CN108736022A - The preparation method and its resulting materials of a kind of hetero-junctions PdAg nano wires and application - Google Patents
The preparation method and its resulting materials of a kind of hetero-junctions PdAg nano wires and application Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 57
- 229910021124 PdAg Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
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- 238000005406 washing Methods 0.000 claims abstract description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000903 blocking effect Effects 0.000 claims abstract description 3
- 239000013049 sediment Substances 0.000 claims abstract 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- -1 ammonia Amide Chemical class 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of preparation method of hetero-junctions PdAg nano wires and its resulting materials and application of the material as aminic acid fuel battery anode catalyst, and the preparation method includes the poly-N-isopropyl acrylamide (PNIPAM-NH for blocking ammonia2), Pd metal precursors and Ag metal precursors be mixed to form uniform aqueous solution, reaction generates PNIPAM-NH2Mixed solution after reducing agent then is added into reaction system, is carried out hydro-thermal reaction, is centrifuged after the completion of reaction, sediment washing is dry to get the hetero-junctions PdAg nano wires by-M complexs.Compared with traditional preparation method, the method for the present invention is simple and practicable, and has universality.When hetero-junctions PdAg nano wires obtained are applied to catalysis Oxidation of Formic Acid reaction, compared with being commercialized the black catalyst of Pd, they have better catalytic activity, stability and better anti-poisoning ability.
Description
Technical field
The present invention relates to a kind of preparation method of hetero-junctions PdAg nano wires and its resulting materials and applications, belong to PdAg and receive
Rice noodles technical field.
Background technology
With the high speed development of modern society, the energy has become one of an important factor for restricting social development.Fuel electricity
Chi Yinqi has many advantages, such as that energy conversion efficiency is high, pollution is small, fuel is diversified, has become the hot topic of researcher research
One of field.Direct methanoic acid fuel cell (DFAFCs) has simple battery structure, started quickly at low temperature, energy density height, combustion
The advantages that material storage and transportation facilitates, is highly suitable as the power supply of the compact electric apparatus such as mobile phone, laptop.Although domestic and international more families grind
Study carefully the model machine that mechanism has developed various DFAFCs in succession, but really to realize commercialization, it is also necessary to further promote fuel
The performance of cell catalyst, and further decrease production cost.
Currently, being Pt and Pd to the highest single component catalyst of Oxidation of Formic Acid activity.It has been generally acknowledged that formic acid is on the surfaces Pt
Oxidation follows the progress of dual path mechanism, first, formate dehydrogenase directly generates the direct way of carbon dioxide, second is that formic acid dehydration is first
Generate carbonyl species COads, carbonyl species reoxidize generate carbon dioxide degradation pathways.And generated in dehydration approach
COadsIt can be firmly adsorbed on the surface of Pt atoms, occupy active site, to reduce the catalytic performance of Pt.Compared to
Pt, formic acid are mainly aoxidized with direct dehydrogenation approach on the surfaces Pd, reduce the generation for poisoning species, to being catalyzed Oxidation of Formic Acid
Reaction has better performance.However in acidic electrolyte bath, Pd easily dissolves, and stability is poor, and Pd can also be catalyzed first
The selfdecomposition of acid, the selectivity of reaction is poor, while the selfdecomposition of formic acid may will produce a small amount of COads, urged to poison Pd
Agent.In order to solve problem above, it needs to work out stability to be preferably catalyzed with the lower Pd bases of catalysis formic acid selfdecomposition ability
Agent.
Invention content
Goal of the invention：In view of the above technical problems, it is an object of the invention to propose a kind of to prepare ultra-fine hetero-junctions PdAg
The method of nano wire, and the nano wire that is prepared react the catalyst application of (FAOR) as Oxidation of Formic Acid, show compared with
High catalytic activity and stability.
Technical solution：The present invention adopts the following technical scheme that：
A kind of preparation method of hetero-junctions PdAg nano wires, includes the poly-N-isopropyl acrylamide for blocking ammonia
(PNIPAM-NH2), Pd metal precursors and Ag metal precursors are mixed to form uniform aqueous solution, and reaction generates PNIPAM-NH2-
Mixed solution after reducing agent then is added into reaction system, is carried out hydro-thermal reaction, centrifuges, sink after the completion of reaction by M complexs
Starch washing is dry to get the hetero-junctions PdAg nano wires.
This method is with PNIPAM-NH2As pattern directed agents and stabilizer, PNIPAM-NH2It is formed with metal ion
PNIPAM-NH2- M complexs can carry out hydro-thermal reaction as presoma in water heating kettle.
The PNIPAM-NH2Molar concentration in terms of monomer, with the molar ratios of the sum of two kinds of metal precursors be (1~
4):1, PNIPAM-NH2Average molecular weight be preferably 2500.
The molar ratio of the sum of the reducing agent and two kinds of metal precursors is (150~600):1.
The reducing agent is formaldehyde, and the concentration of HCHO is preferably 40%.
The Pd metal precursors are K2PdCl4Or PdCl2；The Ag metal precursors are AgNO3。
The molar ratio of the Pd metal precursors and Ag metal precursors is 1:(0.3~3).
The reaction temperature of the hydro-thermal reaction is 140~200 DEG C, and the reaction time is 4~6h.
Hetero-junctions PdAg nano-materials obtained by the preparation method, the material are urged as aminic acid fuel battery anode
Agent application, has excellent performance.
First, the present invention improves the activity of catalyst by regulating and controlling the composition of Pd base catalyst, that is, introduces Ag elements, shape
At alloy, the Oxidation of Formic Acid performance of Pd base catalyst can be significantly improved.This performance raising is mainly based upon following two effects
It answers, first, difunctional effect, the second metal is conducive to provide oxygen-containing group under low potential, to contribute to COadsOxidation,
Second is that electronic effect, after forming alloy, the electronic structure of Pd changes, and can regulate and control Pd and COadsBetween adsorption energy, subtract
Few COadsAbsorption on a catalyst improves reactivity.
Other than introducing second of metal, the heterojunction structure of material of the present invention, i.e., in multicomponent elctro-catalyst, catalyst is not
With between component interaction and contact interface, the high catalytic activity of catalyst, selectivity can be assigned.In a catalyst not
With certain effect generated by interfacial contact between component and/or active site, it can significantly enhance catalytic performance, this is remote
Catalytic performance after being simply mixed better than corresponding one pack system or one pack system.
In addition, other than component regulates and controls, the pattern of nanocatalyst be also an important factor for influencing catalyst performance it
One.One-dimensional nano line of the present invention can expose more surface atoms, have abundant active site.And with zero dimension
Nano-particle is compared, and it is ripe that one-dimensional nano line can effectively inhibit catalyst that dissolving, reunion and Ostwald occur during the reaction
Phenomena such as change, has better structural stability.In addition, the anisotropy of one-dimensional nano line itself can accelerate the biography of electronics
It is defeated, to improve catalytic kinetics, improve catalytic performance.
Technique effect：Compared with traditional preparation method, the method for the present invention is simple and practicable, and has universality.It will system
When the hetero-junctions PdAg nano wires obtained are applied to catalysis Oxidation of Formic Acid reaction, compared with being commercialized the black catalyst of Pd, they have
Better catalytic activity, stability and better anti-poisoning ability.It specifically includes：
(1) alternating growth of PdAg alloy crystals and Ag elemental crystals produces the contact between highdensity heterogeneity
Interface forms unique hetero-junctions, can significantly enhance catalytic performance, is much better than one pack system or after one pack system is simply mixed
Catalytic performance.
(2) one-dimensional nano line can expose more surface atoms, have abundant active site, and it is certainly
The anisotropy energy of body accelerates the transmission of electronics, to improve the performance of catalysis reaction.
(3) compared with zero-dimension nano particle, it is molten that one-dimensional nano line can effectively inhibit catalyst to occur during the reaction
Phenomena such as solution, reunion and Ostwald are cured, has better structural stability.
(4) introducing of this hydrophilic metals of Ag can more adsorbed water molecules, generate oxygenated species under low potential, have
Help intermediate product COadsRemoving, to improve the antitoxinization performance of catalyst.
(5) bimetallic introducings can bring electronic effect, and the electronic structure of Pd is made to change, and regulate and control Pd and COads
Between adsorption energy, reduce COadsAbsorption, further increase the anti-poisoning ability of catalyst.
Test result shows that ultra-fine PdAg nano wires obtained are black compared to commercialization Pd, show preferably catalysis formic acid
Activity, stability and the anti-poisoning ability of oxidation reaction.
Description of the drawings
Fig. 1 is the high power transmission electron microscope figure (HRTEM) of PdAg nano wires prepared by the method for the present invention.
Fig. 2 is the lattice of PdAg nano wires prepared by the method for the present invention.
Fig. 3 is the X-ray diffractogram (XRD) of PdAg nano wires prepared by the method for the present invention.
Fig. 4 is the linear sweep graph of PdAg nano wires prepared by the method for the present invention.
Fig. 5 is that PdAg nano wires prepared by the method for the present invention and commercialization Pd are black in 0.5M H2SO4In cyclic voltammogram
(CV)。
Fig. 6 is that PdAg nano wires prepared by the method for the present invention and commercialization Pd are black in 0.5M H2SO4In+1M HCOOH solution
Cyclic voltammogram.
Fig. 7 is that PdAg nano wires prepared by the method for the present invention and commercialization Pd are black in 0.5M H2SO4In+1M HCOOH solution
Chronoa mperometric plot.
Specific implementation mode
Technical solutions according to the invention are further described in detail below by specific embodiment, but it is necessary to
It points out that following embodiment is served only for the description to invention content, does not constitute limiting the scope of the invention.
Embodiment 1
A kind of overlength, the preparation method of ultra-fine hetero-junctions PdAg nano wires, include the following steps：
(1) PNIPAM-NH is synthesized2- M complex precursors：By 2mL 0.05mM PNIPAM-NH2(average molecular weight is
2500, Sigma-Aldrich companies are purchased from, following embodiment is identical) and 0.5mL 0.05mM K2PdCl4And 0.5mL
0.05mM AgNO3Mixing reacts and PNIPAM-NH is made2- M complex precursors.
(2)PNIPAM-NH2The reduction of-M complex precursors：To PNIPAM-NH2Reducing agent is added in the aqueous solution of-M
(a concentration of 40%) is put into hydrothermal reaction kettle after ultrasonic mixing 1mL HCHO, is reacted 3 hours in 140 DEG C, until PNIPAM-
NH2- M is reduced completely.Then for several times by the mixed solution centrifuge washing of product water and ethyl alcohol, it is extra to remove nanowire surface
Polymer after be drying to obtain overlength, ultra-fine hetero-junctions Pd1Ag1Nano wire.
Embodiment 2
A kind of overlength, ultra-fine hetero-junctions Pd1Ag2The preparation method of nano wire, includes the following steps：
(1) PNIPAM-NH is synthesized2- M complex precursors：By 2mL 0.05mM PNIPAM-NH2(average molecular weight is
2500) with 0.5mL 0.05mM K2PdCl4With 1mL 0.05mM AgNO3Mixing reacts and PNIPAM-NH is made2Before-M complexs
Drive body.
(2)PNIPAM-NH2The reduction of-M complex precursors：To PNIPAM-NH2Reducing agent is added in the aqueous solution of-M
(a concentration of 40%) is put into hydrothermal reaction kettle after ultrasonic mixing 1mL HCHO, is reacted 3 hours in 140 DEG C, until PNIPAM-
NH2- M is reduced completely.Then for several times by the mixed solution centrifuge washing of product water and ethyl alcohol, it is extra to remove nanowire surface
Polymer after be drying to obtain overlength, ultra-fine hetero-junctions Pd1Ag2Nano wire.
Embodiment 3
A kind of overlength, ultra-fine hetero-junctions Pd2Ag1The preparation method of nano wire, includes the following steps：
(1) PNIPAM-NH is synthesized2- M complex precursors：By 2mL 0.05mM PNIPAM-NH2(average molecular weight is
2500) with 1mL 0.05mM K2PdCl4With 0.5mL 0.05mM AgNO3Mixing reacts and PNIPAM-NH is made2Before-M complexs
Drive body.
(2)PNIPAM-NH2The reduction of-M complex precursors：To PNIPAM-NH2Reducing agent is added in the aqueous solution of-M
(a concentration of 40%) is put into hydrothermal reaction kettle after ultrasonic mixing 1mL HCHO, is reacted 3 hours in 140 DEG C, until PNIPAM-
NH2- M is reduced completely.Then for several times by the mixed solution centrifuge washing of product water and ethyl alcohol, it is extra to remove nanowire surface
Polymer after be drying to obtain overlength, ultra-fine hetero-junctions Pd2Ag1Nano wire.
Embodiment 4
A kind of overlength, ultra-fine hetero-junctions Pd3Ag1The preparation method of nano wire, includes the following steps：
(1) PNIPAM-NH is synthesized2- M complex precursors：By 2mL 0.05mM PNIPAM-NH2(average molecular weight is
2500) with 1.5mL 0.05mM K2PdCl4With 1mL 0.05mM AgNO3Mixing reacts and PNIPAM-NH is made2Before-M complexs
Drive body.
(2)PNIPAM-NH2The reduction of-M complex precursors：To PNIPAM-NH2Reducing agent is added in the aqueous solution of-M
(a concentration of 40%) is put into hydrothermal reaction kettle after ultrasonic mixing 1mL HCHO, is reacted 3 hours in 140 DEG C, until PNIPAM-
NH2- M is reduced completely.Then for several times by the mixed solution centrifuge washing of product water and ethyl alcohol, it is extra to remove nanowire surface
Polymer after be drying to obtain overlength, ultra-fine hetero-junctions Pd3Ag1Nano wire.
Embodiment 5
A kind of overlength, ultra-fine hetero-junctions Pd1Ag3The preparation method of nano wire, includes the following steps：
(1) PNIPAM-NH is synthesized2- M complex precursors：By 2mL 0.05mM PNIPAM-NH2(average molecular weight is
2500) with 0.5mL 0.05mM K2PdCl4With 1.5mL 0.05mM AgNO3Mixing reacts and PNIPAM-NH is made2- M complexs
Presoma.
(2)PNIPAM-NH2The reduction of-M complex precursors：To PNIPAM-NH2Reducing agent is added in the aqueous solution of-M
(a concentration of 40%) is put into hydrothermal reaction kettle after ultrasonic mixing 1mL HCHO, is reacted 3 hours in 140 DEG C, until PNIPAM-
NH2- M is reduced completely.Then for several times by the mixed solution centrifuge washing of product water and ethyl alcohol, it is extra to remove nanowire surface
Polymer after be drying to obtain overlength, ultra-fine hetero-junctions Pd1Ag3Nano wire.
Embodiment 6
It is substantially the same manner as Example 1, it the difference is that only：PNIPAM-NH2Molar concentration in terms of monomer, with two kinds
The molar ratio of the sum of metal precursor is 1:1；Pd metal precursors are PdCl2；
The molar ratio of the sum of formaldehyde and two kinds of metal precursors is 150:1；
The molar ratio of Pd metal precursors and Ag metal precursors is 1:0.3；
The reaction temperature of hydro-thermal reaction is 160 DEG C, reaction time 6h.
Embodiment 7
It is substantially the same manner as Example 1, it the difference is that only：PNIPAM-NH2Molar concentration in terms of monomer, with two kinds
The molar ratio of the sum of metal precursor is 4:1；
The molar ratio of the sum of formaldehyde and two kinds of metal precursors is 600:1；
The molar ratio of Pd metal precursors and Ag metal precursors is 1:3；
The reaction temperature of hydro-thermal reaction is 180 DEG C, reaction time 4h.
Embodiment 8
It is substantially the same manner as Example 1, it the difference is that only：PNIPAM-NH2Molar concentration in terms of monomer, with two kinds
The molar ratio of the sum of metal precursor is 2.5:1；
The molar ratio of the sum of formaldehyde and two kinds of metal precursors is 375:1；
The molar ratio of Pd metal precursors and Ag metal precursors is 1:1.65；
The reaction temperature of hydro-thermal reaction is 200 DEG C, reaction time 5h.
As shown in the TEM of Fig. 1, obtained catalyst be wavy one-dimensional nano line, the height of nano wire is soft
Property make its be interweaved together, formed three-dimensional net structure.The length of flexible nano line can reach hundreds of nanometers, average grain diameter
About 3nm.Fig. 2 is hetero-junctions Pd1Ag1The lattice of nano wire, by measurement obtain two kinds of spacing of lattice 0.228nm and
0.236nm, wherein 0.228nm correspond to the face-centered cubic phase of PdAg alloys, and 0.236nm corresponds to the face-centered cubic phase of Ag, by
This finds out gained Pd1Ag1Nano wire is made of PdAg alloys and simple substance Ag.Fig. 3 is ultra-fine hetero-junctions Pd1Ag1The XRD of nano wire
Figure, by being compared with standard spectrogram, hetero-junctions Pd in Fig. 21Ag1The peaks XRD one kind peak of nano wire is located at pure Pd (Pd, JCPDS
No.65-6174) between pure Ag (Ag, JCPDS no.65-8428) base peak, another kind of peak is located at pure Ag (Ag, JCPDS
No.65-8428) on base peak, it is therefore seen that gained Pd1Ag1Nano wire is made of PdAg alloys and simple substance Ag.Fig. 4 is hetero-junctions
Pd1Ag1The linear sweep graph of nano wire, it can be clearly seen that, obtained catalyst is formed with PdAg alloys and Ag.With commercialization
Pd is black as a comparison, to hetero-junctions Pd1Ag1Nano wire is probed into the ability of catalysis Oxidation of Formic Acid.Fig. 5 is hetero-junctions
Pd1Ag1Nano wire and commercialization Pd are black in 0.5M H2SO4In CV figure.Hetero-junctions Pd can be calculated from figure1Ag1Nano wire
Electrochemical surface area (ECSA) be 3.19m2g-1.Fig. 6 is respectively hetero-junctions Pd1Ag1Nano wire and commercialization Pd are black in 0.5M
H2SO4Area specific activity in+0.5M HCOOH, it is found that the face base specific activity of nano-wire catalyst obtained is all higher than quotient
The black catalyst of industry Pd shows that nano-wire catalyst has better catalytic activity.Fig. 7 is Pd1Ag1Nano wire and commercialization
Chronoa mperometric plot black Pd, after 3000s, hetero-junctions Pd1Ag1Nanometer line attenuation 45.9%, and it is commercialized the black decaying of Pd
76.2%, it was demonstrated that hetero-junctions Pd1Ag1Nano wire has better electrochemical stability.
Claims (9)
1. a kind of preparation method of hetero-junctions PdAg nano wires, which is characterized in that include the poly-N-isopropyl propylene for blocking ammonia
Amide (PNIPAM-NH2), Pd metal precursors and Ag metal precursors be mixed to form uniform aqueous solution, reaction generates PNIPAM-
NH2- M complexs, then into reaction system be added reducing agent after, mixed solution is subjected to hydro-thermal reaction, after the completion of reaction from
The heart, sediment washing are dry to get the hetero-junctions PdAg nano wires.
2. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the PNIPAM-NH2
Molar concentration in terms of monomer, be 1~4 with the molar ratios of the sum of two kinds of metal precursors:1.
3. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the reducing agent and two
The molar ratio of the sum of kind metal precursor is 150~600:1.
4. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the Pd metal fronts
Body is K2PdCl4Or PdCl2；The Ag metal precursors are AgNO3。
5. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the Pd metal fronts
The molar ratio of body and Ag metal precursors is 1:0.3~3.
6. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the reducing agent is first
Aldehyde.
7. the preparation method of hetero-junctions PdAg nano wires according to claim 1, which is characterized in that the hydro-thermal reaction
Reaction temperature is 140~200 DEG C, and the reaction time is 4~6h.
8. the hetero-junctions PdAg nano-materials obtained by any one of the claim 1-7 preparation methods.
9. application of the hetero-junctions PdAg nano-materials as aminic acid fuel battery anode catalyst described in claim 8.
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