CN103406128A - Preparation method of nano-particles with nano-grade porous structure - Google Patents
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Abstract
The invention relates to a preparation method of nano-particles with a nano-grade porous structure. The method comprises the steps that: (1) metals A, M, and N with a certain ratio are smelted in an arc furnace, such that alloy AMN is obtained; (2) with smelting and band-manufacturing processes, the alloy AMN is prepared into a thin band; (3) the alloy AMN thin band is soaked in a corrosion liquid and is corroded for 1-48h, such that the active metal A is dissolved; (4) cleaned nano-grade porous metal N or nano-grade porous alloy MN is placed in an organic solvent; and ultrasonic processing is carried out for 1-1000min, such that the nano-particles with nano-grade porous structure is prepared. The method provided by the invention has the advantages that: (1) various metal components in the alloy can be well controlled; (2) the method is simple; and (3) large amount of the nano-particle sample with the nano-grade porous structure can be prepared, such that the method is suitable for large-scale productions.
Description
Technical field
The invention belongs to catalysis and electro-catalysis technical field, relate to a kind of preparation method with nano particle of nano-porous structure, relate in particular to a kind of preparation method who can be used for the nanoporous nanoparticle catalyst of Proton Exchange Membrane Fuel Cells.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of energy conversion device of clean and effective.In fuel cell, oxidation reaction occurs in fuel molecule under the effect of anode catalyst, produce electronics and proton, electronics passes to negative electrode by external circuit, proton is diffused into negative electrode by PEM, electronics and proton generate water by oxygen reduction under the effect of cathod catalyst, complete whole electrochemical reaction.If use hydrogen to act as a fuel, in this process except producing electric energy unique product be water, to environment without any injury.Add operating temperature low, compact conformation, the advantages such as noiselessness, Proton Exchange Membrane Fuel Cells is subject to government organs, enterprise and researcher's extensive concern.
At present, the main cause of obstruction Proton Exchange Membrane Fuel Cells application is expensive.Because the anode and cathode reaction is all to occur under the effect of catalyst, and the highest active catalyst is platinum.The use of a large amount of platinum catalysts directly causes the raising of fuel cell cost.In order to reduce the cost of fuel cell, method commonly used is that the material with carbon element that the alloy catalyst of platinum or platinum is prepared into to the particle of several nanosizeds and loads on conduction is such as on carbon dust.This method has improved the utilization rate of platinum to a certain extent, but also has a series of major defects.Such as: 1) between catalyst (platinum and platinum alloy nano particle) and carrier (material with carbon element), connect and take physisorption as main, structural stability is poor; 2) corrosion of carbon dust can cause the interruption that catalyst is connected with external circuit, makes catalyst lose effective active; 3) catalyst needs to add binding agent in the process of making the membrane electrode assembly zoarium, thereby the partially catalyzed agent is lost and being connected of external circuit, and reduces the utilization rate of platinum.Research shows, unsupported Pt nanoparticle shows higher activity than loaded catalyst, but in this structure, between Pt nanoparticle, serious accumulation can occur, lose effective active area and life-span on the one hand, intergranular gap is not enough to allow the gas molecule of reactant and product freely transmit on the other hand.
As everyone knows, by the active component in resistant alloy, can prepare the nano porous metal material.This structure has higher specific area and three-dimensional continuous nanometer hole wall, is conducive to the transmission of electronics.But; the method of traditional alloy smelting can only be prepared the alloy of block, even in conjunction with following process, also can only obtain micron particles or sheet material; sample size after corrosion is too large, and the transmission of material in the inside, nanoscale duct becomes the key factor that limits this class material application.If nano porous metal can be prepared into to micron, the following particle of 500 nanometers especially, the transmission of material in duct will be improved greatly, thereby in heterocatalysis and electro-catalysis field, the important application prospect will be arranged.A kind of obvious method for preparing the nanoporous particle is to utilize chemistry or physics synthetic method, first prepare alloy nanoparticle, then in conjunction with further erosion removal or part, remove the more active component in alloy, can obtain the nano particle with nano pore structure under certain condition.Yet these preparation methods are subjected to the impact of the factors such as temperature, concentration, predecessor chemical characteristic usually, attainable material system is more limited, affects the homogeneity of product structure, component.And the quantity of the single batch of nano particle with nano-porous structure that can prepare is difficult to realize producing in batches and meeting practical application request generally in the extremely several gram ranks of milligram.Another thinking is that aforementioned nanoporous sheet material or bulky grain are pulverized, then research finds that traditional ball mill grinding technology can only be by material disintegrating to micro-meter scale, and the particle diameter skewness, the fuel factor produced in mechanical milling process and mechanical presses effect also can destroy original nano-porous structure.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method with nano particle of nano-porous structure, a kind of easy, a large amount of methods that prepare the nanoporous nano particle that can be used for Proton Exchange Membrane Fuel Cells particularly are provided.
Technical scheme of the present invention is as follows:
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) metal A, M and N component are placed in to electric arc furnaces in proportion and are smelted into alloy A MN, wherein:
A is active metal, is selected from Zn, Mg or Al,
N is inert metal, is selected from a kind of in Pt, Pd, Au, Ru, Ir, Ag or any two combination,
M is the moderate active metal, is selected from Ni, Co, Cu, Ti or Fe;
By atom number percentage: A, be that 40%～99.9%, N is that 0.1%～60%, M is 0%～60%; Each constituent atoms percentage sum is 100%;
(2) by melting and belt making process, by the alloy A MN band of laminating;
(3) alloy A MN thin slice band is immersed in corrosive liquid, corrosion 1～48h, by active metal A stripping wherein;
When the atomic percent of moderate active metal M is 0%, etch rear taking-up thin slice band and clean up, make nano porous metal N;
Perhaps, when atomic percent 0%<M of moderate active metal M≤60%, moderate active metal M part stripping that simultaneously will be wherein, etch rear taking-up thin slice band and clean up, and makes nanoporous alloy MN;
The nano porous metal N that (4) will clean up or nanoporous alloy MN are placed in organic solvent, and ultrasonic 1～1000min, make the nano particle with nano-porous structure.
Preferred according to the present invention, the described active metal A of step (1) is Al, and atom number percentage is 65～85%; Described inert metal N is a kind of in Pt, Pd, Ru, Ir or any two combination, and atom number percentage is 5～30%; Described metal M is Ni, Cu, Ti or Fe, and atom number percentage is 0～20%; Each constituent atoms number percentage sum is 100%;
Preferred, described active metal A is Al, and atom number percentage is 70～80%; Described inert metal N is a kind of in Pt, Pd, Ru or any two combination, and atom number percentage is 10～20%; Described metal M is Ni, Cu or Ti, and atom number percentage is 5～10%; Each constituent atoms number percentage sum is 100%.
Preferred according to the present invention, the strip of foil tape thickness of the described alloy A MN of step (2) is 10～200 μ m.
Preferred according to the present invention, the described corrosive liquid of step (3) is acidity or alkaline solution, and acid etching solution is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetic acid, and alkaline corrosion liquid is NaOH or KOH; The concentration of corrosive liquid is preferably 0.1～2mol/L;
Preferred, when in step (1), active metal A was Al, corrosive liquid was the NaOH solution of 0.1～2mol/L.
Preferred according to the present invention, the described organic solvent of step (4) is methyl alcohol, ethanol, isopropyl alcohol, acetone, benzene or toluene, more preferably absolute ethyl alcohol; Described ultrasonic time is preferably 1～100min.
The nano particle with nano-porous structure that the inventive method is prepared is comprised of metal, can be both one-component, can be also the alloy that multi-element metal forms; Described nano particle with nano-porous structure is comprised of the three-dimensional porous structure of nanoscale, and size is at 10～500nm; The hole wall of described three-dimensional porous structure and pore size are all at 2～50nm, and hole wall and pore size all are less than particle size.
The nano particle with nano-porous structure that the inventive method is prepared can be used for catalyst of fuel batter with proton exchange film, also can be used for catalysis and field of petrochemical industry.
Preparation method of the present invention prepares nano porous metal or alloy by corroding a certain proportion of alloy material, then the ultrasonic nano particle with nano-porous structure of preparing in suitable solution.The key of the method is the ratio of alloy and the dispersion liquid system when ultrasonic.When active metal in alloy (being A) ratio height to a certain extent the time, in alloy, there are a large amount of crystal boundaries and are connected weakness in the nano porous metal of the segregation of active metal after causing corroding, the existence of these vulnerable areas makes Ultrasonic Pulverization become possibility.Although there is the part of a large amount of connection weaknesses, but the ultrasonic dispersion technology of traditional aqueous systems but can not be by the effective Ultrasonic Pulverization of nano porous metal to nanoscale, this be because hydrone the absorption of nano-porous gold metal surface can reinforcing material toughness, the polarity of water and the Ultrasonic Pulverization that surface tension also is unfavorable for nano porous metal simultaneously.And while adopting non-aqueous organic solvent system such as ethanol as dispersion, nano porous metal can effectively be crushed to nanoscale.The innovative point of this invention is: (1), by the raw-material input component of regulation and control and ratio, optionally prepares the nano-porous materials of different materials and pore structure, can design efficient catalysis material for different catalytic applications; (2) by the selection to dispersion, by simple ultrasonic technique, realize the quick preparation in macroscopic quantity of nanoporous nano particle, and can effectively control the size of nano particle.Metal-based nano porous nano particle in conjunction with above two prepared acquisitions of innovative point can be widely used in each catalysis and electro-catalysis process, can avoid traditional nano material runs in the commercial Application process easy reunion, easily inactivation, stop up the problem such as mass transfer channel.
The advantage of the method is 1) can well control the component of various metals in alloy; 2) method is simple; 3) can prepare in a large number the nano particle sample with nano-porous structure, be beneficial to large-scale production.
The accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the PtNi alloy nanoparticle sample with nano-porous structure that makes of embodiment 1.
Fig. 2 is the transmission electron microscope photo of the PtNi alloy nanoparticle sample with nano-porous structure that makes of embodiment 1.
Fig. 3 is the optical photograph of the PtNi alloy nanoparticle sample with nano-porous structure after ultrasonic firm end and ultrasonic rear placement 20h that embodiment 1 makes; Wherein, the left side is the optical photograph of ultrasonic firm end, and the right is the optical photograph after ultrasonic rear placement 20h.
Fig. 4 is the PtNi alloy nanoparticle sample with nano-porous structure that makes of embodiment 1 and the hydrogen reduction curve of the carbon supported platinum catalyst that market is buied.
Fig. 5 is the electron scanning micrograph of the PtNi alloying pellet that obtains after ultrasonic in water of Comparative Examples 1.
Fig. 6 is the PtNi alloying pellet sample that makes of Comparative Examples 1 optical photograph after ultrasonic firm end and ultrasonic rear placement 5h in water; Wherein, the left side is the optical photograph of ultrasonic firm end, and the right is the optical photograph after ultrasonic rear placement 5h.
Fig. 7 is the electron scanning micrograph of the PtCo alloy nanoparticle sample with nano-porous structure that makes of embodiment 2.
Fig. 8 is the electron scanning micrograph of the PtCo alloying pellet that obtains of Comparative Examples 2 after ultrasonic in water.
The specific embodiment
The present invention will be further described below by specific embodiment, but be not limited to this.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pt, Ni, Al, be that the ratio weighing of 1:1:8 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtNiAl alloy;
(2) by chilling band method processed, the PtNiAl alloy is made to wide 5mm, long 30mm, the thin slice band of thick 100 μ m;
(3) in 0.5mol/L NaOH solution, by PtNiAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making platinum nickel nanoporous alloy;
(4) platinum nickel nanoporous alloy is placed in to ethanol, ultrasonic 5min, make the PtNi alloy nanoparticle with nano-porous structure.
By the PtNi alloy nanoparticle Sample Scan electron micrograph with nano-porous structure that makes as shown in Figure 1, as shown in Figure 1: PtNi alloy nanoparticle size is all below 500nm, most of particle size is between 100-300nm, and a lot of particles only have tens nanometers.
The transmission electron microscope photo of the PtNi alloy nanoparticle sample with nano-porous structure made as shown in Figure 2, as shown in Figure 2: particle length is in the 150nm left and right, width is in the 60nm left and right, and whole particle is three-D nano-porous structure, and the hole wall size is at 3-6nm.Above result proves, through excessive erosion and ultrasonicly in ethanol can prepare the nanoporous nano particle.
When platinum nickel nanoporous alloy is placed in the ultrasonic firm end of ethanol, make the optical photograph of the PtNi alloy nanoparticle with nano-porous structure as shown in Fig. 3 (left side), ultrasonic end is placed the optical photograph of the PtNi alloy nanoparticle with nano-porous structure after 20h afterwards as shown in Fig. 3 (right side).As can be seen from Figure 3, ultrasonic rear platinum nickel nanoporous alloy sample is pulverized, apparent see more even; Through the natural subsidence of 20h, most of platinum nickel nanoporous alloy sample still is suspended in solution, illustrates that the PtNi alloy nanoparticle with nano-porous structure made is less, and this result and Fig. 1,2 confirm mutually.
The PtNi alloy nanoparticle sample with nano-porous structure made is carried out to the hydrogen reduction performance test, and the hydrogen reduction curve as shown in Figure 4; The carbon supported platinum catalyst sample that market is buied carries out the hydrogen reduction performance test, and the hydrogen reduction curve as shown in Figure 4.More as can be known: the PtNi alloy nanoparticle with nano-porous structure shows good hydrogen reduction curve, proves that oxygen is unrestricted in the transmission of the inside, nanoporous particle duct; With carbon supported platinum catalyst, compare, the PtNi alloy nanoparticle with nano-porous structure shows higher hydrogen reduction catalytic activity, can substitute carbon supported platinum catalyst at fuel battery negative pole.
Comparative Examples 1
Platinum nickel nanoporous alloy ultrasonic 30min in water by embodiment 1 step (3) makes, obtain the PtNi alloying pellet.
The PtNi alloying pellet electron scanning micrograph obtained after will be ultrasonic in water as shown in Figure 5, as shown in Figure 5: although some size of PtNi alloying pellet tens to the hundreds of nanometer, a large amount of grain thicknesses is at the 1-2 micron, length is 10 microns left and right; Namely the ultrasonic PtNi alloying pellet size obtained generally can only reach micron order in water.
When platinum nickel nanoporous alloy is placed in the ultrasonic firm end of water, make the optical photograph of PtNi alloying pellet as shown in Fig. 6 (left side), ultrasonic end is placed the optical photograph of the PtNi alloying pellet after 5h as shown in Fig. 6 (right side).As can be seen from Figure 6, ultrasonic rear PtNi alloying pellet sample is pulverized, apparent see more even, but the natural subsidence through 5h, most of sample is deposited to the bottom of test tube, illustrates that the PtNi alloying pellet after ultrasonic in water is larger, and this result and Fig. 5 confirm mutually.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pt, Co, Al, be that the ratio weighing of 1:1:8 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtCoAl alloy;
(2) by chilling band method processed, the PtCoAl alloy is made to wide 5mm, long 100mm, the thin slice band of thick 80 μ m;
(3) in the HCl of 0.1mol/L solution, by PtCoAl alloy immersion corrosion 48h, by wherein active metal component Al stripping and by the Co part stripping of moderate active metal; Etch rear taking-up thin slice band and clean up, making platinum cobalt nanoporous alloy;
(4) platinum cobalt nanoporous alloy is placed in to methyl alcohol, ultrasonic 5min, make the PtCo alloy nanoparticle with nano-porous structure.
The electron scanning micrograph of the PtCo alloy nanoparticle sample with nano-porous structure made as shown in Figure 7, as shown in Figure 7: particle length is all below 200nm, most of length is in the 100nm left and right, width is in the 60-80nm left and right, whole particle is three-D nano-porous structure, and the hole wall size is at 8-10nm.Above result proves, through excessive erosion and ultrasonicly in methyl alcohol can prepare nanoporous PtCo alloy nanoparticle.
Comparative Examples 2
Platinum cobalt nanoporous alloy ultrasonic 30min in water by embodiment 2 steps (3) make, obtain the PtCo alloying pellet.
As shown in Figure 8, as shown in Figure 8: PtCo alloying pellet thickness is at the 1-2 micron, and length is 10 microns left and right for electron scanning micrograph after the PtCo alloying pellet is ultrasonic in water.With embodiment 2 gained samples, compare, size obviously increases.Proof can well be controlled the size of nanoporous nano particle to the selection of dispersion.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pt, Cu, Al, be that the ratio weighing of 1.5:0.5:8 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtCuAl alloy;
(2) by chilling band method processed, the PtCuAl alloy is made to wide 3mm, long 35mm, the thin slice band of thick 200 μ m;
(3) in 1.0mol/L NaOH solution, by PtCuAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making platinoid nanoporous alloy;
(4) platinoid nanoporous alloy is placed in to ethanol, ultrasonic 8min, make the platinoid nanoporous nano particle with nano-porous structure, particle length is in the 100-300nm left and right, width is in the 50-150nm left and right, and whole particle is three-D nano-porous structure, and the hole wall size is at 5-8nm.Above result proves, through excessive erosion and ultrasonicly in ethanol can prepare nanoporous PtCu alloy nanoparticle.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pd, Cu, Al, be that the ratio weighing of 0.5:2:7.5 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PdCuAl alloy;
(2) by chilling band method processed, the PdCuAl alloy is made to wide 4mm, long 30mm, the thin slice band of thick 50 μ m;
(3) in 0.5mol/L NaOH solution, by PdCuAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making palladium copper nanoporous alloy;
(4) palladium copper nanoporous alloy is placed in to isopropyl alcohol, ultrasonic 20min, make the palladium copper nanoporous nano particle with nano-porous structure, particle length is in the 200-450nm left and right, width is in the 80-200nm left and right, and whole particle is three-D nano-porous structure, and the hole wall size is at 5-15nm.Above result proves, through excessive erosion and ultrasonicly in isopropyl alcohol can prepare nanoporous PdCu alloy nanoparticle.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pt, Cu, Zn, be that the ratio weighing of 2:1:7 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtCuZn alloy;
(2) by chilling band method processed, the PtCuZn alloy is made to wide 3mm, long 35mm, the thin slice band of thick 200 μ m;
(3) in 1.0mol/L HCl solution, by PtCuZn alloy immersion corrosion 48h, by active metal component A stripping wherein; Etch rear taking-up thin slice band and clean up, making platinoid nanoporous alloy;
(4) platinoid nanoporous alloy is placed in to ethanol, ultrasonic 10min, make the platinoid nanoporous nano particle with nano-porous structure.
A kind of preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) by Pt, Al, be that the ratio weighing of 3:7 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtAl alloy;
(2) by chilling band method processed, the PtAl alloy is made to wide 3mm, long 35mm, the thin slice band of thick 200 μ m;
(3) in 2.0mol/L NaOH solution, by PtAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making platinum nanometer perforated metal;
(4) platinum nanometer perforated metal is placed in to ethanol, ultrasonic 10min, make the platinum nanometer perforated nano particle with nano-porous structure, particle length is in the 80-400nm left and right, width is in the 50-150nm left and right, and whole particle is three-D nano-porous structure, and the hole wall size is at 3-8nm.
Comparative Examples 3
Platinum nanometer perforated metal ultrasonic 30min in water by embodiment 6 steps (3) make, obtain the Pt metallic particles.
The Pt metallic particles thickness obtained after ultrasonic in water is at the 1-3 micron, and length is in 5-20 micron left and right.With embodiment 6, compare, size obviously increases.Proof can well be controlled the size of nanoporous nano particle to the selection of dispersion.
Claims (10)
1. preparation method with nano particle of nano-porous structure comprises that step is as follows:
(1) metal A, M and N component are placed in to electric arc furnaces in proportion and are smelted into alloy A MN, wherein:
A is active metal, is selected from Zn, Mg or Al,
N is inert metal, is selected from a kind of in Pt, Pd, Au, Ru, Ir, Ag or any two combination,
M is the moderate active metal, is selected from Ni, Co, Cu, Ti or Fe;
By atom number percentage: A, be that 40%～99.9%, N is that 0.1%～60%, M is 0%～60%; Each constituent atoms percentage sum is 100%;
(2) by melting and belt making process, by the alloy A MN band of laminating;
(3) alloy A MN thin slice band is immersed in corrosive liquid, corrosion 1～48h, by active metal A stripping wherein;
When the atomic percent of moderate active metal M is 0%, etch rear taking-up thin slice band and clean up, make nano porous metal N;
Perhaps, when atomic percent 0%<M of moderate active metal M≤60%, moderate active metal M part stripping that simultaneously will be wherein, etch rear taking-up thin slice band and clean up, and makes nanoporous alloy MN;
The nano porous metal N that (4) will clean up or nanoporous alloy MN are placed in organic solvent, and ultrasonic 1～1000min, make the nano particle with nano-porous structure.
2. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, the described active metal A of step (1) is Al, and atom number percentage is 65～85%; Described inert metal N is a kind of in Pt, Pd, Ru, Ir or any two combination, and atom number percentage is 5～30%; Described metal M is Ni, Cu, Ti or Fe, and atom number percentage is 0～20%; Each constituent atoms number percentage sum is 100%.
3. the preparation method with nano particle of nano-porous structure according to claim 1 and 2, is characterized in that, the described active metal A of step (1) is Al, and atom number percentage is 70～80%; Described inert metal N is a kind of in Pt, Pd, Ru or any two combination, and atom number percentage is 10～20%; Described metal M is Ni, Cu or Ti, and atom number percentage is 5～10%; Each constituent atoms number percentage sum is 100%.
4. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, the strip of foil tape thickness of the described alloy A MN of step (2) is 10～200 μ m.
5. the preparation method with nano particle of nano-porous structure according to claim 1, it is characterized in that, the described corrosive liquid of step (3) is acidity or alkaline solution, and acid etching solution is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetic acid, and alkaline corrosion liquid is NaOH or KOH.
6. have according to claim 1 or 5 the preparation method of the nano particle of nano-porous structure, it is characterized in that, the concentration of the described corrosive liquid of step (3) is 0.1～2mol/L.
7. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, when in step (1), active metal A was Al, the described corrosive liquid of step (3) was the NaOH solution of 0.1～2mol/L.
8. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, the described organic solvent of step (4) is methyl alcohol, ethanol, isopropyl alcohol, acetone, benzene or toluene; Described ultrasonic time is 1～100min.
9. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, comprises that step is as follows:
(1) by Pt, Ni, Al, be that the ratio weighing of 1:1:8 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtNiAl alloy;
(2) by chilling band method processed, the PtNiAl alloy is made to wide 5mm, long 30mm, the thin slice band of thick 100 μ m;
(3) in 0.5mol/L NaOH solution, by PtNiAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making platinum nickel nanoporous alloy;
(4) platinum nickel nanoporous alloy is placed in to ethanol, ultrasonic 5min, make the PtNi alloy nanoparticle with nano-porous structure.
10. the preparation method with nano particle of nano-porous structure according to claim 1, is characterized in that, comprises that step is as follows:
(1) by Pt, Cu, Al, be that the ratio weighing of 1.5:0.5:8 is good according to atomic ratio, be placed in electric arc furnaces and be smelted into the PtCuAl alloy;
(2) by chilling band method processed, the PtCuAl alloy is made to wide 3mm, long 35mm, the thin slice band of thick 200 μ m;
(3) in 1.0mol/L NaOH solution, by PtCuAl alloy immersion corrosion 48h, by active metal component Al stripping wherein; Etch rear taking-up thin slice band and clean up, making platinoid nanoporous alloy;
(4) platinoid nanoporous alloy is placed in to ethanol, ultrasonic 8min, make the platinoid nanoporous nano particle with nano-porous structure.
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