CN106960962A - A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst and preparation method thereof - Google Patents
A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN106960962A CN106960962A CN201710284291.5A CN201710284291A CN106960962A CN 106960962 A CN106960962 A CN 106960962A CN 201710284291 A CN201710284291 A CN 201710284291A CN 106960962 A CN106960962 A CN 106960962A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
Alloy fuel cell catalyst is taken off the invention discloses a kind of platinum base of polyaniline-coated carbon carrier, belong to fuel cell catalyst technical field, including carrier and active component, carrier is by polyaniline-coated carbon black, active component is the platinum cobalt metal with coreshell type structure, wherein platinum cobalt alloy is core, and platinum is shell；The weight % of the weight % of carrier 60 of polyaniline-coated carbon black~80；The weight % of the weight % of platinum cobalt metal 20 with coreshell type structure~40；In the core of platinum cobalt alloy, the atomic ratio of platinum and cobalt is 1:0.5~1:3.The platinum base of polyaniline-coated carbon carrier of the present invention takes off alloy fuel cell catalyst, polyaniline is coated on carrier, effectively damage of the acid to carbon carrier in the de- alloy process of reduction, during subsequent catalyst use, polyaniline can extend the service life of de- alloy catalyst than carbon carrier preferential oxidation；The catalytic efficiency of catalyst and the utilization rate of noble metal can be greatly improved, the development of fuel cell will be promoted.
Description
Technical field
The present invention relates to the platinum of a kind of fuel-cell catalyst and preparation method thereof, more particularly to polyaniline-coated carbon carrier
Base takes off alloy fuel cell catalyst and preparation method thereof, belongs to fuel cell catalyst technical field.
Technical background
Fuel cell is general using hydrogen as fuel, and its cathod catalyst is mainly platinum group catalyst, but platinum resource has
Limit, it is expensive, hamper the commercialization of fuel cell.
Core-shell type nano-structured calalyst is that a kind of metallic nano-particle is coated on into the outer of another metallic nano-particle
Layer, is linked together by chemical bond or other active forces between the two.It is except with several metallic individualisms
Outside Shi Zishen property, the new features produced after some various metals are combined are also equipped with, the catalysis than single metallic is lived
Property is more preferable.Using relatively inexpensive transition metal as core, platinum (Pt) is coated on to the outer layer of core as skin, substantially reduced
Pt consumption in catalyst；The adsorption for adjusting oxygen can also be helped by being acted synergistically the metal produced simultaneously between, improve oxygen also
Original reaction (ORR) catalytic performance.
US20100197490 describes a kind of method that a kind of platinum cladding base metal prepares nucleocapsid catalyst, this method
First by the non-noble metal salt such as Fe, Co, Ni, W, Cu, 2-10nm particle is reduced into the method for electronation, is done in atmosphere
After dry, heat up 600 DEG C to 800 DEG C, made annealing treatment, depending on annealing time is because of different metal.After the completion of annealing, by the nanometer
In particle immersion platinum salt solution, a thin layer Pt shells are deposited on the surface of ISTon-noble metal particles using electrochemical displacement method, so as to make
Standby core-shell type nanocatalyst.Although this method can make complete core-shell catalyst, operating process is complicated, needs consumption
Mass energy, prepares high cost.
CN200610019303 describes a kind of a kind of method that nucleocapsid catalyst is prepared with chemical replacement method, and this method is
Base metal salt is configured to solution, a certain amount of surfactant is added, the reduction of excess is then added into mixed solution
Agent, is made non-noble metal nano metal solution, then addition precious metal salt solution enters into non-noble metal nano metal solution
Row chemical replacement, obtains the catalyst with core-casing structure solution that noble metal is wrapped in non-noble metal nanoparticles surface, obtains non-load
Load type nucleocapsid catalyst.Carbon carrier is finally added in non-supported nucleocapsid catalyst solution to be adsorbed, and obtains loaded core
Shell catalyst.The advantage of this method is that operating process is simple, prepares low cost, but catalyst particle size is bigger than normal, and catalyst is only
It is connected by suction-operated with carbon carrier, it is easy to come off in electrochemical reaction process, so as to reduce catalytic efficiency.
Platinum base alloy catalyst is prepared with de- alloyage, is the difference based on oxidation-reduction potential between metal pair, utilizes electricity
Chemical method removes the relatively active metal on platinum base alloy, increasingly complex to prepare core-shell type or structure of the surface rich in Pt
Nanoparticle.Generally, it is that alloy catalyst is directly placed into strong acid to carry out de- alloy treatment to take off alloy operation, is then placed into
Washed in deionized water.And the damage of carbon carrier can be caused during strong acid treatment, it is unfavorable for the life-span of catalyst.
Therefore it provides a kind of carrier damage reduces, the fuel-cell catalyst of catalyst long service life and its preparation side
Method just turns into the technical barrier that the technical field is badly in need of solving.
The content of the invention
An object of the present invention is to provide a kind of carrier damage to reduce, and the fuel cell of catalyst long service life is urged
Agent.
The foregoing invention purpose of the present invention reaches by the following technical programs：
A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst, including carrier and active component, its
It is characterised by：The carrier is by polyaniline-coated carbon black, and the active component is the platinum cobalt metal with coreshell type structure, wherein
Platinum cobalt alloy is core, and platinum is shell；The weight % of the weight % of carrier 60 of polyaniline-coated carbon black~80；Platinum with coreshell type structure
The weight % of the weight % of cobalt metal 20~40；In the core of the platinum cobalt alloy, the atomic ratio between platinum and cobalt is 1:0.5~1:3.
Preferably, the particle diameter distribution of the platinum cobalt metal with coreshell type structure is in 2~4nm.
Preferably, the platinum cobalt metal with coreshell type structure is dispersed on carrier.
Alloy fuel cell is taken off it is a further object of the present invention to provide a kind of platinum base of above-mentioned polyaniline-coated carbon carrier to urge
The preparation method of agent.
The foregoing invention purpose of the present invention reaches by the following technical programs：
A kind of platinum base of polyaniline-coated carbon carrier takes off the preparation method of alloy fuel cell catalyst, and its specific steps is such as
Under：
(1) carbon carrier pre-treatment：Weigh appropriate carbon carrier, be scattered in concentrated acid handle, be then washed with deionized to
Neutrality, suction filtration drying, grind into powder is standby；
(2) preparation of carbon-polyaniline：The carbon dust after step (1) processing is weighed, HClO is dispersed in4In solution, ice bath
Under the conditions of, the aqueous solution of aniline is added, ammonium persulfate (APS) is dissolved in HClO by magnetic agitation4In solution, it is slowly added dropwise into anti-
Answer and reacted at system, 0 DEG C a period of time, after reaction terminates, washing suction filtration drying is pulverized last, dried at 80 DEG C, by upper
State step synthesis carbon：Polyaniline (C:PANI) mass ratio is 1:0.5~1:2 carbon-polyaniline complex carrier (C-PANI)；
(3) using heating using microwave auxiliary ethylene glycol-NaBH4The method of reduction prepares catalyst：By what is obtained in step (2)
Carbon-polyaniline (C-PANI) complex carrier is dispersed in ethylene glycol (EG), and ethylene glycol is removed can also suppress catalysis as reducing agent
The growth of agent particle diameter, ultrasound is well mixed it, in above-mentioned homogeneous solution, by Pt:Co atomic ratios are 1:0.5~1:3 difference
Add H2PtCl6·6H2O/EG solution and CoCl2Under/EG solution, magnetic agitation, above-mentioned mixed solution pH value is adjusted with KOH/EG
Save as 9~11, weigh excessive NaBH4It is dissolved in 10mL ethylene glycol, is slowly added dropwise to reaction system, question response to bubble-free is produced
Afterwards, in 130 DEG C~180 DEG C microwave reductions, 0.5~2h is reacted, after reaction terminates, the drying of centrifuge washing suction filtration, consolidate
The platinum cobalt alloy-catalyst (PtCo/C-PANI) of the polyaniline-coated carbon carrier of body, grind into powder；
(4) the platinum cobalt alloy-catalyst of the polyaniline-coated carbon carrier for the solid for obtaining step (3) by acid vapor or
Acid solution carries out de- alloy treatment, is then centrifuged for washing to solution in neutrality, final catalyst, i.e. polyaniline are obtained after drying
The platinum base for coating carbon carrier takes off alloy fuel cell catalyst.
Preferably, in the step (1), the concentrated acid is dense HNO3。
Preferably, in the step (1), described be washed with deionized to neutral comprises the following steps that：In oil bath plus
0.5h is handled at 130 DEG C of heat, reaction is poured into after terminating cools down dilution in deionized water, then filtering and washing.
Preferably, in the step (2), the carbon dust is 0.2g, the HClO4Concentration be 1mol/L.
Preferably, in the step (2), described aniline and the mol ratio of ammonium persulfate (APS) is 1:1.
Preferably, in the step (3), the concentration of the KOH/EG is 2mol/L.
Preferably, in the step (3), by adjust ultrasonic time, pH value, presoma incorporation time, reaction temperature and
Time controls catalyst particle size size and its distribution situation on carrier, and wherein reaction temperature is not higher than 180 DEG C, too high
Reaction temperature can make ethylene glycol go bad, and solution is changed into glassy yellow.
Preferably, in the step (4), described de- alloy takes off alloy for gas phase or liquid phase takes off alloy.
Preferably, the de- alloy of the gas phase is：Add after appropriate volatile acid, will be equipped with ptfe autoclave
The sand core crucible of the platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in reactor, keeps the liquid level of acid to be less than core
3cm.Reactor after encapsulation is put into baking oven and heated, and reaction is cooled to room temperature after terminating；The equal water of de- alloy catalyst of gained
Neutrality is washed till to be placed in drying in baking oven.
Preferably, the de- alloy of the liquid phase is：The platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in 1mol/L
H2SO4In solution, 6h is soaked at room temperature；The de- alloy catalyst of gained is washed to neutrality, is placed in after being dried in baking oven and obtains De-
PtCo/C-PANI。
Preferably, described de- alloy treatment is divided into the de- alloy of gas phase and liquid phase two kinds of situations of de- alloy, and gas phase takes off alloy
Use volatile dense HNO3, HCl, the reaction time be 10~60min；Liquid phase takes off alloy and uses dilute H2SO4。
Preferably, described dilute H2SO4The concentration of solution is 0.5mol/L~2mol/L, and the reaction time is 3~12h.
By carrying out structural characterization to final product, it was demonstrated that be effectively prepared for coating the carbon carrier of polyaniline；Party's legal system
On a surface of the carbon, particle diameter distribution is dispersed in 2~4nm, and on carrier for the active metal component load of standby catalyst；It is de-
The Co atoms of skim-coat are effectively removed after alloy treatment, are prepared by core of platinum cobalt alloy, platinum layer fires for the core-shell type nano of shell
Expect cell catalyst.
The present invention compared with prior art, with following gain effect：
(1) microwave radiation technology ethylene glycol-sodium borohydride reduction prepares catalyst, can ensure catalyst particle size and distribution
The Co ions in presoma are effectively reduced while uniform, atom utilization is improved；
(2) the de- alloy of appropriateness prepares core-shell catalyst, can effectively improve the Activity and stabill of catalyst, go in addition
The transition metal atoms of skim-coat, can reduce damage of the dissociated ion to fuel cell membrane material；
(3) polyaniline is coated on carrier, effectively damage of the acid to carbon carrier in the de- alloy process of reduction, in subsequent catalyst
During agent use, polyaniline can extend the service life of de- alloy catalyst than carbon carrier preferential oxidation；The present invention can
To greatly improve the catalytic efficiency of catalyst and the utilization rate of noble metal, the development of fuel cell will be promoted.
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 the FTIR spectrograms of carbon-polyaniline (C-PANI) complex carrier synthesized in the embodiment of the present invention 1.
Fig. 2 be the embodiment of the present invention 1 in take off alloy after De-PtCo/C-PANI transmission electron microscope photo.
Fig. 3 be the embodiment of the present invention 1 in take off alloy before and after PtCo/C-PANI, De-PtCo/C-PANI catalyst XPS spectrum
Figure.
Fig. 4 is that the De-PtCo/C of De-PtCo/C-PANI catalyst and uncoated polyaniline in the embodiment of the present invention 1 is catalyzed
Agent takes off the CV test charts after alloy.
Embodiment
Embodiment 1
(1) 2g carbon (carbon black) carrier is weighed, the dense HNO of 200ml are scattered in3In, 0.5h is handled at 130 DEG C of oil bath heating,
Reaction is poured into after terminating cools down dilution in deionized water, then filtering and washing, dries in 60 DEG C of vacuum drying oven, pulverize
End is standby；
(2) preparation of carbon-polyaniline：Gained carbon dust 0.2g in step (2) is weighed, 40ml 1mol/L are dispersed in
HClO4In solution, under condition of ice bath, the aqueous solution that 20ml contains 0.1~0.4g aniline, magnetic agitation are added；By 0.2450~
0.98g ammonium persulfate (APS) is dissolved in 1mol/L HClO4(mol ratio of aniline and ammonium persulfate is 1 in solution:1), slowly
It is added dropwise into reaction system, 10h is reacted at 0 DEG C, after reaction terminates, washing suction filtration drying is pulverized last, and 80 DEG C of baking 1h are pressed
Above-mentioned steps synthesize carbon：Polyaniline (C:PANI) mass ratio is 1:0.5~1:2 carbon-polyaniline complex carrier (C-PANI)；
(3) weigh carbon-polyaniline complex carrier 80mg obtained by step (2), ultrasonic disperse in 40ml ethylene glycol (EG),
In above-mentioned homogeneous solution, by Pt:Co atomic ratios are 1:0.5~1:3 are separately added into H2PtCl6·6H2O/EG solution and CoCl2/EG
Under solution, magnetic agitation, above-mentioned mixed solution pH value is adjusted to 10 with 2mol/L KOH/EG, 1.5g NaBH are weighed4, it is dissolved in
In 10mL ethylene glycol, it is slowly added dropwise to reaction system, after question response to bubble-free is produced, in 160 DEG C of microwave reductions, reaction
0.5h, after reaction terminates, the drying of centrifuge washing suction filtration obtains the platinum cobalt alloy-catalyst of the polyaniline-coated carbon carrier of solid
(PtCo/C-PANI), grind into powder；
(4) catalyst for obtaining step (3) carries out the de- alloy of gas phase：5ml is added in ptfe autoclave to wave
After hair property acid, the sand core crucible that will be equipped with the platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in reactor, keeps acid
Liquid level be less than core 3cm, the reactor after encapsulation is put into baking oven 60 DEG C of heating, and the reaction time is 10~60min, reaction knot
Room temperature is cooled to after beam；The de- alloy catalyst of gained is washed to neutrality, is placed in after being dried in baking oven and obtains De-PtCo/C-
PANI。
Fig. 1 is the FTIR for carbon-polyaniline complex carrier (C-PANI complex carriers) that the present embodiment step (2) is prepared
(fourier conversion infrared spectrum analysis instrument (Fourier Transform infrared spectroscopy)) spectrogram,
1560cm-1 and 1475cm-1 vibration absorption peak is the stretching vibration peak of C=C and C=N in quinone ring and phenyl ring respectively,
1293cm-1 and 1238cm-1 absworption peak correspond to the C-N stretching vibration peaks of quinoid and benzene formula structure.1135cm-1 and
796cm-1 is in the C-H faces of phenyl ring respectively and out-of-plane bending vibration characteristic absorption band, and 796cm-1 characteristic peak illustrates aniline
Polymerization be Isosorbide-5-Nitrae contraposition polymerization, polyaniline molecule be in chain structure.Compared with the spectrogram of carbon and polyaniline (PANI), C-PANI
The characteristic peak of complex carrier functional group is similar with PANI's, it was demonstrated that grow PANI on C, while illustrating the chemistry of PANI on C
Basic change does not occur for structure.
Fig. 2 is the transmission electron microscope photo of De-PtCo/C-PANI after the de- alloy that the present embodiment step (4) is prepared
(JEOL J-3100 transmission electron microscope mirrors amplify 2850000 times under 200kV).The catalysis prepared as can be seen from Figure 2
Agent grain diameter is 2-4nm, and is uniformly dispersed on carrier.
Fig. 3 is XPS (x-ray photoelectron spectroscopic technique) spectrum analysis that the present embodiment takes off catalyst before and after alloy, from upper
To lower respectively PtCo/C-PANI, De-PtCo/C-PANI XPS spectrum figure.Analyzed by XPS surface-elements, take off position after alloy
The peak of (correspondence Co 2p combine energy) diminishes between 780~800ev, almost disappears；And (correspondence Pt 4f knots between 70~80ev
Close can) peak significant change does not occur.This shows that the Co atoms of catalyst coating are effectively sloughed, and forms the nucleocapsid using Pt as shell
Structure catalyst.In addition, the peak of 530~540ev positions (correspondence O 1s) diminishes after de- alloy, this is due to catalyst surface Co
Oxide be also removed during acid treatment.
Fig. 4 is that the De-PtCo/C of De-PtCo/C-PANI catalyst and uncoated polyaniline in the embodiment of the present invention 1 is catalyzed
Agent takes off the CV test charts after alloy, and the PtCo/C catalyst of uncoated polyaniline takes off the De-PtCo/C of alloy preparation at 0.6V
Put the oxidation peak for occurring in that carrier；And the PtCo/C-PANI catalyst for coating polyaniline takes off De-PtCo/C- prepared by alloy
The carrier oxidation peak of 0.6V positions is obviously reduced in PANI CV figures, while hydrogen adsorption peak substantially becomes big, after this explanation acid treatment
De-PtCo/C-PANI catalyst exposes more Pt catalytic sites, while can effectively reduce acid treatment after coating polyaniline
Damage to carrier, is conducive to the long-acting of catalyst to use.
Embodiment 2
(1) 2g carbon (amorphous carbon) carrier is weighed, the dense HNO of 200ml are scattered in3In, handled at 130 DEG C of oil bath heating
0.5h, reaction is poured into after terminating cools down dilution in deionized water, then filtering and washing, dries in 60 DEG C of vacuum drying oven, grind
Clay into power standby；
(2) preparation of carbon-polyaniline：Carbon dust 0.2g obtained by step (1) is weighed, the concentration for being dispersed in 40ml is
1mol/L HClO4In solution, under condition of ice bath, add 20ml and contain in the aqueous solution of 0.1~0.4g aniline, magnetic agitation,
0.2450~0.98g ammonium persulfates (APS) are dissolved in 1mol/L HClO4(mol ratio of aniline and ammonium persulfate is in solution
1:1), it is slowly added dropwise into reaction system, 10h is reacted at 0 DEG C, after reaction terminates, washing suction filtration drying is pulverized last, 80
DEG C dry 1h, by above-mentioned steps synthesize C:PANI mass ratioes are 1:0.5~1:2 carbon-polyaniline complex carrier (C-PANI)；
(3) weigh carbon-polyaniline complex carrier 80mg obtained by step (2), ultrasonic disperse in 40ml ethylene glycol (EG),
In above-mentioned homogeneous solution, by Pt:Co atomic ratios are 1:0.5~1:3 are separately added into H2PtCl6·6H2O/EG solution and CoCl2/EG
Under solution, magnetic agitation, above-mentioned mixed solution pH value is adjusted to 10 with 2mol/L KOH/EG, 1.5g NaBH is weighed4, it is molten
In 10mL ethylene glycol, it is slowly added dropwise to reaction system, after question response to bubble-free is produced, in 160 DEG C of microwave reductions,
0.5h is reacted, after reaction terminates, the drying of centrifuge washing suction filtration obtains the platinum cobalt alloy catalysis of the polyaniline-coated carbon carrier of solid
Agent (PtCo/C-PANI), grind into powder；
(4) the platinum cobalt alloy-catalyst (PtCo/C-PANI) of the polyaniline-coated carbon carrier for the solid for obtaining step (3)
Carry out liquid phase and take off alloy：The platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in 1mol/L H2SO4In solution, at room temperature
Soak 6h；The de- alloy catalyst of gained is washed to neutrality, is placed in after being dried in baking oven and obtains De-PtCo/C-PANI.
Embodiment 3
(1) 2g carbon carriers are weighed, the dense HNO of 200ml are scattered in3In, 0.5h, reaction knot are handled at 130 DEG C of oil bath heating
Poured into after beam and dilution is cooled down in deionized water, then filtering and washing, dried in 60 DEG C of vacuum drying oven, grind into powder is standby
With；
(2) preparation of carbon-polyaniline：Carbon dust 0.2g obtained by weighing step (1), is dispersed in 40ml 1mol/L's
HClO4In solution, under condition of ice bath, add 20ml and contain in the aqueous solution of 0.1~0.4g aniline, magnetic agitation, by 0.2450
~0.98g ammonium persulfates (APS) be dissolved in 1mol/L HClO4 solution (mol ratio of aniline and ammonium persulfate be 1:1), slowly
It is added dropwise into reaction system, 10h is reacted at 0 DEG C, after reaction terminates, washing suction filtration drying is pulverized last, and 80 DEG C of baking 1h are pressed
Above-mentioned steps synthesize C:PANI mass ratioes are 1:0.5~1:2 carbon-polyaniline complex carrier (C-PANI)；
(3) weigh carbon-polyaniline complex carrier 80mg obtained by step (2), ultrasonic disperse in 40ml ethylene glycol (EG),
In above-mentioned homogeneous solution, CoCl is added2Under/EG solution, magnetic agitation, with 2mol/L KOH/EG by above-mentioned mixed solution pH value
10 are adjusted to, 1.5g NaBH is weighed4, it is dissolved in 10mL ethylene glycol, is slowly added dropwise to reaction system, question response to bubble-free is produced
After life, in 130 DEG C of microwave reductions, 0.5h is reacted, after reaction terminates, Pt is pressed in reaction solution:Co atomic ratios are 1:0.5~
1:3 add H2PtCl6·6H2O/EG solution, the heating using microwave 10min at 130 DEG C, reaction solution is cooled to centrifuge washing after room temperature
Suction filtration is dried, and obtains the platinum cobalt alloy-catalyst (PtCo/C-PANI) of the polyaniline-coated carbon carrier of solid, grind into powder.
(4) the platinum cobalt alloy-catalyst (PtCo/C-PANI) of the polyaniline-coated carbon carrier for the solid for obtaining step (3)
Carry out liquid phase and take off alloy：The platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in 1mol/L H2SO4In solution, at room temperature
Soak 6h；The de- alloy catalyst of gained is washed to neutrality, is placed in after being dried in baking oven and obtains De-PtCo/C-PANI.
The present invention is directed to the deficiencies in the prior art, and the carrier of catalyst is protected by coated with conductive polymer
Shield, carries out de- alloy treatment to catalyst, the core shell structure prepared takes off alloy as catalyst by acid solution or acid vapor afterwards
Agent its carrier damage reduces, and is conducive to extending the service life of catalyst.
Claims (10)
1. a kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst, including carrier and active component, it is special
Levy and be：The carrier is by polyaniline-coated carbon black, and the active component is the platinum cobalt metal with coreshell type structure, wherein platinum
Cobalt alloy is core, and platinum is shell；The weight % of the weight % of carrier 60 of polyaniline-coated carbon black~80；Platinum cobalt with coreshell type structure
The weight % of the weight % of metal 20~40；In the core of the platinum cobalt alloy, the atomic ratio of platinum and cobalt is 1:0.5~1:3.
2. the platinum base of polyaniline-coated carbon carrier according to claim 1 takes off alloy fuel cell catalyst, its feature exists
In：The particle diameter distribution of the platinum cobalt metal with coreshell type structure is in 2~4nm.
3. the platinum base of polyaniline-coated carbon carrier according to claim 2 takes off alloy fuel cell catalyst, its feature exists
In：The platinum cobalt metal with coreshell type structure is dispersed on carrier.
4. the platinum base of polyaniline-coated carbon carrier any one of claim 1-3 takes off the preparation of alloy fuel cell catalyst
Method, its step is as follows：
(1) carbon carrier pre-treatment：Appropriate carbon carrier is weighed, is scattered in concentrated acid and handles, be then washed with deionized to neutrality,
Suction filtration, drying, grind into powder is standby；
(2) preparation of carbon-polyaniline：The carbon dust after step (1) processing is weighed, HClO is dispersed in4In solution, condition of ice bath
Under, the aqueous solution of aniline is added, magnetic agitation dissolves ammonium persulfate into HClO4In solution, it is slowly added dropwise into reaction system, 0 DEG C
Lower reaction a period of time, after reaction terminates, suction filtration is washed, drying is pulverized last, dries, closed by above-mentioned steps at 80 DEG C
Into carbon：Polyaniline mass ratio is 1:0.5~1:2 carbon-polyaniline complex carrier；
(3) using heating using microwave auxiliary ethylene glycol-NaBH4The method of reduction prepares catalyst：By the carbon obtained in step (2)-poly-
Aniline complex carrier is dispersed in ethylene glycol, and ethylene glycol is ultrasonic except that can also suppress the growth of catalyst particle size as reducing agent
It is well mixed it, in above-mentioned homogeneous solution, by Pt:Co atomic ratios are 1:0.5~1:3 are separately added into H2PtCl6·6H2O/
EG solution and CoCl2Under/EG solution, magnetic agitation, above-mentioned mixed solution pH value is adjusted to 9~11 with KOH/EG, weighed
Measure NaBH4It is dissolved in ethylene glycol, is slowly added dropwise to reaction system, it is micro- at 130 DEG C~180 DEG C after question response to bubble-free is produced
Wave heating is reduced, and reacts 0.5~2h, after reaction terminates, is centrifuged, washing, suction filtration, and drying obtains the polyaniline-coated carbon of solid
The platinum cobalt alloy-catalyst of carrier, grind into powder；
(4) the platinum cobalt alloy-catalyst of the polyaniline-coated carbon carrier for the solid for obtaining step (3) is molten by acid vapor or acid
Liquid carries out de- alloy treatment, is then centrifuged for washing to solution in neutrality, final catalyst, i.e. polyaniline-coated are obtained after drying
The platinum base of carbon carrier takes off alloy fuel cell catalyst.
5. the platinum base of polyaniline-coated carbon carrier according to claim 4 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：In the step (1), the concentrated acid is dense HNO3；It is described to be washed with deionized in the step (1)
Comprised the following steps that to neutral：Handle 0.5h at 130 DEG C of oil bath heating, reaction poured into after terminating in deionized water cool down it is dilute
Release, then, suction filtration, washing.
6. the platinum base of polyaniline-coated carbon carrier according to claim 5 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：In the step (2), the carbon dust is 0.2g, the HClO4Concentration be 1mol/L；The step
(2) in, described aniline and the mol ratio of ammonium persulfate are 1:1.
7. the platinum base of polyaniline-coated carbon carrier according to claim 6 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：In the step (3), the concentration of the KOH/EG is 2mol/L.
8. the platinum base of polyaniline-coated carbon carrier according to claim 7 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：In the step (4), described de- alloy takes off alloy for gas phase or liquid phase takes off alloy.
9. the platinum base of polyaniline-coated carbon carrier according to claim 8 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：The gas phase takes off alloy：Add after appropriate volatile acid, will be equipped with ptfe autoclave
The sand core crucible of the platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in reactor, keeps the liquid level of acid to be less than core
3cm, the reactor after encapsulation is put into baking oven and heated, and reaction is cooled to room temperature after terminating；The equal water of de- alloy catalyst of gained
Neutrality is washed till to be placed in drying in baking oven.
10. the platinum base of polyaniline-coated carbon carrier according to claim 8 takes off the preparation side of alloy fuel cell catalyst
Method, it is characterised in that：The liquid phase takes off alloy：The platinum cobalt alloy-catalyst of polyaniline-coated carbon carrier is placed in 1mol/L
H2SO4In solution, 6h is soaked at room temperature；The de- alloy catalyst of gained is washed to neutrality, is placed in after being dried in baking oven and obtains De-
PtCo/C-PANI。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232210A (en) * | 2018-01-18 | 2018-06-29 | 兰州交通大学 | A kind of high stability, low-load amount ultra-dispersed noble metal electrocatalyst preparation method |
| CN111129518A (en) * | 2019-12-30 | 2020-05-08 | 一汽解放汽车有限公司 | Modified carbon carrier, preparation method thereof and application thereof in fuel cell |
| CN111725524A (en) * | 2019-03-22 | 2020-09-29 | 青岛创启新能催化科技有限公司 | Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103372467A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Support for electrode catalyst and method of manufacturing the same, electrode catalyst and fuel cell |
| CN104475126A (en) * | 2014-12-11 | 2015-04-01 | 北京化工大学 | 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 |
| CN104600326A (en) * | 2014-12-19 | 2015-05-06 | 上海交通大学 | Preparation method of carbon-supported nano platinum alloy catalyst |
| CN104600327A (en) * | 2014-12-19 | 2015-05-06 | 上海交通大学 | Preparation method of carbon-supported nano platinum alloy catalyst |
| CN105908001A (en) * | 2016-06-13 | 2016-08-31 | 大连理工大学 | Si-containing nanometer porous Pd material and preparation method thereof |
-
2017
- 2017-04-26 CN CN201710284291.5A patent/CN106960962B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103372467A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Support for electrode catalyst and method of manufacturing the same, electrode catalyst and fuel cell |
| CN104475126A (en) * | 2014-12-11 | 2015-04-01 | 北京化工大学 | 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 |
| CN104600326A (en) * | 2014-12-19 | 2015-05-06 | 上海交通大学 | Preparation method of carbon-supported nano platinum alloy catalyst |
| CN104600327A (en) * | 2014-12-19 | 2015-05-06 | 上海交通大学 | Preparation method of carbon-supported nano platinum alloy catalyst |
| CN105908001A (en) * | 2016-06-13 | 2016-08-31 | 大连理工大学 | Si-containing nanometer porous Pd material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232210A (en) * | 2018-01-18 | 2018-06-29 | 兰州交通大学 | A kind of high stability, low-load amount ultra-dispersed noble metal electrocatalyst preparation method |
| CN111725524A (en) * | 2019-03-22 | 2020-09-29 | 青岛创启新能催化科技有限公司 | Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell |
| JP2022521545A (en) * | 2019-03-22 | 2022-04-08 | ジョンソン、マッセイ、フュエル、セルズ、リミテッド | Fuel cell catalyst |
| CN111725524B (en) * | 2019-03-22 | 2022-10-25 | 青岛创启新能催化科技有限公司 | Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell |
| JP7349500B2 (en) | 2019-03-22 | 2023-09-22 | ジョンソン マッセイ ハイドロジェン テクノロジーズ リミテッド | Fuel cell catalyst |
| CN111129518A (en) * | 2019-12-30 | 2020-05-08 | 一汽解放汽车有限公司 | Modified carbon carrier, preparation method thereof and application thereof in fuel cell |
| CN113101974A (en) * | 2021-04-19 | 2021-07-13 | 宁夏德昊科技产业有限公司 | Method for preparing o-aminophenol by hydrogenation reduction catalysis |
| CN114188553A (en) * | 2021-12-01 | 2022-03-15 | 武汉理工大学 | Pd/Co-C catalyst, and preparation method and application thereof |
| CN115133050A (en) * | 2022-07-06 | 2022-09-30 | 北京化工大学 | Platinum-cobalt alloy catalyst, preparation method and application thereof |
| CN115064711A (en) * | 2022-07-13 | 2022-09-16 | 清科(深圳)氢能科技有限公司 | Preparation method and application of high-activity in-situ nitrogen-doped carbon carrier loaded platinum-based alloy catalyst |
| CN115064711B (en) * | 2022-07-13 | 2024-05-31 | 清科(深圳)氢能科技有限公司 | Preparation method and application of nitrogen-doped carbon carrier-supported platinum-based alloy catalyst |
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