CN107221685A - A kind of two-dimentional inlay structure catalyst and preparation method and application - Google Patents
A kind of two-dimentional inlay structure catalyst and preparation method and application Download PDFInfo
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- CN107221685A CN107221685A CN201710459410.6A CN201710459410A CN107221685A CN 107221685 A CN107221685 A CN 107221685A CN 201710459410 A CN201710459410 A CN 201710459410A CN 107221685 A CN107221685 A CN 107221685A
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- Prior art keywords
- dimentional
- catalyst
- black phosphorus
- inlay structure
- noble metal
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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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- 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
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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 two-dimentional inlay structure catalyst and its preparation and application, the catalyst is, using the black phosphorus alkene of two-dimensional layered structure as carrier, noble metal to be embedded in its layer structure and is prepared from；Wherein, the content of noble metal is the 2 500% of vehicle weight.Gained catalyst of the invention has good durability and high stability, it is possible to increase in the life-span of fuel cell, be used as catalyst of fuel batter with proton exchange film.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of two-dimentional inlay structure catalyst and its preparation side
Method and application.
Background technology
Proton Exchange Membrane Fuel Cells in communications and transportation, is moved with being received significant attention the advantages of its high efficiency, no pollution
The dynamic field such as power supply and stand-by station has broad application prospects.Current Proton Exchange Membrane Fuel Cells is main negative with carbon material
The platinum and platinum base metal of load are as catalyst, with higher catalytic efficiency.But because the durability of existing catalyst is poor, lead
The cost of Proton Exchange Membrane Fuel Cells has been caused to remain high.Therefore, pem fuel electricity of the exploitation with high-durability
Pond catalyst has very important significance.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of two-dimentional inlay structure catalyst and preparation method thereof is with answering
With it has good durability and high stability, it is possible to increase the life-span of fuel cell.
To achieve the above object, the present invention takes following scheme：
A kind of two-dimentional inlay structure catalyst, its be the black phosphorus alkene using two-dimensional layered structure as carrier, noble metal is embedded in it
It is prepared from layer structure；Wherein, the content of noble metal is the 2-500% of vehicle weight.
The black phosphorus alkene of the two-dimensional layered structure contains 2-50 layers.
The noble metal is the one or more in gold, silver, platinum, ruthenium, rhodium, palladium, osmium, iridium.
The preparation method of the two-dimentional inlay structure catalyst, is that black phosphorus alkene and noble metal precursor body are scattered in into solvent
In, it is sufficiently stirred for it is uniformly dispersed；Then add sodium borohydride aqueous solution and be sufficiently stirred for, filter；Products therefrom is in protection
Heat drying under property atmosphere, the ball milling under protective atmosphere obtains the two-dimentional inlay structure catalyst.
Wherein, the mass ratio of black phosphorus alkene and noble metal precursor body is 1:0.05 ~ 10, the noble metal precursor body includes chlorine platinum
Any one in acid, chlorine palladium acid, the chloride of gold chloride and noble metal, nitrate, sulfate；
The solvent is the one or more in water, methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol；
The time of the stirring is 30 ~ 180 minutes；
The concentration of the sodium borohydride aqueous solution is 0.5 ~ 10 mol/L；
The protective atmosphere is made up of the one or more in nitrogen, argon gas, helium；
The temperature of the heat drying is 100 ~ 180 DEG C, and the time is 6 ~ 60 h；
The time of the ball milling is 10 ~ 100 hours.
Gained two dimension inlay structure catalyst has good durability and high stability, is used as PEM combustion
Expect cell catalyst.
The remarkable advantage of the present invention is：The present invention is made expensive by forming metal inlay structure in two-dimensional layer material
Metallic catalyst is fixed on the interlayer of two-dimensional layer material, and the migration to hinder noble metal catalyst is urged with growing up so as to realize
The good durability of agent, the catalyst is used for as catalyst of fuel batter with proton exchange film, is favorably improved fuel electricity
The life-span in pond.
Brief description of the drawings
The structural representation for the two-dimentional inlay structure catalyst that Fig. 1 is prepared for the present invention.
Fig. 2 is residual activity area of the two-dimentional inlay structure catalyst of embodiment 1-8 preparations after cyclic voltammetry
Contrast situation.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 2 layers）10 mL are scattered in 0.05 g noble metal precursor body chloroplatinic acids
In water, it is sufficiently stirred for making it be uniformly dispersed in 30 minutes；
2）To step 2）100 mL concentration are added in gained dispersion liquid for 0.5 mol/L sodium borohydride aqueous solutions, 30 are sufficiently stirred for
Minute；
3）Filtering, products therefrom is under nitrogen protection in 100 DEG C of heat dryings 60 hours；
4）By step 3）Products therefrom is in ball milling 10 hours under nitrogen protection, and obtain platinum insertion black phosphorus alkene interlayer has height
The two-dimentional inlay structure catalyst of durability.
Embodiment 2
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 50 layers）100 mL are scattered in 10 g noble metal precursor body chloroplatinic acids
In ethanol, it is sufficiently stirred for making it be uniformly dispersed in 180 minutes；
2）To step 2）It is 10 mol/L sodium borohydride aqueous solutions that 10mL concentration is added in gained dispersion liquid, is sufficiently stirred for 180 points
Clock；
3）Filtering, products therefrom is under argon gas protection in 180 DEG C of heat dryings 6 hours；
4）By step 3）Products therefrom obtains having for platinum insertion black phosphorus alkene interlayer in ball milling 100 hours under argon gas protection
The two-dimentional inlay structure catalyst of high-durability.
Embodiment 3
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 25 layers）55 mL third are scattered in 5 g noble metal precursor body ruthenic chlorides
In alcohol, it is sufficiently stirred for making it be uniformly dispersed in 80 minutes；
2）To step 2）55 mL concentration are added in gained dispersion liquid for 5 mol/L sodium borohydride aqueous solutions, 80 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is under helium protection in 140 DEG C of heat dryings 30 hours；
4）By step 3）Products therefrom is in ball milling 60 hours under helium protection, and obtain ruthenium metal insertion black phosphorus alkene interlayer has height
The two-dimentional inlay structure catalyst of durability.
Embodiment 4
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 30 layers）With 0.6 g noble metal mixing presomas（Gold chloride and chlorination
Palladium in molar ratio 1:1 mixing）It is 1 to be scattered in volume ratio:In 1 50 mL water/propyl alcohol mixed liquor, it is sufficiently stirred for making it in 100 minutes
It is uniformly dispersed；
2）To step 2）30 mL concentration are added in gained dispersion liquid for 6 mol/L sodium borohydride aqueous solutions, 100 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is in volume ratio 1:It is small in 150 DEG C of heat dryings 20 under 1 nitrogen/helium mix gas shield
When；
4）By step 3）Products therefrom is in volume ratio 1:Ball milling 60 hours, obtains porpezite under 1 nitrogen/helium mix gas shield
Alloy is embedded in the two-dimentional inlay structure catalyst with high-durability of black phosphorus alkene interlayer.
Embodiment 5
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 20 layers）With 0.8 g noble metal mixing presomas（Silver nitrate and chlorine platinum
Acid in molar ratio 1:2 mixing）It is scattered in 60 mL water, is sufficiently stirred for making it be uniformly dispersed in 60 minutes；
2）To step 2）70 mL concentration are added in gained dispersion liquid for 4 mol/L sodium borohydride aqueous solutions, 60 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is in volume ratio 1:It is small in 110 DEG C of heat dryings 50 under 3 nitrogen/argon oxygen mixture protection
When；
4）By step 3）Products therefrom is in volume ratio 1:The 3 lower ball milling of nitrogen/argon oxygen mixture protection 30 hours, obtains platinum silver
Alloy is embedded in the two-dimentional inlay structure catalyst with high-durability of black phosphorus alkene interlayer.
Embodiment 6
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 20 layers）With 1 g noble metal mixing presomas（Radium chloride and chloroplatinic acid
In molar ratio 2:1 mixing）It is scattered in 80 mL water, is sufficiently stirred for making it be uniformly dispersed in 120 minutes；
2）To step 2）60 mL concentration are added in gained dispersion liquid for 7 mol/L sodium borohydride aqueous solutions, 120 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is under argon gas protection in 120 DEG C of heat dryings 30 hours；
4）By step 3）Products therefrom obtains having for platinum-rhodium alloy insertion black phosphorus alkene interlayer in ball milling 70 hours under argon gas protection
The two-dimentional inlay structure catalyst of high-durability.
Embodiment 7
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 20 layers）With 1 g noble metal mixing presomas（Osmium potassium chloride and chlorine platinum
Acid in molar ratio 2:1 mixing）It is scattered in 10 mL ethylene glycol, is sufficiently stirred for making it be uniformly dispersed in 100 minutes；
2）To step 2）40 mL concentration are added in gained dispersion liquid for 7 mol/L sodium borohydride aqueous solutions, 100 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is under argon gas protection in 120 DEG C of heat dryings 30 hours；
4）By step 3）Products therefrom obtains having for platinum osmium alloy insertion black phosphorus alkene interlayer in ball milling 70 hours under argon gas protection
The two-dimentional inlay structure catalyst of high-durability.
Embodiment 8
1）By 1 g black phosphorus alkene（The number of plies of black phosphorus alkene used is 40 layers）With 2 g noble metal mixing presomas（Iridium chloride and chloroplatinic acid
In molar ratio 10:1 mixing）It is scattered in 15 mL ethylene glycol, is sufficiently stirred for making it be uniformly dispersed in 160 minutes；
2）To step 2）80 mL concentration are added in gained dispersion liquid for 6 mol/L sodium borohydride aqueous solutions, 160 points are sufficiently stirred for
Clock；
3）Filtering, products therefrom is under nitrogen protection in 170 DEG C of heat dryings 10 hours；
4）By step 3）Products therefrom obtains having for platinumiridio insertion black phosphorus alkene interlayer in ball milling 60 hours under nitrogen protection
The two-dimentional inlay structure catalyst of high-durability.
The structural representation for the two-dimentional inlay structure catalyst that Fig. 1 is prepared for the present invention.
Fig. 2 is residual activity area of the two-dimentional inlay structure catalyst of embodiment 1-8 preparations after cyclic voltammetry
Contrast situation.From Figure 2 it can be seen that after the cyclic voltammetry of 10000 circles, the residual activity area of Pt/C catalyst is only just
15% begun, and the residual activity area of catalyst prepared by the present invention has exceeded initial 40%, shows catalyst of the present invention
With good durability.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (6)
1. a kind of two-dimentional inlay structure catalyst, it is characterised in that：The catalyst is the black phosphorus alkene work with two-dimensional layered structure
For carrier, noble metal is embedded in its layer structure and is prepared from；
Wherein, the content of noble metal is the 2-500% of vehicle weight.
2. two-dimentional inlay structure catalyst according to claim 1, it is characterised in that：The black phosphorus of the two-dimensional layered structure
Alkene contains 2-50 layers.
3. two-dimentional inlay structure catalyst according to claim 1, it is characterised in that：The noble metal be gold, silver, platinum,
One or more in ruthenium, rhodium, palladium, osmium, iridium.
4. a kind of preparation method of two-dimentional inlay structure catalyst as claimed in claim 1, it is characterised in that：By black phosphorus alkene with it is expensive
Metal precursor is scattered in solvent, is sufficiently stirred for making it be uniformly dispersed；Then add sodium borohydride aqueous solution and be sufficiently stirred for,
Filtering；Products therefrom heat drying under protective atmosphere, the ball milling under protective atmosphere obtains the two-dimentional inlay structure
Catalyst.
5. the preparation method of two-dimentional inlay structure catalyst according to claim 4, it is characterised in that：Black phosphorus alkene and noble metal
The mass ratio of presoma is 1:0.05~10；
The solvent is the one or more in water, methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol；
The time of the stirring is 30 ~ 180 minutes；
The concentration of the sodium borohydride aqueous solution is 0.5 ~ 10 mol/L；
The protective atmosphere is made up of the one or more in nitrogen, argon gas, helium；
The temperature of the heat drying is 100 ~ 180 DEG C, and the time is 6 ~ 60 h；
The time of the ball milling is 10 ~ 100 hours.
6. a kind of application of two-dimentional inlay structure catalyst as claimed in claim 1 in Proton Exchange Membrane Fuel Cells is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983378A (en) * | 2017-11-09 | 2018-05-04 | 北京化工大学 | A kind of rhodium/phosphorus alkene loaded catalyst and its preparation method and application |
| CN108336382A (en) * | 2018-01-09 | 2018-07-27 | 东南大学 | It is a kind of using graphene black phosphorus alkene hetero-junctions as hydrogen fuel cell of electrode and preparation method thereof |
| CN108483416A (en) * | 2018-05-08 | 2018-09-04 | 戚明海 | A kind of black phosphorus and preparation method thereof of boride modification |
| CN109432437A (en) * | 2018-11-12 | 2019-03-08 | 暨南大学 | A kind of targeting iridium (III) complex decorating black phosphorus compound and its preparation method and application |
| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983378A (en) * | 2017-11-09 | 2018-05-04 | 北京化工大学 | A kind of rhodium/phosphorus alkene loaded catalyst and its preparation method and application |
| CN108336382A (en) * | 2018-01-09 | 2018-07-27 | 东南大学 | It is a kind of using graphene black phosphorus alkene hetero-junctions as hydrogen fuel cell of electrode and preparation method thereof |
| CN108483416A (en) * | 2018-05-08 | 2018-09-04 | 戚明海 | A kind of black phosphorus and preparation method thereof of boride modification |
| CN109432437A (en) * | 2018-11-12 | 2019-03-08 | 暨南大学 | A kind of targeting iridium (III) complex decorating black phosphorus compound and its preparation method and application |
| CN109432437B (en) * | 2018-11-12 | 2021-10-22 | 暨南大学 | Targeted iridium (III) complex modified black phosphorus compound and preparation method and application thereof |
| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
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