CN110429287A - A kind of preparation and application of hollow PtCu octahedron alloy - Google Patents
A kind of preparation and application of hollow PtCu octahedron alloy Download PDFInfo
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- CN110429287A CN110429287A CN201910706199.2A CN201910706199A CN110429287A CN 110429287 A CN110429287 A CN 110429287A CN 201910706199 A CN201910706199 A CN 201910706199A CN 110429287 A CN110429287 A CN 110429287A
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- octahedron
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a kind of synthetic methods of hollow PtCu octahedron nanocatalyst, it is characterized by comprising following steps: (1) rich Cu octahedron PtCu nanocatalyst being added in organic solvent DMF, metal platinum and the concentration of copper are 0.01~0.05mg/mL, are stirred 5~8 minutes at room temperature；(2) DMF solution of metal platinum salt is added into homogeneous mixture solotion obtained by step (1), the concentration of metal platinum is 0.0001~0.0003mg/mL, is stirred 3~10 minutes at room temperature；(3) it is transferred in autoclave and reacts 2~12 hours to mixed solution obtained by step (2), temperature is controlled at 80~160 DEG C；(4) it will be washed after the cooling of step (3) products therefrom, up to hollow PtCu octahedron Nanoalloy after centrifuge separation.
Description
Technical field
The present invention relates to a kind of synthetic method of hollow PtCu octahedron nanocatalyst for fuel cell and firing
Expect the application of battery.
Background technique
Pt metal oxygen reduction, biomass fuel and in terms of do not replace.But
Since Pt is rare, price, cause the commercialization of fuel cell at high cost, so the utilization efficiency of optimization Pt and extension elctro-catalyst
Durability be final large-scale use fuel cell two key factors.In addition, the shape of alloy nano catalyst, size
Serve with performance of the ingredient to catalyst it is conclusive, therefore prepare shape, size and the controllable Pt based alloy of ingredient are urged
Agent is most important.The present invention is the two-step method of seed using richness Cu octahedron PtCu nanocatalyst, has successfully synthesized sky
Heart PtCu octahedron Nanoalloy is urged in alkaline cathode redox reactions relative to similar metal electricity as elctro-catalyst
Agent shows highest mass activity, and endurance quality is also much higher than the Pt/C elctro-catalyst of business.Therefore such is hollow
PtCu octahedron nanocatalyst has certain application prospect in a fuel cell.
Summary of the invention
The technical problem to be solved by the present invention is obtaining hollow PtCu octahedron alloyed nanocrystal.This kind of crystal closes
At method novelty, pattern is unified, has excellent catalytic properties in a fuel cell.
The technical scheme is that a kind of preparation and application of hollow PtCu octahedron alloy, include the following steps:
(1) rich Cu octahedron PtCu nanocatalyst being added in organic solvent DMF, the concentration of metal platinum and copper is 0.01~
0.05mg/mL is stirred 5~8 minutes at room temperature；Added organic solvent DMF needs mixed with richness Cu octahedron PtCu nanocatalyst
It closes uniform；(2) DMF solution of metal platinum salt is added into homogeneous mixture solotion obtained by step (1), the concentration of metal platinum is
For 0.0001~0.0003mg/mL, the volume ratio of the DMF solution of mixed solution and metal platinum salt is 450:1 ~ 550:1, at room temperature
Stirring 3~10 minutes；(3) it is transferred in autoclave and reacts 2~12 hours to mixed solution obtained by step (2), temperature control
System is at 80~160 DEG C；(4) it will be washed after the cooling of step (3) products therefrom, it is octahedra up to hollow PtCu after centrifuge separation
Nanoalloy.
The hollow PtCu octahedron alloy is that current platinum base and palladium base Nanoalloy are recorded in the literature in alkalinity
The nano metal elctro-catalyst of highest mass activity is shown in redox reactions.
Application of the hollow PtCu octahedron nanocatalyst in fuel cell.
Beneficial effects of the present invention: it can control by this method and synthesize hollow PtCu octahedron nanocatalyst.This kind closes
Gold crystals by adopting structure novel, high income, catalytic performance is excellent, have replace current business platinum black or the black catalyst of pallium-on-carbon can
Energy.
Detailed description of the invention
Fig. 1 is the transmission electron microscope test result figure of hollow PtCu octahedron Nanoalloy；
Fig. 2 is the high resolution transmission electron microscope test result figure of hollow PtCu octahedron nanocatalyst；
Fig. 3 is the catalytic performance comparison of hollow PtCu octahedron nanocatalyst and the black redox reactions of business pallium-on-carbon
Figure.
Specific embodiment
Embodiment 1:
A kind of preparation and application of hollow PtCu octahedron alloy, feature include the following steps:
(1) rich Cu octahedron PtCu nanocatalyst being added in organic solvent DMF, the concentration of metal platinum and copper is 0.01~
0.05mg/mL is stirred 5~8 minutes at room temperature；Added organic solvent DMF needs mixed with richness Cu octahedron PtCu nanocatalyst
It closes uniform；
(2) be added the DMF solution of metal platinum salt into homogeneous mixture solotion obtained by step (1), the concentration of metal platinum be for
0.0001~0.0003mg/mL, the volume ratio of the DMF solution of mixed solution and metal platinum salt are 450:1, stir 3 at room temperature~
10 minutes；
(3) it is transferred in autoclave and reacts 2.5 hours to mixed solution obtained by step (2), temperature is controlled at 115 DEG C；
(4) it will be washed after the cooling of step (3) products therefrom, up to hollow PtCu octahedron nano-catalytic after centrifuge separation
Agent.Products therefrom is cooling, be centrifugated and spends ethyl alcohol carries out after washing three times distributed and saved in ethanol solution.
Embodiment 2:
A kind of preparation and application of hollow PtCu octahedron alloy, feature include the following steps:
(1) rich Cu octahedron PtCu nanocatalyst being added in organic solvent DMF, the concentration of metal platinum and copper is 0.01~
0.05mg/mL is stirred 5~8 minutes at room temperature；Added organic solvent DMF needs mixed with richness Cu octahedron PtCu nanocatalyst
It closes uniform；
(2) be added the DMF solution of metal platinum salt into homogeneous mixture solotion obtained by step (1), the concentration of metal platinum be for
0.0001~0.0003mg/mL, the volume ratio of the DMF solution of mixed solution and metal platinum salt are 550:1, stir 3 at room temperature~
10 minutes；
(3) it is transferred in autoclave and reacts 5 hours to mixed solution obtained by step (2), temperature is controlled at 115 DEG C；
(4) it will be washed after the cooling of step (3) products therefrom, up to hollow PtCu octahedron nano-catalytic after centrifuge separation
Agent.Products therefrom is cooling, be centrifugated and spends ethyl alcohol carries out after washing three times distributed and saved in ethanol solution.
Embodiment 3:
A kind of preparation and application of hollow PtCu octahedron alloy, feature include the following steps:
(1) rich Cu octahedron PtCu nanocatalyst being added in organic solvent DMF, the concentration of metal platinum and copper is 0.01~
0.05mg/mL is stirred 5~8 minutes at room temperature；Added organic solvent DMF needs mixed with richness Cu octahedron PtCu nanocatalyst
It closes uniform；
(2) be added the DMF solution of metal platinum salt into homogeneous mixture solotion obtained by step (1), the concentration of metal platinum be for
0.0001~0.0003mg/mL, the volume ratio of the DMF solution of mixed solution and metal platinum salt are 500:1, stir 3 at room temperature~
10 minutes；
(3) it is transferred in autoclave and reacts 8 hours to mixed solution obtained by step (2), temperature is controlled at 115 DEG C；
(4) it will be washed after the cooling of step (3) products therefrom, up to hollow PtCu octahedron nano-catalytic after centrifuge separation
Agent.Products therefrom is cooling, be centrifugated and spends ethyl alcohol carries out after washing three times distributed and saved in ethanol solution.
Reversed embodiment 1
(1) by the acetylacetone,2,4-pentanedione platinum of 0.028 g, the CuCl of 0.012 g2.2H2O, 0.280 g cetyl trimethyl chlorination
Ammonium, the diethylene glycol (DEG) of 87.6 ul, the oleyl amine of 35 ml are added in the reaction kettle that volume is 40 ml, under the conditions of magnetic agitation will
Said mixture stirs.
(2) reaction kettle 180 DEG C are heated to react 10 hours.
(3) products obtained therefrom is centrifuged and is repeatedly washed.
By that can find compared with reversed embodiment 1, the hollow PtCu dodecahedron nanometer frame in reversed embodiment is in oxygen
The catalytic activity that catalytic activity in gas reduction reaction compares the hollow PtCu octahedron alloy that this experiment obtains wants low.
Reversed embodiment 2
(1) by the XC-72 of 50 mg, the CuCl of 22.0 mg2.2H2O is added in the three-neck flask of the ethyl alcohol equipped with 30 ml and stirs,
Add 0.25 mol NaBH4With 0.01 M NaOH (2550 uL).
(2) above-mentioned mixed solution 70 DEG C are heated to react 1 hour.
(3) 19.1 mM K are added into mixed solution obtained by step (2)2PtCl4(3400 uL), and 3 are reacted at 70 DEG C
Hour.
(4) products obtained therefrom is centrifuged and is repeatedly washed with aqueous solution.
By that can find compared with reversed embodiment 2, the hollow ball shape PtCu nanocatalyst in reversed embodiment is in oxygen
The catalytic activity that catalytic activity in gas reduction reaction compares the hollow PtCu octahedron alloy that this experiment obtains wants low.
The activity of hollow PtCu octahedron nanocatalyst prepared by the above method is to redox reactions and business carbon
It carries platinum black to make comparisons, in oxygen reduction reaction (ORR), quality specific activity is 18.5 times of business pallium-on-carbon black (Pt/C).
Claims (8)
1. a kind of preparation method of hollow PtCu octahedron alloy, characterized by the following steps: (1) by rich Cu octahedral
Body PtCu nanocatalyst is added in organic solvent dimethylformamide (DMF), stirs 5~8 minutes at room temperature；It is added organic molten
Agent DMF needs are uniformly mixed with richness Cu octahedron PtCu nanocatalyst；(2) to homogeneous mixture solotion obtained by step (1)
The middle DMF solution that metal platinum salt is added, is stirred 3~10 minutes at room temperature；(3) transfer of mixed solution obtained by step (2) is supreme
It is reacted in pressure reaction kettle；(4) it will be washed after the cooling of step (3) products therefrom, up to hollow PtCu octahedral after centrifuge separation
Body Nanoalloy.
2. a kind of method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: institute in step (1)
The concentration of the rich Cu octahedron PtCu nanocatalyst metal platinum and copper stated is 0.01~0.05mg/mL.
3. a kind of preparation method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: step (2)
Described in metal platinum salt be acetylacetone,2,4-pentanedione platinum.
4. a kind of preparation method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: step (2)
The concentration of the metal platinum is 0.0001~0.0003mg/mL.
5. a kind of preparation method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: step (2)
Described in mixed solution and metal platinum salt DMF solution volume ratio be 450:1 ~ 550:1.
6. a kind of preparation method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: step (3)
Described at 80~160 DEG C, the reaction time is 2-12 hours for reaction temperature control in a high pressure reaction kettle.
7. a kind of preparation method of hollow PtCu octahedron alloy according to claim 1, it is characterised in that: the sky
Heart octahedron PtCu nanocrystal size is uniform, in 24.0nm or so；The thickness of wall is in 2.2 nm or less.
8. the hollow PtCu octahedron alloy as described in one of claim 1-7 is in a fuel cell as electrocatalyst for cathode pair
The application of the reduction of oxygen.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883588A (en) * | 2022-05-07 | 2022-08-09 | 贵州大学 | Ultrahigh-stability oxygen reduction catalyst for room-temperature hydrogen fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103352254A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Method for preparing octahedral platinoid alloy nanocrystals and octahedral platinoid alloy nanocrystal prepared through adopting same |
| CN108258258A (en) * | 2018-01-22 | 2018-07-06 | 贵州大学 | A kind of synthetic method of rich Cu octahedrons PtCu nanocatalysts for fuel cell and application |
-
2019
- 2019-08-01 CN CN201910706199.2A patent/CN110429287A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103352254A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Method for preparing octahedral platinoid alloy nanocrystals and octahedral platinoid alloy nanocrystal prepared through adopting same |
| CN108258258A (en) * | 2018-01-22 | 2018-07-06 | 贵州大学 | A kind of synthetic method of rich Cu octahedrons PtCu nanocatalysts for fuel cell and application |
Non-Patent Citations (2)
| Title |
|---|
| QIANG YUAN ET AL.: "Composition-driven shape evolution to Cu-rich PtCu octahedral alloy nanocrystals as superior bifunctional catalysts for methanol oxidation andoxygen reduction reaction", 《NANOSCALE》 * |
| YALING XIONG ET AL.: "Facile synthesis of PtCu3 alloy hexapods and hollow nanoframes as highly active electrocatalysts for methanol oxidation", 《CRYSTENGCOMM》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883588A (en) * | 2022-05-07 | 2022-08-09 | 贵州大学 | Ultrahigh-stability oxygen reduction catalyst for room-temperature hydrogen fuel cell |
| CN114883588B (en) * | 2022-05-07 | 2023-10-20 | 贵州大学 | Ultra-high stability oxygen reduction catalyst for room temperature hydrogen fuel cell |
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