CN106876732A - Icosahedron shape Pd@PdFe nanocrystals and catalyst preparation, application - Google Patents
Icosahedron shape Pd@PdFe nanocrystals and catalyst preparation, application Download PDFInfo
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- CN106876732A CN106876732A CN201710148367.1A CN201710148367A CN106876732A CN 106876732 A CN106876732 A CN 106876732A CN 201710148367 A CN201710148367 A CN 201710148367A CN 106876732 A CN106876732 A CN 106876732A
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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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
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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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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses icosahedron shape Pd@PdFe nanocrystals, it is core shell structure, its kernel is that average grain diameter is the icosahedron shape Pd nanocrystals of 21nm, and its shell is 3~4 PdFe alloy-layers of atomic layer level thickness, and PdFe alloyed layers are { 111 } crystal face.The invention also discloses the preparation method of above-mentioned icosahedron shape Pd@PdFe nanocrystals.The invention also discloses a kind of Pd@PdFe/C metal nano catalyst.The invention also discloses the preparation method of above-mentioned Pd@PdFe/C metal nano catalyst.The invention also discloses application of the above-mentioned Pd@PdFe/C metal nanos catalyst in the Cathodic oxygen reduction of Proton Exchange Membrane Fuel Cells.Gained nanocrystal size of the invention is homogeneous, good dispersion, relative low price, and with catalytic reaction activity higher.
Description
Technical field
The present invention relates to noble metal nano catalyst technical field, more particularly to icosahedron shape Pd@PdFe nanocrystals
And preparation method thereof, a kind of Pd@PdFe/C metal nanos catalyst and its preparation, application.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of TRT that chemical energy directly can be converted into electric energy, with power
Density is big, energy conversion efficiency is high, environmental protection, advantages of simple structure and simple.Its conventional cathodic oxygen reduction catalyst is carried for carbon
Platinum, wherein metal platinum are very rare and expensive, therefore greatly limit Proton Exchange Membrane Fuel Cells
Development.A kind of oxygen reduction catalyst of Cheap highly effective is found as the commercialized top priority of Proton Exchange Membrane Fuel Cells.Closely
Nian Lai, with the development of nanocrystal synthetic technology, the research of core shell structure and many metal nano catalyst has attracted numerous grinding
The attention of the person of studying carefully.On the one hand, the thickness of core shell structure and shell can be produced a very large impact to the performance of catalyst；On the other hand,
The performance of alloy effect, nanocrystalline dimensional effect and crystal face effect also with catalyst is closely bound up.Therefore, exploring has nucleocapsid knot
The synthesis of many metal nano catalyst of structure has very important significance.Found through the retrieval to existing associated materials, alloy
And the catalytic performance of the catalyst with core shell structure can all be significantly improved.Patent such as Application No. 201110051751.2 is public
Open a kind of local reduction way and prepare preparation side of the high alloy PdFe/C metal nanos catalyst as cathodic oxygen reduction catalyst
Method；A kind of Pd@PtNi/C metal nanos catalyst of the patent disclosure of Application No. 201410495751.5 as negative electrode oxygen also
The preparation method of raw catalyst.Relatively relatively inexpensive metal has all been used to replace precious metals pt due to the two, so as to substantially reduce
The synthesis cost of catalyst.
The content of the invention
Based on the technical problem that background technology is present, the present invention proposes icosahedron shape Pd@PdFe nanocrystals and urges
Prepared by agent, application, and using Pd icosahedrons as nucleus, PdFe alloys both may be used as the partially synthetic nanocrystal of shell structurre
To reduce the synthesis cost of catalyst, and can be made using crystal face grain boundary effect, the special core shell structure and alloy effect of metal
Pd@PdFe nanocrystals with particular crystal plane and core shell structure have catalytic performance higher.
Icosahedron shape Pd@PdFe nanocrystals proposed by the present invention, it is core shell structure, and its kernel is for average grain diameter
The icosahedron shape Pd nanocrystals of 21nm, its shell is 3~4 PdFe alloy-layers of atomic layer level thickness, PdFe alloy-layer tables
Face is { 111 } crystal face.
Preferably, wherein the mass ratio of kernel Pd elements, shell Pd elements and shell Fe elements is 82~89：16~19：3
~10.
The preparation method of the above-mentioned icosahedron shape Pd@PdFe nanocrystals that the present invention is also proposed, comprises the following steps：Often
Under temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecylene solution, obtain mixed solution A；To mixed solution A
The hexane solution of middle addition icosahedron shape Pd nanocrystals, is passed through nitrogen, stirs, and then rising high-temperature carries out pyroreaction,
Room temperature is cooled to, is cleaned, be dried to obtain icosahedron shape Pd@PdFe nanocrystals.
Preferably, the mass volume ratio (mg/ml) of tri-iron dodecacarbonyl and 1- octadecylene solution is 1.5~2.5：7~9,
The mass volume ratio (mg/ml) of palladium acetylacetonate and 1- octadecylene solution is 4.5~5.5：7~9.
Preferably, the mass volume ratio (mg/ml) of tri-iron dodecacarbonyl and 1- octadecylene solution is 1.8：8, acetylacetone,2,4-pentanedione
The mass volume ratio (mg/ml) of palladium 1- octadecylene solution is 5：8.
Preferably, the concentration of the hexane solution of icosahedron shape Pd nanocrystals is 4~4.5mg/ml, preferably
4.25mg/ml。
Preferably, the volume ratio of the hexane solution of icosahedron shape Pd nanocrystals and 1- octadecylene solution for 1.8~
2.2：7~9, preferably 2：8.
Preferably, the temperature of pyroreaction is 175~185 DEG C, and the time of pyroreaction is 1~2h.
Preferably, the temperature of pyroreaction is 180 DEG C, and the time of pyroreaction is 1.5h.
Preferably, the concrete operations of cleaning are as follows：Material is centrifuged after will be cooled to room temperature, and centrifugation gained is produced
Thing carries out supersound washing with non-polar solven, repeats above-mentioned centrifugation and supersound washing step 3 time.
Preferably, the rotating speed of centrifugation is 13000~15000 turns/min, and the time of centrifugation is 7~10min.
Preferably, the supersound washing time is 1~2min.
Preferably, non-polar solven is hexane.
Preferably, the hexane solution of icosahedron shape Pd nanocrystals is prepared as follows：Under normal temperature, successively by first
Aldehyde, oleyl amine are injected into the toluene solution stirring of palladium acetylacetonate, and then heating up carries out pyroreaction, is cooled to room temperature, washs, so
Disperse to obtain the hexane solution with icosahedron shape Pd nanocrystals in hexane again afterwards.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) is 23~25：9~11, the volume ratio of formaldehyde and toluene is 0.04~0.06：9~11, oleyl amine and first
The volume ratio of benzene is 0.03~0.05：9~11.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) is 24：10, the volume ratio of formaldehyde and toluene is 0.05：10, the volume ratio of oleyl amine and toluene is
0.04：10.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the temperature of pyroreaction is 95
~105 DEG C, the time of pyroreaction is 7~9h.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the temperature of pyroreaction is 100
DEG C, the time of pyroreaction is 8h.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the concrete operations of washing are as follows：
Material is centrifuged after will be cooled to room temperature, centrifugation products therefrom is carried out into supersound washing with non-polar solven, in repetition
State centrifugation and supersound washing step 3 time.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the rotating speed of centrifugation is
14000~15000 turns/min, the time of centrifugation is 7~10min.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the supersound washing time be 1~
2min。
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, non-polar solven is hexane.
A kind of Pd@PdFe/C metal nano catalyst that the present invention is also proposed, the Pd@PdFe/C metal nano catalyst
For carbon blacksurface is loaded with above-mentioned icosahedron shape Pd@PdFe nanocrystals, Pd in the Pd@PdFe/C metal nano catalyst
Mass fraction be 20%.
The preparation method of the above-mentioned Pd@PdFe/C metal nano catalyst that the present invention is also proposed, will contain above-mentioned 20 face
The hexane solution of bodily form Pd@PdFe nanocrystals is slowly injected into containing obtaining mixed solution B in carbon black hexane solution, at ultrasound
Reason, cleaning, is dried to obtain Pd@PdFe/C metal nano catalyst.
Preferably, the concentration of carbon black is 0.5~1.5mg/ml, preferably 1mg/ml in carbon black hexane solution.
Preferably, in the hexane solution of above-mentioned icosahedron shape Pd@PdFe nanocrystals, the concentration of Pd elements for 0.5~
1.5mg/ml, preferably 1mg/ml.
Preferably, in mixed solution B, the mass ratio of Pd elements and carbon black is 0.195~0.204：0.8, preferably 0.2：
0.8。
Preferably, the ultrasonically treated time is 2~4h, preferably 3h.
Preferably, drying temperature is 70~90 DEG C, preferably 80 DEG C.
Preferably, the concrete operations of cleaning are as follows：Material after ultrasound is centrifuged, by centrifugation products therefrom pole
Property solvent carries out supersound washing, then repeats above-mentioned centrifugation and supersound washing step 3 time.
Preferably, the rotating speed of centrifugation is 14000~15000 turns/min, and the time of centrifugation is 7~10min.
Preferably, the supersound washing time is 1~2min.
Preferably, polar solvent is ethanol.
The above-mentioned Pd@PdFe/C metal nanos catalyst that also proposes of the present invention in fuel battery cathode with proton exchange film oxygen also
As the application of catalyst in former course of reaction.
Agitating mode in the present invention is magnetic agitation.
Seeded growth method, bimetallic coreduction sedimentation have been used in the inventive method, icosahedron shape Pd@have been finally given
PdFe nanocrystals, and obtain Pd@PdFe/C metal nano catalyst by carbon black loadings.The inventive method and traditional nanometer
Opacity in lens method is compared, and synthesis cost is greatly lowered, and the simpler convenience of synthetic operation.Gained catalyst of the invention
Have in the Cathodic oxygen reduction of fuel cell and have great advantage, unit mass activity is more public than U.S. Johnson Mattney
The commercial Pt/C catalyst performances lifting for taking charge of production is nearly 3 times, and unit area activity improves 26 times than commercial Pt/C catalyst, fills
Divide and show significant advantage of the structure in catalytic reaction.Therefore, Pd@PdFe/C metal nano catalyst of the invention is in matter
Proton exchange film fuel cell catalysis technical field possesses wide application prospect.
Brief description of the drawings
Fig. 1 is the transmission electron microscope figure of the gained icosahedron shape Pd nanocrystals of the embodiment of the present invention 4.
Fig. 2 is the transmission electron microscope figure of the gained icosahedron shape Pd@PdFe nanocrystals of the embodiment of the present invention 4.
Fig. 3 is the angle of elevation annular dark of the single icosahedron forming core shell structure Pd@PdFe of the gained of the embodiment of the present invention 4.
Fig. 4 for the gained icosahedron forming core shell structure Pd@PdFe of the embodiment of the present invention 4 local angle of elevation annular dark with
And distribution diagram of element.
Fig. 5 is the transmission electron microscope figure of the gained Pd@PdFe/C metal nano catalyst of the embodiment of the present invention 4.
Fig. 6 is the gained Pd@PdFe/C metal nanos catalyst of the embodiment of the present invention 4 bent with the electro-catalysis electric current of comparative sample
Line.
Fig. 7 is the gained Pd@PdFe/C metal nanos catalyst of the embodiment of the present invention 4 and comparative sample when current potential is 0.9V
Mass activity block diagram.
Fig. 8 is the gained Pd@PdFe/C metal nanos catalyst of the embodiment of the present invention 4 and comparative sample when current potential is 0.9V
Area activated block diagram.
Specific embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of Pd@PdFe/C metal nano catalyst proposed by the present invention, the Pd@PdFe/C metal nano catalyst is
Carbon blacksurface is loaded with above-mentioned icosahedron shape Pd@PdFe nanocrystals, Pd in the Pd@PdFe/C metal nano catalyst
Mass fraction is 20%.
The preparation method of above-mentioned Pd@PdFe/C metal nano catalyst proposed by the present invention, comprises the following steps：
Under normal temperature, formaldehyde, oleyl amine are injected into the toluene solution stirring of palladium acetylacetonate successively, then heating up carries out high temperature
Reaction, is cooled to room temperature, washs, and then disperses to obtain the hexane solution with icosahedron shape Pd nanocrystals in hexane again；
Under normal temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecylene solution, obtain mixed solution A；
To the hexane solution that icosahedron shape Pd nanocrystals are added in mixed solution A, nitrogen is passed through, stirred, then risen high-temperature and enter
Row pyroreaction, is cooled to room temperature, cleaning, is dried to obtain icosahedron shape Pd@PdFe nanocrystals；
Icosahedron shape Pd PdFe nanocrystals are disperseed in hexane, to be then slowly injected into and contain carbon black hexane again
Mixed solution B is obtained in solution, ultrasonically treated, cleaning is dried to obtain Pd@PdFe/C metal nano catalyst.
Embodiment 2
The preparation method of above-mentioned Pd@PdFe/C metal nano catalyst proposed by the present invention, comprises the following steps：
Under normal temperature, formaldehyde, oleyl amine are injected into the toluene solution stirring of palladium acetylacetonate, palladium acetylacetonate and toluene successively
Mass volume ratio (mg/ml) be 23：11, the volume ratio of formaldehyde and toluene is 0.04：11, the volume ratio of oleyl amine and toluene is
0.03：11, then heating up carries out pyroreaction, and the temperature of pyroreaction is 95 DEG C, and the time of pyroreaction is 9h, is cooled to room
Temperature, material is centrifuged after will be cooled to room temperature, and the rotating speed of centrifugation is 14000 turns/min, the time of centrifugation
It is 10min, centrifugation products therefrom is carried out into supersound washing 1min with non-polar solven, then repeats above-mentioned centrifugation and ultrasound
Washing step 3 times, then disperses to obtain the hexane solution with icosahedron shape Pd nanocrystals in hexane again；
Under normal temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecylene solution, tri-iron dodecacarbonyl and
The mass volume ratio (mg/ml) of 1- octadecylene solution is 1.5：9, the mass volume ratio of palladium acetylacetonate and 1- octadecylene solution
(mg/ml) it is 4.5：9, obtain mixed solution A；It is that 4mg/ml icosahedron shapes Pd is nanocrystalline to concentration is added in mixed solution A
The hexane solution of body, the hexane solution of icosahedron shape Pd nanocrystals is 2.2 with the volume ratio of 1- octadecylene solution：7, it is passed through
Nitrogen, stirring, then rising high-temperature carries out pyroreaction, and the temperature of pyroreaction is 185 DEG C, and the time of pyroreaction is 1h,
Room temperature is cooled to, material is centrifuged after will be cooled to room temperature, the rotating speed of centrifugation is 15000 turns/min, centrifugation point
From time be 7min, centrifugation products therefrom is carried out into supersound washing 2min with non-polar solven, then repeat above-mentioned centrifugation point
From with supersound washing step 3 time, be dried to obtain icosahedron shape Pd@PdFe nanocrystals；
Icosahedron shape Pd PdFe nanocrystals are disperseed in hexane again, wherein the concentration of Pd elements is 1.5mg/
Ml, is then slowly injected into concentration to obtain mixed solution B in the carbon black hexane solution of 0.5mg/ml, Pd elements in mixed solution B
It is 0.204 with the mass ratio of carbon black：0.8, ultrasonically treated 4h, material after ultrasound is centrifuged, the rotating speed of centrifugation
It is 14000 turns/min, the time of centrifugation is 10min, and centrifugation products therefrom is carried out into supersound washing 1min with polar solvent,
Then above-mentioned centrifugation and supersound washing step 3 time are repeated, 70 DEG C are dried to obtain Pd@PdFe/C metal nano catalyst.
Embodiment 3
The preparation method of above-mentioned Pd@PdFe/C metal nano catalyst proposed by the present invention, comprises the following steps：
Under normal temperature, formaldehyde, oleyl amine are injected into the toluene solution stirring of palladium acetylacetonate, palladium acetylacetonate and toluene successively
Mass volume ratio (mg/ml) be 25：9, the volume ratio of formaldehyde and toluene is 0.06：9, the volume ratio of oleyl amine and toluene is
0.05：9, then heating up carries out pyroreaction, and the temperature of pyroreaction is 105 DEG C, and the time of pyroreaction is 7h, is cooled to room
Temperature, material is centrifuged after will be cooled to room temperature, and the rotating speed of centrifugation is 15000 turns/min, the time of centrifugation
It is 7min, centrifugation products therefrom is carried out into supersound washing 2min with non-polar solven, then repeats above-mentioned centrifugation and ultrasound
Washing step 3 times, then disperses to obtain the hexane solution with icosahedron shape Pd nanocrystals in hexane again；
Under normal temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecylene solution, tri-iron dodecacarbonyl and
The mass volume ratio (mg/ml) of 1- octadecylene solution is 2.5：7, the mass volume ratio of palladium acetylacetonate and 1- octadecylene solution
(mg/ml) it is 5.5：7, obtain mixed solution A；It is Pd nanometers of 4.5mg/ml icosahedron shapes to concentration is added in mixed solution A
The hexane solution of crystal, the hexane solution of icosahedron shape Pd nanocrystals is 1.8 with the volume ratio of 1- octadecylene solution：9, lead to
Enter nitrogen, stir, then rising high-temperature carries out pyroreaction, the temperature of pyroreaction is 175 DEG C, the time of pyroreaction is
2h, is cooled to room temperature, and material is centrifuged after will be cooled to room temperature, and the rotating speed of centrifugation is 13000 turns/min, centrifugation
The time of separation is 10min, and centrifugation products therefrom is carried out into supersound washing 1min with non-polar solven, then repeats above-mentioned centrifugation
Separate and supersound washing step 3 time, be dried to obtain icosahedron shape Pd@PdFe nanocrystals；
Icosahedron shape Pd PdFe nanocrystals are disperseed in hexane again, wherein the concentration of Pd elements is 0.5mg/
Ml, is then slowly injected into concentration to obtain mixed solution B in the carbon black hexane solution of 1.5mg/ml, in mixed solution B, Pd elements
It is 0.195 with the mass ratio of carbon black：0.8, ultrasonically treated 2h, material after ultrasound is centrifuged, the rotating speed of centrifugation
It is 15000 turns/min, the time of centrifugation is 7min, and centrifugation products therefrom is carried out into supersound washing 2min with polar solvent,
Then above-mentioned centrifugation and supersound washing step 3 time are repeated, 90 DEG C are dried to obtain Pd@PdFe/C metal nano catalyst.
Embodiment 4
The preparation method of above-mentioned Pd@PdFe/C metal nano catalyst proposed by the present invention, comprises the following steps：
Mean size is prepared for 21nm, concentration are the solution of the icosahedron shape Pd nanocrystals of 4.25mg/ml：Normal temperature
Under, palladium acetylacetonate toluene solution and 0.04ml oleyl amines that 10ml concentration is 8mmol/L are implanted sequentially toward beaker, add magnetic
Son, is placed in and 10min is stirred on agitator.50 μ L formaldehyde are injected into above-mentioned mixed solution again, continue to stir 10min, obtained
Homogeneous solution.Then reaction solution is transferred in reactor, is placed in and 8h is reacted in 100 DEG C of baking ovens, acquisition is containing mean size
The solution of the icosahedron shape Pd nanocrystals of 21nm；Solution centrifugal containing icosahedron shape Pd nanocrystals, hexane are washed
Acquisition 8.5mg icosahedron shape Pd nanocrystals are washed, it is dispersed in 2ml hexanes again, it is 4.25mg/ml's to obtain concentration
The hexane solution of icosahedron shape Pd nanocrystals.
Prepare the icosahedron shape Pd@PdFe nanocrystals that mean size is 22nm：Under normal temperature, add successively in there-necked flask
Enter 1.8mg tri-iron dodecacarbonyls, 5mg palladium acetylacetonates, 8ml 1- octadecylene solution, plus magneton stirs.Again toward in solution
Injection 2ml concentration is the hexane solution of the icosahedron shape Pd nanocrystals of 4.25mg/ml, is passed through nitrogen, and by mixed solution
110 DEG C of reaction 0.5h are placed in, then stop being passed through nitrogen, seal reaction system, mixed liquor is placed in 180 DEG C of reaction 1h, then
Centrifugation, hexane washing, disperses again, you can obtain the hexane solution of icosahedron shape Pd@PdFe nanocrystals.
As shown in Fig. 2 products therefrom size uniform, good dispersion, individual particle size is about 22nm.Elemental redistribution is shown in figure
4, also demonstrate that the structure is made up of with the shell of PdFe alloys Pd cores along the linear surface sweeping that the dotted line shown in figure is carried out.
Prepare the Pd@PdFe/C metal nano catalyst for fuel battery cathode with proton exchange film oxygen reduction reaction：Through
The total amount of palladium is 10.26mg in the hexane solution of measurement gained icosahedron shape Pd@PdFe nanocrystals, to cause final product
The mass fraction of middle palladium is 20%, is added thereto to the carbon black hexane solution that 41ml concentration is 1mg/ml, ultrasonic 3 hours,
It is centrifuged under 15000 turns/min, and continues to be cleaned with deionized water under same rotational speed 3 times, 80 DEG C of drying 2h, products therefrom is as schemed
Shown in 5, as Pd@PdFe/C metal nano catalyst.
To the test of the electrocatalysis characteristic of Proton Exchange Membrane Fuel Cells Cathodic oxygen reduction with compare：
Take the gained Pd@PdFe/C metal nano catalyst of 5mg embodiments 4 and be dissolved in 1mL water and alcohol mixed solution (water and second
The volume ratio of alcohol is 1：3) in, after ultrasound forms pastel in 1 hour, a certain amount of glass-carbon electrode table for being added drop-wise to a diameter of 5mm is taken
Face, is added dropwise the Nafion solution that 15 μ L mass fractions are 0.05% again after drying, as working electrode and in 0.1mol/ after drying
Its catalysis activity to redox reactions is determined in L potassium hydroxide solutions.
To oxygen is constantly passed through in potassium hydroxide solution, sweep speed is 10mV/s, and electrode rotating speed is 1600 turns/min, institute
Obtain current curve as shown in Figure 6.Reference picture 7, the mass activity that the present invention reaches when current potential is by 0.9V is 0.30A/mg, and
The mass activity of commercial Pt/C catalyst is only the catalytic performance of the 0.12A/mg. metallic catalysts compared to commercial Pt/C
Catalyst lifts about 3 times.Additionally, as shown in Figure 8, the area activated of Pd improves 26 times than commercial Pt/C catalyst, fully aobvious
Show advantage of the present invention gained Pd@PdFe/C metallic catalysts in Cathodic oxygen reduction.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (10)
1. icosahedron shape Pd@PdFe nanocrystals, it is characterised in that it is core shell structure, and its kernel is for average grain diameter
The icosahedron shape Pd nanocrystals of 21nm, its shell is 3~4 PdFe alloy-layers of atomic layer level thickness, PdFe alloy-layer tables
Face is { 111 } crystal face.
2. icosahedron shape Pd@PdFe nanocrystals according to claim 1, it is characterised in that wherein kernel Pd elements, shell
Layer Pd elements are 82~89 with the mass ratio of shell Fe elements：16~19：3~10.
3. a kind of preparation method of icosahedron shape Pd@PdFe nanocrystals as claimed in claim 1 or 2, it is characterised in that bag
Include following steps：Under normal temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecylene solution, obtain mixed solution
A；To the hexane solution that icosahedron shape Pd nanocrystals are added in mixed solution A, nitrogen is passed through, stirred, then rise high-temperature
Pyroreaction is carried out, room temperature is cooled to, cleaned, be dried to obtain icosahedron shape Pd@PdFe nanocrystals.
4. the preparation method of icosahedron shape Pd@PdFe nanocrystals according to claim 3, it is characterised in that 12 carbonyls
The mass volume ratio (mg/ml) of base three-iron and 1- octadecylene solution is 1.5~2.5：7~9, palladium acetylacetonate and 1- octadecylenes are molten
The mass volume ratio (mg/ml) of liquid is 4.5~5.5：7~9；Preferably, the hexane solution of icosahedron shape Pd nanocrystals
Concentration is 4~4.5mg/ml；Preferably, the volume ratio of the hexane solution of icosahedron shape Pd nanocrystals and 1- octadecylene solution
It is 1.8~2.2：7~9.
5. according to claim 3 or 4 icosahedron shape Pd@PdFe nanocrystals preparation method, it is characterised in that high temperature
The temperature of reaction is 175~185 DEG C, and the time of pyroreaction is 1~2h；Preferably, the concrete operations of cleaning are as follows：Will cooling
Material is centrifuged after to room temperature, and centrifugation products therefrom is carried out into supersound washing with non-polar solven, repeats above-mentioned centrifugation
Separate and supersound washing step 3 time；Preferably, the rotating speed of centrifugation be 13000~15000 turns/min, centrifugation when
Between be 7~10min；Preferably, the supersound washing time is 1~2min；Preferably, non-polar solven is hexane.
6. according to claim any one of 3-5 icosahedron shape Pd@PdFe nanocrystals preparation method, its feature exists
In the hexane solution of icosahedron shape Pd nanocrystals is prepared as follows：Under normal temperature, formaldehyde, oleyl amine are injected into successively
The toluene solution stirring of palladium acetylacetonate, then heating up carries out pyroreaction, is cooled to room temperature, washs, and is then dispersed in again
The hexane solution with icosahedron shape Pd nanocrystals is obtained in hexane；Preferably, the hexane of icosahedron shape Pd nanocrystals is molten
In the preparation method of liquid, the mass volume ratio (mg/ml) of palladium acetylacetonate and toluene is 23~25：9~11, formaldehyde and toluene
Volume ratio is 0.04~0.06：9~11, the volume ratio of oleyl amine and toluene is 0.03~0.05：9~11；Preferably, icosahedron
In the preparation method of the hexane solution of shape Pd nanocrystals, the temperature of pyroreaction is 95~105 DEG C, and the time of pyroreaction is
7~9h；
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, the concrete operations of washing are as follows：Will be cold
But be centrifuged to material after room temperature, centrifugation products therefrom carried out into supersound washing with non-polar solven, repeat it is above-mentioned from
The heart is separated and supersound washing step 3 time；Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystals, from
The rotating speed that the heart is separate is 14000~15000 turns/min, and the time of centrifugation is 7~10min；Preferably, icosahedron shape Pd
In the preparation method of the hexane solution of nanocrystal, the supersound washing time is 1~2min；Preferably, icosahedron shape Pd nanometers
In the preparation method of the hexane solution of crystal, non-polar solven is hexane.
7. a kind of Pd@PdFe/C metal nano catalyst, it is characterised in that the Pd@PdFe/C metal nanos catalyst is charcoal
Black area load is just like icosahedron shape Pd@PdFe nanocrystals described in claim 1 or 2, the Pd@PdFe/C metal nanos
The mass fraction of Pd is 20% in catalyst.
8. a kind of preparation method of Pd@PdFe/C metal nano catalyst as claimed in claim 7, it is characterised in that will contain
The hexane solution of icosahedron shape Pd@PdFe nanocrystals is slowly injected into containing in carbon black hexane solution described in claim 1 or 2
Mixed solution B is obtained, ultrasonically treated, cleaning is dried to obtain Pd@PdFe/C metal nano catalyst.
9. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 8, it is characterised in that carbon black hexane
The concentration of carbon black is 0.5~1.5mg/ml in solution；Preferably, PdFe nanometers of icosahedron shape Pd@described in claim 1 or 2
In the hexane solution of crystal, the concentration of Pd elements is 0.5~1.5mg/ml；Preferably, in mixed solution B, Pd elements and carbon black
Mass ratio be 0.195~0.204：0.8；Preferably, the ultrasonically treated time is 2~4h；Preferably, drying temperature be 70~
90℃；Preferably, the concrete operations of cleaning are as follows：Material after ultrasound is centrifuged, products therefrom polarity will be centrifuged
Solvent carries out supersound washing, then repeats above-mentioned centrifugation and supersound washing step 3 time；Preferably, the rotating speed of centrifugation
It is 14000~15000 turns/min, the time of centrifugation is 7~10min；Preferably, the supersound washing time is 1~2min；It is excellent
Selection of land, polar solvent is ethanol.
10. a kind of Pd@PdFe/C metal nanos catalyst as claimed in claim 7 in fuel battery cathode with proton exchange film oxygen also
As the application of catalyst in former course of reaction.
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