CN106876732B - Icosahedron shape Pd@PdFe nanocrystal and catalyst preparation, application - Google Patents
Icosahedron shape Pd@PdFe nanocrystal and catalyst preparation, application Download PDFInfo
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Abstract
The invention discloses icosahedron shape Pd@PdFe nanocrystals, it is core-shell structure, its kernel is the icosahedron shape Pd nanocrystal that average grain diameter is 21nm, and shell is the PdFe alloy-layer of 3~4 atomic layer level thickness, and PdFe alloyed layer is { 111 } crystal face.The invention also discloses the preparation methods of above-mentioned icosahedron shape Pd@PdFe nanocrystal.The invention also discloses a kind of Pd@PdFe/C metal nano catalyst.The invention also discloses the preparation methods of above-mentioned Pd@PdFe/C metal nano catalyst.The invention also discloses application of the above-mentioned Pd@PdFe/C metal nano catalyst in the Cathodic oxygen reduction of Proton Exchange Membrane Fuel Cells.Gained nanocrystal size of the invention is uniform, good dispersion, relative low price, and catalytic reaction activity with 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 nano catalyst and its preparation, application.
Background technique
Proton Exchange Membrane Fuel Cells is a kind of power generator that can directly convert chemical energy to electric energy, has power
Density is big, energy conversion efficiency is high, environmentally protective, advantages of simple structure and simple.Its common cathodic oxygen reduction catalyst is carbon load
Platinum, wherein metal platinum is very rare and expensive, therefore greatly limits Proton Exchange Membrane Fuel Cells
Development.The oxygen reduction catalyst for finding a kind of Cheap highly effective becomes 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 more metal nano catalyst has attracted numerous grind
The attention for the person of studying carefully.On the one hand, the thickness of core-shell structure and shell can produce a very large impact the performance of catalyst；On the other hand,
Alloy effect, nanocrystalline dimensional effect and crystal face effect are also closely bound up with the performance of catalyst.Therefore, exploring has nucleocapsid knot
The synthesis of more metal nano catalyst of structure has very important significance.Through the retrieval discovery to existing associated materials, alloy
And the catalytic performance of the catalyst with core-shell structure can all significantly improve.Such as application No. is 201110051751.2 patent public affairs
It has opened a kind of local reduction way and has prepared preparation side of the high alloy PdFe/C metal nano catalyst as cathodic oxygen reduction catalyst
Method；Application No. is a kind of Pd@PtNi/C metal nano catalyst of 201410495751.5 patent disclosure as cathode oxygen also
The preparation method of raw catalyst.Since the two has all used relatively relatively inexpensive metal to replace precious metals pt, to substantially reduce
The synthesis cost of catalyst.
Summary of the invention
Technical problems based on background technology the invention proposes icosahedron shape Pd@PdFe nanocrystal and are urged
Agent preparation, application, using Pd icosahedron as nucleus, PdFe alloy both may be used as the partially synthetic nanocrystal of shell structurre
To reduce the synthesis cost of catalyst, and crystal face grain boundary effect, the special core-shell structure and alloy effect of metal can be utilized, made
Pd@PdFe nanocrystal catalytic performance with higher with particular crystal plane and core-shell structure.
Icosahedron shape Pd@PdFe nanocrystal proposed by the present invention, is core-shell structure, and kernel is that average grain diameter is
The icosahedron shape Pd nanocrystal of 21nm, shell are the PdFe alloy-layer of 3~4 atomic layer level thickness, PdFe alloy-layer table
Face is { 111 } crystal face.
Preferably, wherein the mass ratio of kernel Pd element, shell Pd element and shell Fe element is 82~89:16~19:3
~10.
The preparation method for the above-mentioned icosahedron shape Pd@PdFe nanocrystal that the present invention also proposes includes the following steps: often
Under temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecene solution, mixed solution A is obtained；To mixed solution A
The middle hexane solution that icosahedron shape Pd nanocrystal is added, is passed through nitrogen, stirs, and then increases temperature and carries out pyroreaction,
It is cooled to room temperature, cleans, be dried to obtain icosahedron shape Pd@PdFe nanocrystal.
Preferably, tri-iron dodecacarbonyl and the mass volume ratio (mg/ml) of 1- octadecene solution are 1.5~2.5:7~9,
Palladium acetylacetonate and the mass volume ratio (mg/ml) of 1- octadecene solution are 4.5~5.5:7~9.
Preferably, tri-iron dodecacarbonyl and the mass volume ratio (mg/ml) of 1- octadecene solution are 1.8:8, acetylacetone,2,4-pentanedione
The mass volume ratio (mg/ml) of palladium 1- octadecene solution is 5:8.
Preferably, the concentration of the hexane solution of icosahedron shape Pd nanocrystal is 4~4.5mg/ml, preferably
4.25mg/ml。
Preferably, the volume ratio of the hexane solution of icosahedron shape Pd nanocrystal and 1- octadecene solution be 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
Object carries out supersound washing with nonpolar solvent, repeats above-mentioned centrifuge separation and supersound washing step 3 time.
Preferably, the revolving speed of centrifuge separation is 13000~15000 turns/min, and the time of centrifuge separation is 7~10min.
Preferably, the supersound washing time is 1~2min.
Preferably, nonpolar solvent is hexane.
Preferably, the hexane solution of icosahedron shape Pd nanocrystal is prepared as follows: under room temperature, successively by first
Aldehyde, oleyl amine are injected into the toluene solution stirring of palladium acetylacetonate, and then heating carries out pyroreaction, is cooled to room temperature, and wash, so
Disperse to obtain the hexane solution with icosahedron shape Pd nanocrystal in hexane again afterwards.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystal, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) is 23~25:9~11, and 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 nanocrystal, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) is 24:10, and the volume ratio of formaldehyde and toluene is 0.05:10, and 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 nanocrystal, 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 nanocrystal, 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 nanocrystal, the concrete operations of washing are as follows:
Material is centrifuged after will be cooled to room temperature, centrifugation products therefrom with nonpolar solvent is carried out supersound washing, in repetition
State centrifuge separation and supersound washing step 3 time.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystal, the revolving speed of centrifuge separation is
14000~15000 turns/min, the time of centrifuge separation is 7~10min.
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystal, the supersound washing time be 1~
2min。
Preferably, in the preparation method of the hexane solution of icosahedron shape Pd nanocrystal, nonpolar solvent is hexane.
A kind of Pd@PdFe/C metal nano catalyst that the present invention also proposes, the Pd@PdFe/C metal nano catalyst
There are above-mentioned icosahedron shape Pd@PdFe nanocrystal, Pd in the Pd@PdFe/C metal nano catalyst for carbon blacksurface load
Mass fraction be 20%.
The preparation method for the above-mentioned Pd@PdFe/C metal nano catalyst that the present invention also proposes will contain above-mentioned 20 face
The hexane solution of bodily form Pd@PdFe nanocrystal 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 nanocrystal, the concentration of Pd element is 0.5~
1.5mg/ml, preferably 1mg/ml.
Preferably, in mixed solution B, the mass ratio of Pd element and carbon black is 0.195~0.204:0.8, preferably 0.2:
0.8。
Preferably, the time of ultrasonic treatment 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 being centrifuged, products therefrom pole will be centrifuged
Property solvent carry out supersound washing, then repeat above-mentioned centrifuge separation and supersound washing step 3 time.
Preferably, the revolving speed of centrifuge separation is 14000~15000 turns/min, and the time of centrifuge separation is 7~10min.
Preferably, the supersound washing time is 1~2min.
Preferably, polar solvent is ethyl alcohol.
The above-mentioned Pd@PdFe/C metal nano catalyst that the present invention also proposes fuel battery cathode with proton exchange film oxygen also
As the application of catalyst in former reaction process.
Agitating mode in the present invention is magnetic agitation.
Crystal seed growth method, bimetallic coreduction sedimentation have been used in the method for the present invention, finally obtain icosahedron shape Pd@
PdFe nanocrystal, and Pd@PdFe/C metal nano catalyst is obtained by carbon black loadings.The method of the present invention 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 than U.S. Johnson Mattney public affairs
The commercial Pt/C catalyst performance of department's production promotes nearly 3 times, and unit area activity improves 26 times than commercial Pt/C catalyst, fills
Divide the significant advantage for showing the structure in catalysis reaction.Therefore, Pd@PdFe/C metal nano catalyst of the invention is in matter
Proton exchange film fuel cell catalysis technical field has wide application prospect.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of 4 gained icosahedron shape Pd nanocrystal of the embodiment of the present invention.
Fig. 2 is the transmission electron microscope figure of 4 gained icosahedron shape Pd@PdFe nanocrystal of the embodiment of the present invention.
Fig. 3 is the angle of elevation annular dark of the single icosahedron forming core shell structure Pd@PdFe of 4 gained of the embodiment of the present invention.
Fig. 4 be 4 gained icosahedron forming core shell structure Pd@PdFe of the embodiment of the present invention local angle of elevation annular dark with
And distribution diagram of element.
Fig. 5 is the transmission electron microscope figure of 4 gained Pd@PdFe/C metal nano catalyst of the embodiment of the present invention.
Fig. 6 is the electro-catalysis electric current song of 4 gained Pd@PdFe/C metal nano catalyst of the embodiment of the present invention and contrast sample
Line.
Fig. 7 is 4 gained Pd@PdFe/C metal nano catalyst of the embodiment of the present invention and contrast sample when current potential is 0.9V
Mass activity histogram.
Fig. 8 is 4 gained Pd@PdFe/C metal nano catalyst of the embodiment of the present invention and contrast sample when current potential is 0.9V
Area activated histogram.
Specific embodiment
In the following, technical solution of the present invention 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 are
Carbon blacksurface load has above-mentioned icosahedron shape Pd@PdFe nanocrystal, 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, includes the following steps:
Under room temperature, successively the toluene solution that formaldehyde, oleyl amine are injected into palladium acetylacetonate is stirred, then heating carries out high temperature
Reaction, is cooled to room temperature, and washs, and then disperses to obtain the hexane solution with icosahedron shape Pd nanocrystal in hexane again；
Under room temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecene solution, mixed solution A is obtained；
Into mixed solution A be added icosahedron shape Pd nanocrystal hexane solution, be passed through nitrogen, stir, then increase temperature into
Row pyroreaction, is cooled to room temperature, and cleaning is dried to obtain icosahedron shape Pd@PdFe nanocrystal；
Icosahedron shape Pd PdFe nanocrystal is dispersed in hexane, to be then slowly injected into containing carbon black hexane again
Mixed solution B is obtained in solution, is ultrasonically treated, and 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, includes the following steps:
Under room temperature, successively the toluene solution that formaldehyde, oleyl amine are injected into palladium acetylacetonate is stirred, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) be 23:11, the volume ratio of formaldehyde and toluene is 0.04:11, and the volume ratio of oleyl amine and toluene is
0.03:11, then heating 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 revolving speed of centrifuge separation is 14000 turns/min, the time of centrifuge separation
For 10min, centrifugation products therefrom is subjected to supersound washing 1min with nonpolar solvent, then repeats above-mentioned centrifuge separation and ultrasound
Washing step 3 times, then disperse to obtain the hexane solution with icosahedron shape Pd nanocrystal in hexane again；
Under room temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecene solution, tri-iron dodecacarbonyl and
The mass volume ratio (mg/ml) of 1- octadecene solution is 1.5:9, the mass volume ratio of palladium acetylacetonate and 1- octadecene solution
(mg/ml) it is 4.5:9, obtains mixed solution A；It is that 4mg/ml icosahedron shape Pd is nanocrystalline that concentration is added into mixed solution A
The hexane solution of body, the hexane solution of icosahedron shape Pd nanocrystal and the volume ratio of 1- octadecene solution are 2.2:7, are passed through
Nitrogen, stirring then increase temperature and carry out pyroreaction, and the temperature of pyroreaction is 185 DEG C, and the time of pyroreaction is 1h,
It is cooled to room temperature, material is centrifuged after will be cooled to room temperature, and the revolving speed of centrifuge separation is 15000 turns/min, centrifugation point
From time be 7min, centrifugation products therefrom with nonpolar solvent is subjected to supersound washing 2min, above-mentioned centrifugation is then repeated and divides
From with supersound washing step 3 time, be dried to obtain icosahedron shape Pd@PdFe nanocrystal；
Icosahedron shape Pd PdFe nanocrystal is dispersed in hexane again, wherein the concentration of Pd element is 1.5mg/
Then ml is slowly injected into the carbon black hexane solution that concentration is 0.5mg/ml and obtains mixed solution B, Pd element in mixed solution B
Mass ratio with carbon black is 0.204:0.8, is ultrasonically treated 4h, material after ultrasound is centrifuged, the revolving speed of centrifuge separation
For 14000 turns/min, the time of centrifuge separation is 10min, and centrifugation products therefrom is carried out supersound washing 1min with polar solvent,
Then above-mentioned centrifuge separation 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, includes the following steps:
Under room temperature, successively the toluene solution that formaldehyde, oleyl amine are injected into palladium acetylacetonate is stirred, palladium acetylacetonate and toluene
Mass volume ratio (mg/ml) be 25:9, the volume ratio of formaldehyde and toluene is 0.06:9, and the volume ratio of oleyl amine and toluene is
0.05:9, then heating 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 revolving speed of centrifuge separation is 15000 turns/min, the time of centrifuge separation
For 7min, centrifugation products therefrom is subjected to supersound washing 2min with nonpolar solvent, then repeats above-mentioned centrifuge separation and ultrasound
Washing step 3 times, then disperse to obtain the hexane solution with icosahedron shape Pd nanocrystal in hexane again；
Under room temperature, tri-iron dodecacarbonyl and palladium acetylacetonate are added in 1- octadecene solution, tri-iron dodecacarbonyl and
The mass volume ratio (mg/ml) of 1- octadecene solution is 2.5:7, the mass volume ratio of palladium acetylacetonate and 1- octadecene solution
(mg/ml) it is 5.5:7, obtains mixed solution A；It is Pd nanometers of 4.5mg/ml icosahedron shape that concentration is added into mixed solution A
The hexane solution of crystal, the hexane solution of icosahedron shape Pd nanocrystal and the volume ratio of 1- octadecene solution are 1.8:9, are led to
Enter nitrogen, stir, then increase temperature and carry out pyroreaction, the temperature of pyroreaction is 175 DEG C, and the time of pyroreaction is
2h is cooled to room temperature, and material is centrifuged after will be cooled to room temperature, and the revolving speed of centrifuge separation is 13000 turns/min, centrifugation
The isolated time is 10min, and centrifugation products therefrom is carried out supersound washing 1min with nonpolar solvent, then repeats above-mentioned centrifugation
Separation and supersound washing step 3 time, are dried to obtain icosahedron shape Pd@PdFe nanocrystal；
Icosahedron shape Pd PdFe nanocrystal is dispersed in hexane again, wherein the concentration of Pd element is 0.5mg/
Then ml is slowly injected into the carbon black hexane solution that concentration is 1.5mg/ml and obtains mixed solution B, in mixed solution B, Pd element
Mass ratio with carbon black is 0.195:0.8, is ultrasonically treated 2h, material after ultrasound is centrifuged, the revolving speed of centrifuge separation
For 15000 turns/min, the time of centrifuge separation is 7min, and centrifugation products therefrom is carried out supersound washing 2min with polar solvent,
Then above-mentioned centrifuge separation 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, includes the following steps:
Prepare the solution for the icosahedron shape Pd nanocrystal that mean size is 21nm, concentration is 4.25mg/ml: room temperature
Under, it is implanted sequentially the palladium acetylacetonate toluene solution and 0.04ml oleyl amine that 10ml concentration is 8mmol/L into beaker, magnetic is added
Son is placed on blender and stirs 10min.50 μ L formaldehyde are injected into above-mentioned mixed solution again, continues to stir 10min, obtain
Homogeneous solution.Then reaction solution is transferred in reaction kettle, is placed in 100 DEG C of baking ovens and reacts 8h, acquisition is containing mean size
The solution of the icosahedron shape Pd nanocrystal of 21nm；It will be centrifuged containing the solution of icosahedron shape Pd nanocrystal, hexane is washed
It washs and obtains 8.5mg icosahedron shape Pd nanocrystal, it is dispersed in again in 2ml hexane, obtaining concentration is 4.25mg/ml's
The hexane solution of icosahedron shape Pd nanocrystal.
It prepares the icosahedron shape Pd@PdFe nanocrystal that mean size is 22nm: under room temperature, successively adding in there-necked flask
Enter 1.8mg tri-iron dodecacarbonyl, 5mg palladium acetylacetonate, 8ml 1- octadecene solution, magneton is added to stir evenly.Again into solution
The hexane solution for injecting the icosahedron shape Pd nanocrystal that 2ml concentration is 4.25mg/ml, is passed through nitrogen, and by mixed solution
110 DEG C of reaction 0.5h are placed in, then stops being passed through nitrogen, seals reaction system, mixed liquor is placed in 180 DEG C of reaction 1h, then
Centrifugation, hexane washing, disperses again, can be obtained the hexane solution of icosahedron shape Pd@PdFe nanocrystal.
As shown in Fig. 2, products therefrom is of uniform size, good dispersion, individual particle size is about 22nm.Elemental redistribution is shown in figure
4, the linear surface sweeping carried out along dotted line shown in figure also demonstrates that the structure is made of Pd core and the shell of PdFe alloy.
Preparation is used for the Pd@PdFe/C metal nano catalyst of fuel battery cathode with proton exchange film oxygen reduction reaction: warp
The total amount of palladium is 10.26mg in the hexane solution of measurement gained icosahedron shape Pd@PdFe nanocrystal, to make final product
The mass fraction of middle palladium is 20%, and the carbon black hexane solution that 41ml concentration is 1mg/ml is added thereto, 3 hours ultrasonic,
It is centrifuged under 15000 turns/min, and continues to be cleaned 3 times, 80 DEG C of drying 2h under same rotational speed with deionized water, 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 compared with:
4 gained Pd@PdFe/C metal nano catalyst of 5mg embodiment is taken to be dissolved in 1mL water and alcohol mixed solution (water and second
The volume ratio of alcohol is 1:3) in, after ultrasonic 1 hour formation paste, take a certain amount of glass-carbon electrode table for being added drop-wise to diameter as 5mm
The Nafion solution that 15 μ L mass fractions are 0.05% is added dropwise, as working electrode and in 0.1mol/ after drying in face again after drying
Its catalytic activity to redox reactions is measured in L potassium hydroxide solution.
Oxygen, scanning speed 10mV/s are constantly passed through into potassium hydroxide solution, electrode revolving speed is 1600 turns/min, institute
It is as shown in Figure 6 to obtain current curve.Referring to Fig. 7, when current potential is 0.9V, present invention mass activity achieved is 0.30A/mg, and
The mass activity of commercial Pt/C catalyst is only the catalytic performance of the 0.12A/mg. metallic catalyst compared to commercial Pt/C
Catalyst promotes about 3 times.In addition, as shown in Figure 8, the area activated of Pd improves 26 times than commercial Pt/C catalyst, sufficiently show
Show advantage of the Pd@PdFe/C metallic catalyst obtained by the present invention in Cathodic oxygen reduction.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (31)
1. icosahedron shape Pd@PdFe nanocrystal, which is characterized in that it is core-shell structure, and kernel is that average grain diameter is
The icosahedron shape Pd nanocrystal of 21nm, shell are the PdFe alloy-layer of 3~4 atomic layer level thickness, PdFe alloy-layer table
Face is { 111 } crystal face.
2. icosahedron shape Pd@PdFe nanocrystal according to claim 1, which is characterized in that wherein kernel Pd element, shell
The mass ratio of layer Pd element and shell Fe element is 82~89:16~19:3~10.
3. a kind of preparation method of icosahedron shape Pd@PdFe nanocrystal as claimed in claim 1 or 2, which is characterized in that packet
It includes following steps: under room temperature, tri-iron dodecacarbonyl and palladium acetylacetonate being added in 1- octadecene solution, mixed solution is obtained
A；The hexane solution of icosahedron shape Pd nanocrystal is added into mixed solution A, is passed through nitrogen, stirs, then increases temperature
Pyroreaction is carried out, is cooled to room temperature, cleans, is dried to obtain icosahedron shape Pd@PdFe nanocrystal.
4. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 3, which is characterized in that 12 carbonyls
Base three-iron and the mass volume ratio (mg/ml) of 1- octadecene solution are 1.5~2.5:7~9, and palladium acetylacetonate and 1- octadecylene are molten
The mass volume ratio (mg/ml) of liquid is 4.5~5.5:7~9.
5. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 3, which is characterized in that 20 faces
The concentration of the hexane solution of bodily form Pd nanocrystal is 4~4.5mg/ml.
6. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 3, which is characterized in that 20 faces
The hexane solution of bodily form Pd nanocrystal and the volume ratio of 1- octadecene solution are 1.8~2.2:7~9.
7. according to the preparation method of the icosahedron shape Pd@PdFe nanocrystal of claim 3 or 4, which is characterized in that high temperature
The temperature of reaction is 175~185 DEG C, and the time of pyroreaction is 1~2h.
8. according to the preparation method of the icosahedron shape Pd@PdFe nanocrystal of claim 3 or 4, which is characterized in that cleaning
Concrete operations it is as follows: material is centrifuged after will be cooled to room temperature, and centrifugation products therefrom is carried out with nonpolar solvent
Supersound washing repeats above-mentioned centrifuge separation and supersound washing step 3 time.
9. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 8, which is characterized in that centrifugation point
From revolving speed be 13000~15000 turns/min, time of centrifuge separation is 7~10min.
10. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 8, which is characterized in that ultrasound is washed
Washing the time is 1~2min.
11. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 8, which is characterized in that nonpolarity
Solvent is hexane.
12. according to the preparation method of the icosahedron shape Pd@PdFe nanocrystal of claim 3 or 4, which is characterized in that two
The hexane solution of decahedron shape Pd nanocrystal is prepared as follows: under room temperature, formaldehyde, oleyl amine being successively injected into levulinic
The toluene solution of ketone palladium stirs, and then heating carries out pyroreaction, is cooled to room temperature, and washs, then disperses again in hexane
Obtain the hexane solution with icosahedron shape Pd nanocrystal.
13. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 5, which is characterized in that 20 faces
The hexane solution of bodily form Pd nanocrystal is prepared as follows: under room temperature, formaldehyde, oleyl amine being successively injected into palladium acetylacetonate
Toluene solution stirring, then heating carry out pyroreaction, be cooled to room temperature, wash, then disperse again in hexane band
The hexane solution of icosahedron shape Pd nanocrystal.
14. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 12, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, the mass volume ratio (mg/ml) of palladium acetylacetonate and toluene is
The volume ratio of 23~25:9~11, formaldehyde and toluene is 0.04~0.06:9~11, the volume ratio of oleyl amine and toluene is 0.03~
0.05:9~11.
15. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 12, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, the temperature of pyroreaction is 95~105 DEG C, pyroreaction when
Between be 7~9h.
16. the preparation method of icosahedron shape Pd@PdFe nanocrystal according to claim 12, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, the concrete operations of washing are as follows: will be cooled to material after room temperature
It is centrifuged, centrifugation products therefrom is subjected to supersound washing with nonpolar solvent, above-mentioned centrifuge separation is repeated and ultrasound is washed
Wash step 3 time.
17. the preparation method of the 6 icosahedron shape Pd@PdFe nanocrystals according to claim 1, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, the revolving speed of centrifuge separation is 14000~15000 turns/min, from
The time of heart separation is 7~10min.
18. the preparation method of the 6 icosahedron shape Pd@PdFe nanocrystals according to claim 1, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, the supersound washing time is 1~2min.
19. the preparation method of the 6 icosahedron shape Pd@PdFe nanocrystals according to claim 1, which is characterized in that 20
In the preparation method of the hexane solution of face bodily form Pd nanocrystal, nonpolar solvent is hexane.
20. a kind of Pd@PdFe/C metal nano catalyst, which is characterized in that the Pd@PdFe/C metal nano catalyst is charcoal
Black area load has icosahedron shape Pd PdFe nanocrystal as claimed in claim 1 or 2, the Pd PdFe/C metal nano
The mass fraction of Pd is 20% in catalyst.
21. a kind of preparation method of Pd@PdFe/C metal nano catalyst as claimed in claim 20, which is characterized in that will contain
It has the right that the hexane solution of the 1 or 2 icosahedron shape Pd@PdFe nanocrystals is required to be slowly injected into containing carbon black hexane solution
In obtain mixed solution B, be ultrasonically treated, cleaning, be dried to obtain Pd@PdFe/C metal nano catalyst.
22. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that carbon black oneself
The concentration of carbon black is 0.5~1.5mg/ml in alkane solution.
23. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that right is wanted
In the hexane solution for seeking the 1 or 2 icosahedron shape Pd@PdFe nanocrystals, the concentration of Pd element is 0.5~1.5mg/ml.
24. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that mixing is molten
In liquid B, the mass ratio of Pd element and carbon black is 0.195~0.204:0.8.
25. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that at ultrasound
The time of reason is 2~4h.
26. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that dry temperature
Degree is 70~90 DEG C.
27. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 21, which is characterized in that cleaning
Concrete operations are as follows: material after ultrasound being centrifuged, centrifugation products therefrom is carried out supersound washing with polar solvent, so
After repeat above-mentioned centrifuge separation and supersound washing step 3 time.
28. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 27, which is characterized in that centrifugation point
From revolving speed be 14000~15000 turns/min, time of centrifuge separation is 7~10min.
29. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 27, which is characterized in that ultrasound is washed
Washing the time is 1~2min.
30. the preparation method of Pd@PdFe/C metal nano catalyst according to claim 27, which is characterized in that polarity is molten
Agent is ethyl alcohol.
31. a kind of Pd@PdFe/C metal nano catalyst as claimed in claim 20 is in fuel battery cathode with proton exchange film oxygen
The application of catalyst is used as during reduction reaction.
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