition Co atomic depositions to Pt-
Au alloy nanoparticles surface, finally enters line replacement with platinum compounds by the Co atoms being deposited on Pt-Au alloys, and carbon is made and carries
Hud typed Pt-Au@Pt nanocatalysts.Catalyst activity prepared by this method is high and stably, prepare it is simple, but cost compared with
Height, prepared catalyst metallic particle diameter is difficult to control, wider range.
Sun seminars are prepared for FePt nanometers orderly in structure using liquid phase chemical pyrolysismethod and the high temperature anneal and urged
Agent.First by being pyrolyzed iron pentacarbonyl (Fe (CO)5) and reduction acetylacetone,2,4-pentanedione platinum obtain the FePt of face-centered cubic (fcc) structure
Nano particle, then covers thermodynamically stable MgO on its surface, and the FePt for making fcc structure by high annealing is converted into face
The heart pros (fct) structurally ordered hud typed FePt nano particles, finally hydrochloric hexadecanethiol (HDT) and oleic acid just oneself
Alkane solution dissolves MgO, and structurally ordered FePt nanocatalysts are made.FePt nanometers of structure ordering nucleocapsid prepared by the method is urged
Agent catalytic activity and stability are high compared with business platinum catalyst Pt/C, good dispersion, but its pt utilization is low, and catalytic activity is still
It is smaller, and be not suitable in HClO4Catalytic oxidation-reduction.
The content of the invention
It is a primary object of the present invention to provide one kind to prepare simply, cost is relatively low, platinum specific surface area is big, utilization rate is high,
High catalytic activity and the good fuel-cell catalyst of stability.
In order to realize the above-mentioned purpose of the present invention, using following technical scheme：
A kind of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst, specially a kind of fuel cell carries nuclear atom with carbon
The orderly hud typed platinum cobalt-platinum alloy catalyst of arrangement, is made up of carrier and active component, and its mass percent composition is：Carrier
Carbon：60%~90%, cobalt：1~20%, platinum：9~20%.
In above-mentioned catalyst, described carrier carbon is XC-72 carbon blacks；Active component is structurally ordered platinum cobalt-platinum alloy, its
In structurally ordered cobalt-platinum alloy be core, platinum layer is shell.
Another mesh of the present invention is to provide a kind of preparation method of the orderly platinum cobalt-platinum alloy catalyst of new structure.
A kind of fuel cell preparation method of carbon supported core-shell platinum cobalt-platinum catalyst, comprises the following steps：
(1) ethylene glycol (EG) is added in powdered carbon, ultrasonic disperse is carried out, is then separately added with agitation soluble cobalt
Ethylene glycol solution and chloroplatinic acid ethylene glycol solution so that in mixed solution the mass ratio of carbon, cobalt ions and platinum ion be (60
~90):(1~20):(9~20), magnetic agitation；
(2) pH of above-mentioned mixed solution is adjusted to after 9~11, stabilization with the ethylene glycol solution of potassium hydroxide, in blanket of nitrogen
80 DEG C~120 DEG C are heated under protection, stirring condition, the ethylene glycol solution of sodium borohydride is added dropwise, holding was entirely reacted
Journey pH is constant, after reaction, obtains carbon and carries cobalt-platinum alloy slurries；
(3) washing is centrifuged extremely as detergent with ethanol, deionized water successively in reaction solution obtained by step (2)
It is neutral and without chlorion, obtain carbon and carry cobalt-platinum alloy particle Pt-Co/C；
(4) carbon for obtaining step (3) carries cobalt-platinum alloy particle and is dried in vacuo, then in oven drying；
(5) carbon for obtaining step (4) carries cobalt-platinum alloy particle under a nitrogen atmosphere, and high annealing is carried out using tube furnace
Processing, obtains structurally ordered hud typed pallium-on-carbon 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 concentrations are 0.01~0.1 mol/L.
Described ultrasonic disperse is carried out at room temperature, and the ultrasonic disperse time is 0.5~2h；The magnetic agitation time is 2~4h.
It is preferred that, 30~50 milliliters of ethylene glycol (EG) are added in 60~90mg powdered carbons.
In step (2), the ethylene glycol solution of sodium borohydride is dissolved in the sodium borohydride mixture (NaBH of ethylene glycol4/ EG),
For the reducing agent of reaction, its concentration is 1~3 mol/L, and the reaction time is 2~4h.The ethylene glycol solution and step of sodium borohydride
(1) volume ratio of gained mixed solution is 1:(2~5).
It is preferred that, the sodium borohydride (NaBH that 15ml is dissolved in ethylene glycol is added dropwise in above-mentioned mixed solution4, 2M) and it is molten
Liquid.
In step (4), described vacuum drying is to be dried in vacuo 24~35h at -60 DEG C~-40 DEG C of condensation temperature.Dry
Case 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, it was demonstrated that it is that, using carbon as carrier, active metal is carried on carbon surface,
Wherein active metal be by core of structure ordering platinum cobalt alloy, platinum for shell core-shell type nano material, particle diameter be 5~
10nm, electron microscopic observation finds distribution uniform.
Advantages of the present invention：
The present invention is using ethylene glycol as solvent, and the mixed liquor of ethylene glycol and sodium borohydride is reducing agent, by controlling to add Pt
The Pt-Co/C alloys of different atomic ratios, the pH control alloy particle diameters of regulation course of reaction are synthesized with the amount of Co presomas.Second
The mixing of glycol and sodium borohydride can generate a kind of Na+B-(OCH2CH2OH)4, its reducing power is more stronger than ethylene glycol, can platinum and
Cobalt atom is restored jointly, obtains Pt-Co alloys.Meanwhile, the larger ethylene glycol of viscosity can be as stabilizer, in course of reaction
Grain growth can be effectively controlled, the nanocatalyst of smaller particle is made.By above-mentioned Pt-Co/C alloys in inert gas conditions
Under, calcining heat, time are controlled by tube furnace, suitable the high temperature anneal is carried out to it, coreshell type structure is made orderly
Change Pt-Co@Pt/C catalyst.
The present invention use ethylene glycol and sodium borohydride mixed liquor for reducing agent, effectively obtained certain atomic ratio and particle diameter compared with
Small Pt-Co/C Nanoalloy materials；In N2Under protection, using temperature-programmed technique, high temperature is carried out to produced Nanoalloy
Annealing, is made the super crystal lattice material of Pt and Co ordered arrangements on atomic level, gained nano particle is using Pt as shell, structure
Ordering Pt-Co alloys are core, can greatly improve the utilization rate and stability of precious metals pt.And calcination process uses N2As
Protective gas, hence it is evident that reduce preparation cost, will promote the further development of ordering structure catalyst.
Below by the drawings and specific embodiments, the present invention will be further described, but is not meant to present invention protection
The limitation of scope.
Brief description of the drawings
Fig. 1 is Pt-Co/C prepared by present invention XRD.
Fig. 2 be the fcc structure Pt-Co@Pt/C that prepare of the present invention under inert gas conditions, through 750 DEG C of high-temperature process 2h
The XRD of face centered tetragonal (fct) configuration Pt-Co@Pt/C-750 alloys is obtained afterwards.
Fig. 3-1 and Fig. 3-2 is Pt-Co/C high resolution electron microscopy figure.
Fig. 4-1 and Fig. 4-2 is Pt-Co/C gained Pt-Co@Pt/C-750 after 750 DEG C of high-temperature process high resolution electron microscopy
Figure.
Embodiment
The fuel cell of the present invention is made up of with hud typed platinum cobalt-platinum catalyst carrier and active component, and 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, and it is former
Material mass percent, which is constituted, is：Carrier：60%~90%, cobalt：1~20%, platinum：9~20%.
The fuel cell of the present invention includes two big steps with the preparation method of hud typed platinum cobalt-platinum catalyst, first with
Co-reducing process, by controlling concentration, pH, reaction temperature and the time of reaction, the Pt-Co/C catalysis of synthesis carbon load type cobalt-platinum alloy
Agent；Then, the catalyst upper step obtained is in N2The orderly hud typed platinum cobalt-platinum catalyst of lower high annealing preparation structure.Specifically
Step is as follows：
(1) 60~90mg charcoal balls are weighed to be placed in three pin bottle, 30~50 milliliters of ethylene glycol (EG) are added, at ambient temperature
0.5~1h of ultrasonic disperse, be then separately added with agitation soluble cobalt ethylene glycol solution and chloroplatinic acid ethylene glycol it is molten
Liquid so that the mass ratio of carbon, cobalt ions and platinum ion is 6~9 in mixed solution:1.5:3, magnetic agitation 3h；
(2) 9~11, stable a period of time are adjusted to being dissolved in the potassium hydroxide solution of ethylene glycol by the pH of above-mentioned mixed solution
Afterwards, 80 DEG C~120 DEG C are heated under nitrogen atmosphere protection, strong agitation, the boron hydrogen that 15~20ml is dissolved in ethylene glycol is added dropwise
Change sodium (NaBH4, 2M) and solution, keep that whole course of reaction pH is constant, the reaction time is 3h, obtains carbon and carries cobalt-platinum alloy slurries；
(3) washing is centrifuged into as detergent with ethanol, ultra-pure water according to this in reaction solution obtained by step (2)
Property and without chlorion, obtain carbon carry cobalt-platinum alloy particle；
(4) carbon for obtaining step (3) carries cobalt-platinum alloy particle and is dried in vacuo 24h, then in 180 DEG C of dry 1h, obtains
The irregular Pt-Co/C of Atomic Arrangement；
(5) carbon for obtaining step (4) carries cobalt-platinum alloy particle under logical condition of nitrogen gas, and carrying out high temperature using tube furnace moves back
Fire processing, obtains the hud typed pallium-on-carbon cobalt of structure ordering-platinum catalyst Pt-Co@Pt/C.
Embodiment 1
(1) 80mg carbon dusts (XC-72 carbon blacks, as follows) are weighed in triangular flask, 40ml ethylene glycol are added, in room temperature condition
Lower ultrasonic 1~2h, makes carbon dust be dispersed in ethylene glycol；
(2) by 7.39mg CoCL2 6H2Os (CoCl2·6H2) and 48.27mg chloroplatinic acids (H O2PtCl6·H2O) it is dissolved in second two
Simultaneously ultrasound 1h makes its uniform to alcohol.Then, under room temperature and strong agitation, above-mentioned Pt and Co presoma is added dropwise, 3h is stirred；
(3) under room temperature and magnetic agitation, with the pH of the above-mentioned reacting slurry of 1M KOH/EG solution regulation to 10, and stably
0.5h；
(4) above-mentioned reaction solution is heated using oil bath pan under nitrogen atmosphere protection, magnetic agitation, makes its temperature up to 80 DEG C, so
Sodium borohydride (the NaBH that 15ml is dissolved in ethylene glycol is slowly added dropwise afterwards4/ EG, 2M) solution, it is reacted 3h；
(5) down to room temperature after reaction terminates, ethanol and deionized water are utilized respectively centrifugation point is carried out to gained slurries
From washing, until without chlorion (Cl-) and it is neutral untill.Gained solid is subjected to suction filtration again, is dried in vacuo at -60 DEG C of temperature
24h；Then in 80 DEG C of oven drying 24h, Pt-Co/C is produced；
(6) the above-mentioned alloy materials of 50mg are weighed in porcelain boat, in N2Under the conditions of, using tube furnace to its at 750 DEG C it is high
Temperature processing 2 hours, produces the hud typed Pt-Co/C@Pt/C catalyst of structure ordering.
Embodiment 2
(1) 90mg carbon dusts are weighed in triangular flask, 40ml ethylene glycol are added, 1~2h of ultrasound, makes carbon dust at ambient temperature
It is dispersed in ethylene glycol；
(2) by 3.70mg CoCL2 6H2Os (CoCl2·6H2) and 23.14mg chloroplatinic acids (H O2PtCl6·H2O) it is dissolved in second two
Simultaneously ultrasound 1h makes its uniform to alcohol.Then, under room temperature and strong agitation, above-mentioned Pt and Co presoma is added dropwise, 3h is stirred；
(3) under room temperature and magnetic agitation, the pH to 10 of above-mentioned reacting slurry, and stable 0.5h are adjusted with 1M KOH/EG；
(4) above-mentioned reaction solution is heated using oil bath pan under nitrogen atmosphere protection, magnetic agitation, makes its temperature up to 80 DEG C, so
Sodium borohydride (the NaBH that 15ml is dissolved in ethylene glycol is slowly added dropwise afterwards4/ EG, 2M) solution, it is reacted 3h；
(5) down to room temperature after reaction terminates, ethanol and deionized water are utilized respectively centrifugation point is carried out to gained slurries
From washing, until without Cl-Untill and it is neutral.Gained solid is subjected to suction filtration again, 25h is dried in vacuo at -45 DEG C of condensation temperature,
80 DEG C of oven drying 24h, produce Pt-Co/C；
(6) weigh in the above-mentioned alloy materials of 50mg and porcelain boat, then N2Under the conditions of, using tube furnace to its at 750 DEG C it is high
Temperature processing 2 hours, produces the hud typed Pt-Co@Pt/C catalyst of structure ordering.
Embodiment 3
(1) 60mg carbon dusts are weighed in triangular flask, 40ml ethylene glycol are added, 1~2h of ultrasound, makes carbon dust at ambient temperature
It is dispersed in ethylene glycol；
(2) by 14.78mg CoCL2 6H2Os (CoCl2·6H2) and 96.54mg chloroplatinic acids (H O2PtCl6·H2O) it is dissolved in second
Simultaneously ultrasound 1h makes its uniform to glycol.Then, under room temperature and strong agitation, above-mentioned Pt and Co presoma is added dropwise, stirs
3h；
(3) under room temperature and magnetic agitation, the pH to 10 of above-mentioned reacting slurry, and stable 0.5h are adjusted with 1M KOH/EG；
(4) above-mentioned reaction solution is heated using oil bath pan under nitrogen atmosphere protection, magnetic agitation, makes its temperature up to 80 DEG C, so
Sodium borohydride (the NaBH that 15ml is dissolved in ethylene glycol is slowly added dropwise afterwards4/ EG, 2M) solution, it is reacted 3h；
(5) down to room temperature after reaction terminates, ethanol and deionized water are utilized respectively centrifugation point is carried out to gained slurries
From washing, until without Cl-Untill and it is neutral.Gained solid is subjected to suction filtration again, 28h is dried in vacuo at -50 DEG C of condensation temperature,
80 DEG C of oven drying 24h, produce Pt-Co/C；
(6) weigh in the above-mentioned alloy materials of 50mg and porcelain boat, then N2Under the conditions of, using tube furnace to its at 700 DEG C it is high
Temperature processing 2 hours, produces the hud typed Pt-Co@Pt/C catalyst of structure ordering.
Embodiment 4
(1) 80mg carbon dusts are weighed in triangular flask, 40ml ethylene glycol are added, 1~2h of ultrasound, makes carbon dust at ambient temperature
It is dispersed in ethylene glycol；
(2) by 14.78mg CoCL2 6H2Os (CoCl2·6H2) and 48.27mg chloroplatinic acids (H O2PtCl6·H2O) it is dissolved in second
Simultaneously ultrasound 1h makes its uniform to glycol.Then, under room temperature and strong agitation, above-mentioned Pt and Co presoma is added dropwise, stirs
3h；
(3) under room temperature and magnetic agitation, the pH to 10 of above-mentioned reacting slurry, and stable 0.5h are adjusted with 1M KOH/EG；
(4) above-mentioned reaction solution is heated using oil bath pan under nitrogen atmosphere protection, magnetic agitation, makes its temperature up to 80 DEG C, so
Sodium borohydride (the NaBH that 15ml is dissolved in ethylene glycol is slowly added dropwise afterwards4/ EG, 2M) solution, it is reacted 3h；
(5) down to room temperature after reaction terminates, ethanol and deionized water are utilized respectively centrifugation point is carried out to gained slurries
From washing, until without chlorion (Cl-) and it is neutral untill.Gained solid is subjected to suction filtration again, the vacuum at -40 DEG C of condensation temperature
35h, 80 DEG C of oven drying 24h are dried, Pt-Co/C is produced；
(6) weigh in the above-mentioned alloy materials of 50mg and porcelain boat, then N2Under the conditions of, using tube furnace to its at 800 DEG C it is high
Temperature processing 2 hours, produces the hud typed Pt-Co@Pt/C catalyst of structure ordering.
Structural characterization is carried out to product prepared by embodiment 1-4, it was demonstrated that it is that, using carbon as carrier, active metal is carried on carbon
Surface, wherein active metal be by core of structure ordering platinum cobalt alloy, platinum be the core-shell type nano material of shell, particle diameter is 5
~10nm, 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, its diffracting spectrum is analyzed.
The XRD of Pt-Co/C samples, there is a wider diffraction maximum in 2 θ=25 ° or so, belongs to carbon carrier (200)
Crystallographic plane diffraction peak.It is the peak nearby occurred at 39.8 °, 46.2 °, 67.5 ° and 82.4 ° in 2 θ, is belonging respectively to Pt face-centered cubics
(fcc) (111) of crystal formation, (200) (220) and (311) crystal face diffractive features peak.Observation finds that Pt characteristic peak peak intensity is weaker,
Show sample particle particle diameter very little and crystal formation is imperfect.As shown in figure 1, the Pt-Co/C prepared for embodiment 1 XRD.
The XRD of Pt-Co@Pt/C samples, the diffraction maximum for having four obvious Pt face-centred cubic structures.With standard Pt/C's
Characteristic peak is compared, and its diffraction maximum is shuffled, and is shown that less Co enters Pt face-centered cubic type lattices, is produced Lattice Contraction, forms Pt-
Co alloy phases.Especially, it has been found that in 2 θ be 23 °, 32.8 °, 53.1 °, 58.6 ° nearby have special diffraction maximum to occur, point
(100) for characterizing structure ordering and intermetallic compound are not belonged to, and (110), (210) and (211) crystallographic plane diffraction peak shows
Pt-Co/C structures are changed into fct by fcc after high-temperature process.Peak is sharp and very strong in Pt-Co@Pt/C-750 collection of illustrative plates, does not have
Other miscellaneous peaks are found, show that Pt or Co are not oxidized, and Pt and Co complete alloying in sample.It is demonstrated experimentally that passing through
To unordered Pt-Co/C in inert gas shielding and certain temperature processing a period of time, the complete alloyings of Pt-Co, and shape can be made
Into the intermetallic compound of structure ordering.As shown in Fig. 2 be embodiment 1 prepare fcc structure Pt-Co@Pt/C in indifferent gas
Under concrete conditions in the establishment of a specific crime, the XRD of face centered tetragonal (fct) configuration Pt-Co@Pt/C-750 alloys is obtained 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.
Found by the high resolution electron microscopy photo analysis to Pt-Co/C samples, catalyst particle is carried on carbon support,
And be evenly distributed, particle size is close (about 3nm), and suggests the formation of Pt-Co alloy phases.As shown in figure 3-1, it is embodiment
1 Pt-Co/C prepared high resolution electron microscopy figure, it can be seen that a large amount of catalyst particles are carried on carbon support, and distribution is equal
Even, particle size is close (about 3nm)；Fig. 3-2 is Fig. 3-1 enlarged drawing, it can be seen that particle lattice striped after amplification several times, warp
Measurement finds that the fringe spacing that arrow is pointed to is 0.195nm, close with Pt (200) interplanar distance (0.19616nm), shows shape
Into Pt-Co alloy phases.
Found by the high resolution electron microscopy photo analysis to Pt-Co@Pt/C samples, the alloying pellet particle diameter after high-temperature calcination
Increase, with good dispersion, particle diameter is about 7nm；And suggest the formation of the intermetallic compound of structure ordering.Such as 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 high resolution electron microscopy figure, with figure
3-1 and Fig. 3-2 contrasts find that the alloying pellet particle diameter after calcining increases, but still shows good dispersion, only small part group
Poly- phenomenon, its particle diameter is about 7nm.Fig. 4-2 is the enlarged drawing of a zonule in Fig. 4-1, through measuring each interplanar distance, has been found
Pt (200) crystal face, it is one layer of Pt to show particle surface.In addition the superlattices crystal face (100) that is found by survey calculation and
(110) intermetallic compound of structure ordering, is suggested the formation of, this is consistent with XRD Measurement results.
The mixed liquor that the present invention uses ethylene glycol and sodium borohydride has for reducing agent by the high temperature anneal preparation structure
The hud typed platinum cobalt of sequence-platinum catalyst Pt-Co@Pt/C, its quality group turns into charcoal：60%-90%, Co：1-20%, platinum：9-20%.
Structure ordering catalyst prepared by the present invention has the advantages that Pt carrying capacity is low, catalytic activity is high and chemical stability is high, will promote
Enter fuel cell further to develop.
Claims (7)
1. a kind of fuel cell carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：It is made up of carrier and active component,
Its mass percent is constituted：Carrier carbon：60%~90%, cobalt：1~20%, platinum：9~20%；Described carrier is XC-72
Carbon black；Described active component is structurally ordered platinum cobalt-platinum alloy, wherein structurally ordered cobalt-platinum alloy is core, platinum layer is shell；
Its preparation method comprises the following steps：
(1) ethylene glycol is added in carbon dust, ultrasonic disperse is carried out, is then separately added with agitation the ethylene glycol of soluble cobalt
The ethylene glycol solution of solution and chloroplatinic acid so that the mass ratio of carbon, cobalt ions and platinum ion is (60~90) in mixed solution:(1
~20):(9~20), magnetic agitation；
(2) pH of above-mentioned mixed solution is adjusted to 9~11 with the ethylene glycol solution of potassium hydroxide, it is stable after, nitrogen atmosphere protection,
80 DEG C~120 DEG C are heated under stirring condition, the ethylene glycol solution of sodium borohydride is added dropwise, whole course of reaction pH is kept not
Become, after reaction, obtain carbon and carry cobalt-platinum alloy slurries；
(3) washing is centrifuged to neutrality and without chlorine as detergent with ethanol, deionized water successively in gained reaction solution
Ion, obtains carbon and carries cobalt-platinum alloy particle；
(4) obtained carbon is carried into cobalt-platinum alloy particle to be dried in vacuo, then in oven drying；
(5) obtained carbon is carried into cobalt-platinum alloy particle under a nitrogen atmosphere, carries out the high temperature anneal using tube furnace, tied
The orderly hud typed pallium-on-carbon cobalt-platinum catalyst of structure.
2. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Described
Soluble cobalt is cobalt chloride, cobalt nitrate or cobaltous sulfate, and described carbon dust is XC-72 carbon blacks.
3. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Described
In the ethylene glycol solution of chloroplatinic acid, Pt ion concentrations are 0.01~0.1 mol/L.
4. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Hydroboration
The concentration of the ethylene glycol solution of sodium is 1~3 mol/L.
5. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Hydroboration
The volume ratio of mixed solution of the ethylene glycol solution of sodium with adding is 1:(2~5).
6. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Described
Vacuum drying temperature is -60 DEG C~-40 DEG C, and vacuum drying time is 24~35h.
7. fuel cell according to claim 1 carbon supported core-shell platinum cobalt-platinum catalyst, it is characterised in that：Described
The temperature of high annealing is 600 DEG C~1000 DEG C, and the time is 2~6h.
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| US8741801B2 (en) * | 2009-11-23 | 2014-06-03 | The Research Foundation For The State University Of New York | Catalytic platinum and its 3d-transition-metal alloy nanoparticles |
| CN101912778B (en) * | 2010-09-01 | 2012-11-07 | 郴州高鑫铂业有限公司 | Method for preparing carbon-supported nano Pt-M fuel cell catalyst |
| CN103055893B (en) * | 2012-12-25 | 2015-10-28 | 北京化工大学 | Supported cobalt platinum superlattices alloy nano particle composite catalyst and preparation method thereof |
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