CN108963273A - A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof - Google Patents
A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof Download PDFInfo
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- CN108963273A CN108963273A CN201810680087.XA CN201810680087A CN108963273A CN 108963273 A CN108963273 A CN 108963273A CN 201810680087 A CN201810680087 A CN 201810680087A CN 108963273 A CN108963273 A CN 108963273A
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- platinum
- catalyst
- elctro
- branch shape
- presoma
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 230
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 115
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 239000004280 Sodium formate Substances 0.000 claims description 10
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 10
- 235000019254 sodium formate Nutrition 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229960003975 potassium Drugs 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000001508 potassium citrate Substances 0.000 claims description 5
- 229960002635 potassium citrate Drugs 0.000 claims description 5
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 5
- 235000011082 potassium citrates Nutrition 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 filters Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of Proton Exchange Membrane Fuel Cells, a kind of branch shape platinum elctro-catalyst and the preparation method and application thereof is disclosed.The method: (S1) is soluble in water by platinum presoma, complexing agent, obtains mixed solution；Reducing agent is mixed with mixed solution, stands, obtains the solution of platinum colloidal sol；(S2) solution of platinum colloidal sol and carbon carrier are mixed, subsequent processing, obtains branch shape platinum elctro-catalyst；Or mix platinum presoma, complexing agent, carbon carrier with water, obtain the mixed liquor of carbon-containing carrier；Reducing agent is mixed with the mixed liquor of carbon-containing carrier, is stood, subsequent processing obtains branch shape platinum elctro-catalyst.Platinum elctro-catalyst of the invention is branch shape platinum elctro-catalyst, has high index activity crystal face abundant, while having high stability and high catalytic activity；Method of the invention is simple, environmentally protective, low energy consumption, low in cost, it is easy to accomplish the bulk industrial of elctro-catalyst produces.
Description
Technical field
The invention belongs to Electro Catalysts for PEMFC fields, and in particular to a kind of branch shape platinum elctro-catalyst
And the preparation method and application thereof.The application of branch shape platinum elctro-catalyst of the invention in Proton Exchange Membrane Fuel Cells, catalysis
The oxidation of Proton Exchange Membrane Fuel Cells methanol and hydrogen reduction.
Background technique
In a fuel cell, elctro-catalyst plays the effect of electrochemical reaction " factory ", is the core material of battery, electricity
The development of catalyst is the key that one of fuel cell.Noble metal platinum, palladium or platinum-nickel alloys are to hydrogen, formic acid, methanol, second
The oxidation reaction and oxygen reduction reaction of the fuel molecules such as alcohol all have very high catalytic activity, therefore at this stage commercially and real
The elctro-catalyst overwhelming majority is pallium-on-carbon or palladium on carbon elctro-catalyst.The main target of elctro-catalyst development is to improve to urge
Change activity and stability, the two are indispensable.
The method that electronation prepares platinum catalyst is numerous, most common to have immersion reduction method and polyol reduction method.Gu
Phase immersion reduction method is first to impregnate noble metal precursor body and carbon carrier, and after drying and grinding, high temperature (generally higher than 200 DEG C) exists
Lead to hydrogen reducing in tube furnace, this method energy consumption is high, and noble metal is unevenly distributed on the carbon carrier；Liquid infiltration and reduction method
It is first to impregnate noble metal precursor body and carbon carrier, the reduction of strong reductant room temperature is then added, although this method is simple, fast
Speed and Non-energy-consumption, but prepared elctro-catalyst partial size is big and particle diameter distribution is uneven.Most common polyol reduction method is
The polyalcohols such as ethylene glycol are used as solvent and reducing agent, to heat (120~160 DEG C) 3~8 hours simultaneously, by noble metal precursor
Body is reduced to elctro-catalyst, and since polyalcohol serves protectant simultaneously, elctro-catalyst partial size prepared by this method is small
And be uniformly dispersed, the disadvantage is that energy consumption is high, and the polyalcohols such as ethylene glycol itself aoxidize during the reaction, cannot recycle,
It is at high cost.In addition to this, the platinum catalyst of above-mentioned these chemical reduction methods preparation is platinum grain, these catalyst were using
It is easy curing in journey to grow up, stability is poor.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of branch shape platinum elctro-catalysts
And preparation method thereof.It is method low energy consumption of the invention, simple, low in cost, it is easy to accomplish the volume industrial metaplasia of elctro-catalyst
It produces.Elctro-catalyst prepared by the present invention is branch shape platinum elctro-catalyst, while having high stability and high catalytic activity.
Another object of the present invention is to provide the applications of above-mentioned branch shape platinum elctro-catalyst.The branch shape platinum electro-catalysis
Application of the agent in Proton Exchange Membrane Fuel Cells, especially Catalytic Proton exchange film fuel battery methanol oxidation and hydrogen reduction.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of branch shape platinum elctro-catalyst, comprising the following steps:
(S1) platinum presoma, complexing agent is soluble in water, obtain mixed solution；Reducing agent is mixed with mixed solution, it is quiet
It sets, obtains the solution of platinum colloidal sol；The complexing agent is more than one in citric acid, sodium citrate or potassium citrate；The reduction
Agent is more than one in formaldehyde, formic acid or sodium formate；(S2) solution of platinum colloidal sol and carbon carrier are mixed, subsequent processing, is obtained
Branch shape platinum elctro-catalyst；
Or
(P1) platinum presoma, complexing agent, carbon carrier are mixed with water, obtains the mixed liquor of carbon-containing carrier；By reducing agent with
The mixed liquor of carbon-containing carrier mixes, and stands, and subsequent processing obtains branch shape platinum elctro-catalyst；The complexing agent is citric acid, lemon
More than one in lemon acid sodium or potassium citrate；The reducing agent is more than one in formaldehyde, formic acid or sodium formate.
Standing described in step (S1) is to be stored at room temperature；The time being stored at room temperature is 24~96 hours.
Mixing described in step (S2), which refers to, to be soaked in carbon carrier in the solution of platinum colloidal sol or by the solution of platinum colloidal sol
Ultrasonic disperse processing is carried out with carbon carrier；The time of the ultrasonic disperse is preferably 0.5~2h；
Subsequent processing described in step (S2), which refers to, is filtered the product of mixing, washs, and is dried.
Standing described in step (P1) is to be stored at room temperature；The time being stored at room temperature is 24-96 hours.
After subsequent processing described in step (P1) refers to standing, ultrasonic disperse, then product is filtered, it washs, it is dry
Processing.The time of the ultrasonic disperse is preferably 0.5~2h.
Platinum presoma described in step (S1) and (P1) is water-soluble platinum presoma, preferably chloroplatinic acid, potassium chloroplatinite,
Chloroplatinous acid, sodium chloroplatinite, potassium chloroplatinate, more than one in platinic sodium chloride；
The molar ratio of complexing agent described in step (S1) and (P1) and platinum presoma is (0.5~5): 1；
The molar ratio of reducing agent described in step (S1) and (P1) and platinum presoma is (10~200): 1；It is preferred that reducing agent
When for formaldehyde, the molar ratio of formaldehyde and platinum presoma is 10:1~100:1；When reducing agent is formic acid, formic acid and platinum presoma
Molar ratio is 50:1~200:1；When reducing agent is sodium formate, the molar ratio of sodium formate and platinum presoma is 20:1~100:1.
The dosage of carbon carrier and platinum presoma meets the following conditions in step (S2) and (P1): platinum accounts for platinum and the total matter of carbon carrier
The 20%~60% of amount, i.e. carrying capacity of the platinum in branch shape platinum elctro-catalyst are 20%~60%.
The dosage relation of platinum presoma and water meets the following conditions in step (S1) and (P1): platinum presoma rubbing in water
Your volumetric concentration is 0.05~0.001mol/L.
Carbon carrier can be carbon black, active carbon, carbon nanotube, carbon fiber, graphene etc. in step (S2) and (P1).
The branch shape platinum elctro-catalyst is prepared by the above method.
Application of the branch shape platinum elctro-catalyst branch shape platinum elctro-catalyst in Proton Exchange Membrane Fuel Cells, especially
It is the application in the oxidation of Catalytic Proton exchange film fuel battery methanol and hydrogen reduction.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) platinum elctro-catalyst of the invention is branch shape platinum elctro-catalyst, not platinum grain, has high index abundant living
Property crystal face, while there is high stability and high catalytic activity；
(2) present invention takes water as a solvent, environmentally protective；Reaction process is room temperature, saves energy consumption；And method of the invention
Simply, low in cost, it is easy to accomplish the bulk industrial of elctro-catalyst produces.
Detailed description of the invention
Fig. 1 is the scanning transmission electron microscope photo of branch shape platinum colloidal sol prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo for loading branch shape platinum elctro-catalyst on the carbon carrier prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, present invention is further described in detail, but embodiments of the present invention are not limited to
This.
Embodiment 1
(1) it is that 0.038mol/L platinum acid chloride solution is added in 100ml water by 8ml concentration, 448mg sodium citrate is then added
Dissolution obtains mixed solution；0.0598mol formic acid is added into mixed solution, stands 96 hours at room temperature, obtains branch shape
Platinum sol solution；
(2) 90mg carbon dust (carbon black) ultrasonic disperse 1h is added into platinum sol solution, filters, filter cake is washed with deionized water
It washs completely, vacuum drying obtains carbon supported platinum catalyst i.e. branch shape platinum elctro-catalyst, the quality hundred of platinum in elctro-catalyst after grinding
Score is 40%.
Fig. 1 is the scanning transmission electron microscope figure of branch shape platinum colloidal sol (branching shape platinum in colloidal sol) manufactured in the present embodiment.From Fig. 1
As can be seen that platinum is apparent racemosus wooden fork shape.Fig. 2 is that branch shape platinum elctro-catalyst manufactured in the present embodiment (is supported on carbon carrier
On branch shape platinum elctro-catalyst) transmission electron microscope photo.Figure it is seen that most platinum are branch shape, in carbon carrier
On be evenly distributed.
Electro-chemical test discovery, the electrochemical surface area of catalyst manufactured in the present embodiment are 58m2·g-1；?
0.5mol·L-1 H2SO4With 50mV s in solution-12000 circle of scanning speed scanning, the electrochemistry for then calculating catalyst is living
Property area attenuation.Test discovery, the catalyst is after stability test, electrochemical surface area residue 58%, and same type
Commercial catalysts electrochemical surface area residue 25% under the same test conditions.When 0.9V (relative to standard hydrogen electrode), this
The hydrogen reduction mass activity of the catalyst of embodiment preparation is 140Ag-1, higher than the mass activity of commercial catalysts by 150%.?
0.5mol·L-1 H2SO4+0.5mol·L-1 CH3The methanol oxidative activity of the catalyst is tested in OH solution, mass activity is
850A·g-1, higher than the mass activity of commercial catalysts by 180%.
Embodiment 2
(1) it is that 0.038mol/L platinum acid chloride solution is added in 100ml water by 8ml concentration, 150mg sodium citrate is then added
Dissolution obtains mixed solution；0.0156mol formic acid is added into mixed solution, stands 24 hours at room temperature, obtains branch shape platinum
Sol solution；
(2) 40mg carbon dust ultrasound is added into platinum sol solution and impregnates 1h, filter, filter cake is washed with water completely, vacuum
It is dry, carbon supported platinum catalyst i.e. branch shape platinum elctro-catalyst is obtained after grinding, the mass percent of platinum is 60% in elctro-catalyst.
Electro-chemical test discovery, the electrochemical surface area of the catalyst are 52m2·g-1；Test discovery, the catalyst is through overstability
After test, electrochemical surface area residue 45%.When 0.9V (relative to standard hydrogen electrode), the hydrogen reduction mass activity of catalyst
For 120Ag-1.In 0.5molL-1 H2SO4+0.5mol·L-1 CH3The methanol oxidation that the catalyst is tested in OH solution is lived
Property, mass activity 650Ag-1。
Embodiment 3
(1) it is that 0.038mol/L potassium chloroplatinite is added in 100ml water by 8ml concentration, it is molten that 220mg citric acid is then added
Solution obtains mixed solution；Sodium formate 413mg is added into mixed solution, stands 48 hours at room temperature, obtains branch shape platinum colloidal sol
Solution；
(2) 120mg carbon dust collecting platinum catalyst ultrasonic disperse 1h is added into platinum sol solution, filters, filter cake is spent
Ionized water washes clean, vacuum drying, obtains carbon supported platinum catalyst i.e. branch shape platinum elctro-catalyst, platinum in elctro-catalyst after grinding
Mass percent be 20%.Electro-chemical test discovery, the electrochemical surface area of the catalyst are 135m2g-1；Test discovery,
The catalyst is after stability test, electrochemical surface area residue 40%.At 0.9V (relative to standard hydrogen electrode), urge
The hydrogen reduction mass activity of agent is 90Ag-1.In 0.5molL-1 H2SO4+0.5mol·L-1 CH3Test should in OH solution
The methanol oxidative activity of catalyst, mass activity 520Ag-1。
Embodiment 4
(1) it is that 0.038mol/L potassium chloroplatinite is added in 100ml water by 8ml concentration, 49mg potassium citrate is then added
Dissolution obtains mixed solution；Sodium formate 2050mg is added into mixed solution, stands 48 hours at room temperature, obtains branch shape platinum
Sol solution；
(2) 120mg carbon dust ultrasonic disperse 1h is added into platinum sol solution, filters, filter cake is washed with deionized dry
Only, it is dried in vacuo, carbon supported platinum catalyst i.e. branch shape platinum elctro-catalyst is obtained after grinding, the mass percent of platinum in elctro-catalyst
It is 20%.Electro-chemical test discovery, the electrochemical surface area of the catalyst are 125m2·g-1；Test discovery, catalyst warp
After overstability test, electrochemical surface area residue 45%.When 0.9V (relative to standard hydrogen electrode), the hydrogen reduction of catalyst
Mass activity is 80Ag-1.In 0.5molL-1 H2SO4+0.5mol·L-1 CH3The methanol of the catalyst is tested in OH solution
Oxidation activity, mass activity are 450A g-1。
Embodiment 5
(1) it is that 0.038mol/L potassium chloroplatinite is added in 100ml water by 8ml concentration, 260mg sodium citrate is then added
Dissolution obtains mixed solution；Formaldehyde 20ml is added into mixed solution, stands 48 hours at room temperature, obtains branch shape platinum colloidal sol
Solution；
(2) 120mg carbon dust ultrasound is added into platinum sol solution and impregnates 1h, filter, filter cake is washed with deionized dry
Only, it is dried in vacuo, carbon supported platinum catalyst is obtained after grinding, the mass ratio of platinum is 20% in elctro-catalyst.Electro-chemical test discovery,
The electrochemical surface area of the catalyst is 140m2·g-1；Test discovery, the catalyst is after stability test, electrochemistry
Active area residue 38%.When 0.9V (relative to standard hydrogen electrode), the hydrogen reduction mass activity of catalyst is 85Ag-1.?
0.5mol·L-1 H2SO4+0.5mol·L-1 CH3The methanol oxidative activity of the catalyst is tested in OH solution, mass activity is
800A·g-1。
Claims (10)
1. a kind of preparation method of branch shape platinum elctro-catalyst, it is characterised in that: the following steps are included:
(S1) platinum presoma, complexing agent is soluble in water, obtain mixed solution；Reducing agent is mixed with mixed solution, stands, obtains
To the solution of platinum colloidal sol；The complexing agent is more than one in citric acid, sodium citrate or potassium citrate；The reducing agent is first
More than one in aldehyde, formic acid or sodium formate；(S2) solution of platinum colloidal sol and carbon carrier are mixed, subsequent processing, obtains branch shape
Platinum elctro-catalyst；
Or
(P1) platinum presoma, complexing agent, carbon carrier are mixed with water, obtains the mixed liquor of carbon-containing carrier；By reducing agent with it is carbon containing
The mixed liquor of carrier mixes, and stands, and subsequent processing obtains branch shape platinum elctro-catalyst；The complexing agent is citric acid, citric acid
More than one in sodium or potassium citrate；The reducing agent is more than one in formaldehyde, formic acid or sodium formate.
2. the preparation method of branch shape platinum elctro-catalyst according to claim 1, it is characterised in that: in step (S2) and (P1)
The dosage of carbon carrier and platinum presoma meets the following conditions: platinum accounts for the 20%~60% of platinum and carbon carrier gross mass, i.e., platinum is in branch
Carrying capacity in wooden fork shape platinum elctro-catalyst is 20%~60%.
3. the preparation method of branch shape platinum elctro-catalyst according to claim 1, it is characterised in that: in step (S1) and (P1)
The molar ratio of the complexing agent and platinum presoma is (0.5~5): 1；
The molar ratio of reducing agent described in step (S1) and (P1) and platinum presoma is (10~200): 1.
4. the preparation method of branch shape platinum elctro-catalyst according to claim 3, it is characterised in that: when reducing agent is formaldehyde,
The molar ratio of formaldehyde and platinum presoma is 10:1~100:1；When reducing agent is formic acid, the molar ratio of formic acid and platinum presoma is
50:1~200:1；When reducing agent is sodium formate, the molar ratio of sodium formate and platinum presoma is 20:1~100:1.
5. the preparation method of branch shape platinum elctro-catalyst according to claim 1, it is characterised in that:
It stands described in step (S1) and (P1) to be stored at room temperature；
Mixing described in step (S2), which refers to, to be soaked in carbon carrier in the solution of platinum colloidal sol or by the solution and carbon of platinum colloidal sol
Carrier carries out ultrasonic disperse processing；
Platinum presoma described in step (S1) and (P1) is water-soluble platinum presoma, and specially chloroplatinic acid, potassium chloroplatinite, chlorine is sub-
Platinic acid, sodium chloroplatinite, potassium chloroplatinate, more than one in platinic sodium chloride.
6. the preparation method of branch shape platinum elctro-catalyst according to claim 5, it is characterised in that:
The time being stored at room temperature is 24~96h.
7. the preparation method of branch shape platinum elctro-catalyst according to claim 1, it is characterised in that: after described in step (S2)
Continuous processing, which refers to, is filtered the product of mixing, washs, is dried；
After subsequent processing described in step (P1) refers to standing, ultrasonic disperse, then product is filtered, it washs, is dried.
8. a kind of branch shape platinum elctro-catalyst obtained by any one of claim 1~7 preparation method.
9. application of the branch shape platinum elctro-catalyst in Proton Exchange Membrane Fuel Cells according to claim 8.
10. application according to claim 9, it is characterised in that: the branch shape platinum elctro-catalyst is exchanged in Catalytic Proton
Application in the oxidation of membrane cell methanol and hydrogen reduction.
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