CN107507986A - A kind of PdSn CuO composites of nano-porous structure prepare and application - Google Patents
A kind of PdSn CuO composites of nano-porous structure prepare and application Download PDFInfo
- Publication number
- CN107507986A CN107507986A CN201710777031.1A CN201710777031A CN107507986A CN 107507986 A CN107507986 A CN 107507986A CN 201710777031 A CN201710777031 A CN 201710777031A CN 107507986 A CN107507986 A CN 107507986A
- Authority
- CN
- China
- Prior art keywords
- percentage content
- pdsn
- atom percentage
- nano
- porous structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of the PdSn CuO composites of nano-porous structure, atom percentage content according to Al is 81 84%, Pd atomic percentage conc is 3 7%, Sn atomic percentage conc is 8 12%, Cu atom percentage content 1 4%, prepare the Al Pd Sn Cu AMORPHOUS ALLOY RIBBONSs that thickness is 10um 30um；Put it into the hydrothermal reaction kettle of a certain amount of corrosive liquid and take off alloy using hydro-thermal reaction, be products therefrom after cleaning-drying, the composite has high specific surface area, Stability Analysis of Structures, and being mutually communicated property is advantageous to the transmission of electronics and ion.The preparation method is simple to operate, easy to implement, and cost is low, economical and efficient.In terms of gained composite is used for into the electrocatalysis characteristic to methanol, conventional commercial palladium-carbon catalyst relatively now, all with more excellent electro catalytic activity and long-time stability.
Description
Technical field
The present invention relates to a kind of PdSn-CuO composite material and preparation method thereofs of nano-porous structure and its in methanol electro-catalysis
The application of aspect of performance, belong to electrochemistry new forms of energy new material technical field.
Background technology
DMFC (DMFCs), which has become in the fuel cell of numerous kinds, has low-temperature operation, high energy
A novel battery equipment of the advantage such as effect and low emission, and apply in portable multifunctional mobile device and various miniature electrics
In instrument.But the wide variety of bottleneck of this technology is that market introduction cost is high, long-time stability are low at present.Pass through
In precious metals pd base catalyst introduce metal oxide CuO, can with the absorption and dissociation of accelerator activator surface methanol molecules,
The absorption containing intermediate carbon He other intermediate products is reduced, the water decomposition that can also activate low potential produces oxygen carrier, so as to
Promote the oxidation containing intermediate carbon on avtive spot.Therefore, the oxidation of these intermediates can be promoted, improve precious metal catalyst
The anti-poisoning ability of agent.
Preparation method can influence the electrocatalysis characteristic of composite catalyst.De- alloyage, i.e., using chemical or electrochemistry
Method, alloy constituent element more active in the larger alloy of difference in Electrode Potential is eroded and leaves the mistake of relatively stable constituent element
Journey.By taking off the material prepared of alloyage, the loose structure mostly with co-continuous, by control constituent element in alloy into
Point, hole wall and aperture size can be adjusted porous material, in addition, by controlling de- alloying technology, not only can be with shape
Into the loose structure of single group member, while alloy porous structure can be formed.Compared with block alloy, nano-porous structure have compared with
High specific surface area so that more catalyst atoms can contact with the material being catalyzed, so as to increase catalytic activity.
The content of the invention
The defects of existing for prior art, the invention provides a kind of PdSn-CuO composites of nano-porous structure
Preparation method and methanol oxidation performance applications.Using the original AMORPHOUS ALLOY RIBBONSs of Al-Pd-Sn-Cu and sodium hydroxide water as raw material,
At certain temperature, it is compound that the PdSn-CuO with uniform nano-porous structure is prepared by the de- alloy approach of step chemistry
Material, this method cost is low, simple to operate, and exploitativeness is strong.The PdSn-CuO composites of gained have preferable methanol electricity
Catalytic performance.
Low in order to solve methanol fuel cell anode catalyzer catalytic performance, the problem of anti-poisoning ability difference, the present invention carries
A kind of PdSn-CuO composites of the nano-porous structure gone out, it is made with aluminium-tin-palladium-copper alloy strips and includes tin, palladium and oxygen
Change the composite with continuous nanoporous-ligament structure of copper, the pore diameter of the nanoporous-ligament structure is
15nm-40nm, ligament width 20nm-60nm.
The preparation method of the PdSn-CuO composites of above-mentioned nano-porous structure, comprises the following steps：
Step 1: be 81-84% according to Al atom percentage content, Pd atomic percentage conc is 3-7%, Sn original
Sub- percentage composition is 8-12%, Cu atom percentage content 1-4%, prepares the Al-Pd-Sn-Cu that thickness is 10um-30um
AMORPHOUS ALLOY RIBBONS；
Step 2: it is 15mm-25mm that Al-Pd-Sn-Cu AMORPHOUS ALLOY RIBBONSs made from step 1 are cut into width, it is long
The non-crystaline amorphous metal batten for 2cm-3cm is spent, it is standby；
Step 3: above-mentioned non-crystaline amorphous metal batten is together placed in molar concentration for 1-5 moles of sodium hydrate aqueous solution
Hydro-thermal reaction is carried out in closed container, wherein, the mass volume ratio of non-crystaline amorphous metal batten and sodium hydrate aqueous solution is 1g/ (80
~400) mL, reaction temperature are reaction time 24-48h at 40-60 DEG C；
Step 4: the batten after step 3 hydro-thermal reaction is cleaned repeatedly with deionized water and absolute ethyl alcohol, it is subsequently placed in
It is dried at room temperature, that is, obtains the PdSn-CuO composites of nano-porous structure.
Further, in the preparation method of the PdSn-CuO composites of nano-porous structure of the invention, for step
The process conditions of the composition of Al-Pd-Sn-Cu AMORPHOUS ALLOY RIBBONSs and the hydro-thermal reaction in step 3 have following preferred side in one
Case：
(1) in step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 1% than the atomic percentage conc that content is 84%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 3 moles, reaction
Temperature is 60 DEG C, reaction time 48h.
(2) in step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 2% than the atomic percentage conc that content is 83%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, reaction
Temperature is 60 DEG C, reaction time 48h.
(3) in step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 2% than the atomic percentage conc that content is 83%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, reaction
Temperature is 50 DEG C, reaction time 36h.
(4) in step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 4% than the atomic percentage conc that content is 81%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 5 moles, reaction
Temperature is 40 DEG C, reaction time 24h.
(5) in step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 3% than the atomic percentage conc that content is 82%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 5 moles, reaction
Temperature is 60 DEG C, reaction time 48h.
(6) in step 1, Sn atom percentage content 12%, Pd atom percentage content 3%, Al atomic percent
It is 2% than the atomic percentage conc that content is 83%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, reaction
Temperature is 60 DEG C, reaction time 48h.
(7) in step 1, Sn atom percentage content 8%, Pd atom percentage content 7%, Al atomic percent
It is 2% than the atomic percentage conc that content is 83%, Cu；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, reaction
Temperature is 60 DEG C, reaction time 48h.
By the nano-porous structure of the preparation method preparation according to the PdSn-CuO composites of above-mentioned nano-porous structure
PdSn-CuO composites be used for methanol fuel cell anode catalyst, in the application of its catalytic performance, the PdSn-
CuO composites are as working electrode material, and the mixed solution of sodium hydroxide and methanol is as working electrolyte, using three electrodes
System, structure methanol fuel cell system carry out anode catalyst catalytic performance application
Compared with prior art, the beneficial effects of the invention are as follows：
The composite obtained using preparation method of the present invention has the PdSn- of nanoporous-ligament structure of co-continuous
CuO composite catalysts, have the advantage that：(1) the preparation method process of the catalyst is simple and easy to control, implementation cost
It is low, it is a kind of method of economical and efficient；(2) nano-porous structure prepared has high specific surface area, Stability Analysis of Structures, mutually passes through
The general character is advantageous to the transmission of electronics and ion；(3) synergy between metal oxide CuO and precious metals pd, be advantageous to carry
The anti-poisoning ability and catalytic performance of high catalyst.
Brief description of the drawings
Fig. 1 is the microscopic appearance photo that 1-4 of the embodiment of the present invention prepares PdSn-CuO composites, wherein, (a) is implementation
Example 1 prepares the microscopic appearance photo of PdSn-CuO composites, and (b) is that embodiment 2 prepares the microcosmic of PdSn-CuO composites
Pattern photo, (c) are the microscopic appearance photo that embodiment 3 prepares PdSn-CuO composites, and (d) is that embodiment 4 prepares PdSn-
The microscopic appearance photo of CuO composites.
Fig. 2 is that PdSn-CuO composites prepared by 1-4 of the embodiment of the present invention use electrochemical operation in the basic conditions
The cyclic voltammetry curve stood to methanol test.
Fig. 3 is that PdSn-CuO composites prepared by the embodiment of the present invention 2 and commercial palladium carbon powder use in the basic conditions
The cyclic voltammetry curve that electrochemical workstation is tested methanol.
Embodiment
A kind of PdSn-CuO composites of nano-porous structure proposed by the present invention, it is to use aluminium-tin-palladium-copper alloy bar
The obtained composite with continuous nanoporous-ligament structure for including tin, palladium and cupric oxide of band, the nanoporous-
The pore diameter of ligament structure is 15nm-40nm, ligament width 70nm-90nm.By the PdSn- of above-mentioned nano-porous structure
CuO composites can improve catalytic performance, strengthen anti-poisoning ability as methanol fuel cell positive pole.
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific
Only the present invention is explained for embodiment, is not intended to limit the invention.
Embodiment 1：Use Al84Pd5Sn10Cu1AMORPHOUS ALLOY RIBBONS prepares the PdSn-CuO composites of nano-porous structure,
Step is as follows：
Step 1: according to Sn atom percentage content 10%, Pd atom percentage content 5%, Al atomic percent
It is 1% than the atomic percentage conc that content is 84%, Cu, prepares the Al that thickness is about 20um84Pd5Sn10Cu1Non-crystaline amorphous metal bar
Band.
Step 2: it is Al by composition84Pd5Sn10Cu1It is 20mm that AMORPHOUS ALLOY RIBBONS, which is cut into width, and length is the non-of 2cm
Peritectic alloy batten.
Step 3: the hydrogen that 0.1g and 40ml molar concentrations are 3 moles is removed on the non-crystaline amorphous metal batten that step 2 obtains
Aqueous solution of sodium oxide is together placed in closed container, is placed in the drying box that reaction temperature is 60 DEG C, is incubated 48h.
Step 4: the batten after step 3 reaction is terminated is cleaned repeatedly with deionized water and absolute ethyl alcohol, room temperature is placed in
The sample obtained after lower drying is the PdSn-CuO composites of nano-porous structure.
The PdSn-CuO composites that (a) in Fig. 1 illustrates the nano-porous structure being prepared by embodiment 1 are micro-
Pattern photo (SEM S-4800, HatchiJapan) is seen, its pore diameter is 28nm, ligament width 30nm.
By the PdSn-CuO composites application of nano-porous structure produced by the present invention, methanol electricity is urged in the basic conditions
In change, comprise the following steps that：
Step 1, according to the methanol of sodium hydroxide+molar concentration 1 of molar concentration 0.5 configure a certain amount of mixed solution.
Step 2, take sample made from 2mg embodiments 1,400ul deionized waters, 100ul absolute ethyl alcohols and 50ulNafion
Solution ultrasonic mixing is uniform, and drawing 150ul homogeneous solutions with liquid-transfering gun drops on a diameter of 1.5cm glass-carbon electrode, is placed in room
It is dried under temperature.The electrode of commercial palladium carbon prepares also such.
Step 3, taking dried glass-carbon electrode, platinum guaze (specification 2cm*2cm) is to electrode, saturation as working electrode
Calomel electrode is reference electrode, is configured in step 1 using model Gamry Reference 600 electrochemical workstation
Cyclic voltammetry is carried out in mixed solution, voltage tester scope is -0.8V--0.3V, sweep speed 50mV/s.In Fig. 2
Fine line shows the PdSn-CuO composite material nanometer loose structure cyclic voltammetry curves that embodiment 1 is prepared.
Embodiment 2：Use Al84Pd5Sn10Cu2AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two and four difference in example 1 is identical, the Cu being only that in step 1 and step 3 atomic percentage conc and corrosion liquid hydrogen
Aqueous solution of sodium oxide concentration is different, i.e.,：
Cu atomic percent is 2% in step 1, and the concentration of sodium hydroxide solution is 1 mole in step 3, reaction temperature
Spend for 60 DEG C, reaction time 48h.Fig. 1 (b) shows the porous knot of PdSn-CuO composite Nanos that the embodiment 2 is prepared
The SEM figures of structure material, its pore diameter is 20nm, ligament width 36nm.The PdSn-CuO that the present embodiment is prepared is answered
Condensation material application is in the basic conditions in the performance test of electro-catalysis methanol.Fig. 2 middle heavy line shows that embodiment 2 is prepared into
The PdSn-CuO composite material nanometer loose structure cyclic voltammetry curves arrived.Fig. 3 shows that PdSn-CuO prepared by embodiment 2 is answered
Condensation material and the commercial palladium carbon powder that mass fraction is 20% are followed using electrochemical workstation to methanol test in the basic conditions
Ring volt-ampere curve.It can draw：Compared to commercial palladium carbon powder, composite prepared by embodiment 2 is as methanol fuel cell
Anode catalyst has very big raising to the oxidation susceptibility of methanol in the basic conditions, the anodic oxidation during forward scan
Current density is 2.5 times or so of commercial palladium carbon powder.
Embodiment 3：Use Al83Pd5Sn10Cu2AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two in example 1 and four difference are identical, are only that in step 1 that sodium hydroxide is rotten in Cu atomic percentage conc and step 3
Liquid concentration, reaction temperature and time difference are lost, i.e.,：
Cu atom percentage content is 2% in step 1, and the concentration of sodium hydrate aqueous solution is 1 mole in step 3,
Reaction temperature is 50 DEG C, reaction time 36h.(c) in Fig. 1 illustrates the nanoporous knot being prepared by embodiment 3
The Pd-Sn composite microscopic appearance photos of structure, its pore diameter are 24nm, ligament width 31nm.It is prepared by the present embodiment
Obtained PdSn-CuO composites application is in the basic conditions in the performance test of electro-catalysis methanol.Thick dashed line in Fig. 2 shows
The PdSn-CuO composite material nanometer loose structure cyclic voltammetry curves that embodiment 3 is prepared are gone out.
Embodiment 4：Use Al81Pd5Sn10Cu4AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two in example 1 and four difference are identical, are only that the atomic percentage conc of Cu in step 1, and the sodium hydroxide in step 3 is rotten
It is different to lose liquid concentration, reaction time and reaction temperature, i.e.,：
Cu atom percentage content is 4% in step 1, and the concentration of sodium hydrate aqueous solution is 5 moles in step 3,
Reaction temperature is 40 DEG C, reaction time 24h.(d) in Fig. 1 illustrates the nanoporous knot being prepared by embodiment 4
The PdSn-CuO composite microscopic appearance photos of structure, its pore diameter are 22nm, ligament width 44nm.By the present embodiment system
Standby obtained Pd-Sn composites application is in the basic conditions in the performance test of electro-catalysis methanol.Fine dotted line in Fig. 2 is shown
The PdSn-CuO composite material nanometer loose structure cyclic voltammetry curves that embodiment 3 is prepared.
Embodiment 5：Use Al82Pd5Sn10Cu3AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two in example 1 and four difference are identical, be only that in step 1 Cu atomic percentage conc and with sodium hydroxide in step 3
Concentration of aqueous solution is different, i.e.,：Cu atom percentage content is 3% in step 1, and sodium hydrate aqueous solution is dense in step 3
Degree is 5 moles.
Embodiment 6：Use Al83Pd3Sn12Cu2AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two in example 1 and four difference are identical, be only that step 1 Al, Pd, Sn, Cu atomic percentage conc and with hydrogen in step 3
Aqueous solution of sodium oxide concentration is different, i.e.,：In step 1, Sn atom percentage content 12%, Pd atom percentage content
The atomic percentage conc that 3%, Al atom percentage content are 83%, Cu is 2%；Sodium hydrate aqueous solution is dense in step 3
Degree is 1 mole.
Embodiment 7：Use Al83Pd7Sn8Cu2AMORPHOUS ALLOY RIBBONS prepares nanoporous PdSn-CuO composites, with implementation
Step two in example 1 and four difference are identical, be only that step 1 Al, Pd, Sn, Cu atomic percentage conc and with hydrogen in step 3
Aqueous solution of sodium oxide concentration is different, i.e.,：In step 1, Sn atom percentage content 8%, Pd atom percentage content 7%,
The atomic percentage conc that Al atom percentage content is 83%, Cu is 2%；The concentration of sodium hydrate aqueous solution is in step 3
1 mole.
To sum up, in preparation process of the present invention, the PdSn-CuO composites with nano-porous structure, hole can be obtained
Gap a diameter of 15nm-40nm, ligament width 20nm-60nm.The PdSn-CuO catalyst of preparation is to the methanol under alkalescence condition
Catalysis has shown good catalytic performance.
When Pd and Sn atomic percents in step 1 all immobilize, Cu atomic percentage conc in virgin alloy band
Pattern and methanol electrocatalysis characteristic to catalyst have important influence.On the one hand, with Cu contents in virgin alloy band
Increase, pore-size is gradually reduced, and because the chemism of Cu atoms is less than Al chemism, therefore can reduce hydrogen-oxygen
Change the de- alloy speed in sodium solution so that nano-porous structure aperture diminishes；On the other hand, with Cu in virgin alloy band
The increase of content, to the catalytic performance first increases and then decreases of sample, the CuO in catalyst sample can produce with Pd cooperate with catalyst
Effect, improves the catalytic performance of catalyst, when Cu contents are low, CuO content is few, not strong enough to the facilitation of methanol oxidation
Strong, catalytic performance is relatively low, and when Cu contents are high, CuO content is more, but excessive CuO can cover a part of Pd
Electro-chemical activity site so that the catalytic performance of catalyst declines.
Pd atom percentage content also has important shadow to the electrocatalysis characteristic of methanol under alkalescence condition in step 1
Ring.With the increase of Pd contents, the methanol oxidation performance of the catalyst sample of preparation shows becoming for first increases and then decreases
Gesture, because when Pd contents are low, Pd avtive spot is few, thus catalytic performance is low, during Pd too high levels, the Pd meetings of low diffusion coefficient
Reduce de- alloy speed so that the hole of catalyst is small, and the Pd avtive spots exposed to outside are also relatively few, therefore methanol oxidation
Can be relatively low.Sn elements in catalyst play synergy, are mutually cooperateed with Pd elements in catalytic process, improve catalysis
The catalytic performance of agent.
As shown in figure 3, the Al in embodiment 283Pd5Sn10Cu2Pd and Cu atom percentage content in virgin alloy band
Respectively 5% and 2%, the relatively commercial palladium carbon powder tool of electrocatalysis characteristic of the catalyst methanol of preparation improves a lot.
Although above in conjunction with accompanying drawing, invention has been described, and the invention is not limited in above-mentioned specific implementation
Mode, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art is at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's
Within protection.
Claims (10)
1. the PdSn-CuO composites of a kind of nano-porous structure, it is characterised in that be made with aluminium-tin-palladium-copper alloy strips
The composite with continuous nanoporous-ligament structure comprising tin, palladium and cupric oxide, the nanoporous-ligament knot
The pore diameter of structure is 15nm-40nm, ligament width 20nm-60nm.
A kind of 2. preparation method of the PdSn-CuO composites of nano-porous structure as claimed in claim 1, it is characterised in that
Comprise the following steps：
Step 1: be 81-84% according to Al atom percentage content, Pd atomic percentage conc is 3-7%, Sn atom hundred
It is 8-12%, Cu atom percentage content 1-4% to divide content, prepares the Al-Pd-Sn-Cu amorphous that thickness is 10um-30um
Alloy strip；
Step 2: it is 15mm-25mm that Al-Pd-Sn-Cu AMORPHOUS ALLOY RIBBONSs made from step 1 are cut into width, length is
2cm-3cm non-crystaline amorphous metal batten, it is standby；
Step 3: the sodium hydrate aqueous solution that above-mentioned non-crystaline amorphous metal batten and molar concentration are 1-5 moles is together placed in closed
Hydro-thermal reaction is carried out in container, wherein, the mass volume ratio of non-crystaline amorphous metal batten and sodium hydrate aqueous solution for 1g/ (80~
400) mL, reaction temperature are reaction time 24-48h at 40-60 DEG C；
Step 4: the batten after step 3 hydro-thermal reaction is cleaned repeatedly with deionized water and absolute ethyl alcohol, room temperature is subsequently placed in
Under be dried, that is, obtain the PdSn-CuO composites of nano-porous structure.
3. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atom percentage content
Atomic percentage conc for 84%, Cu is 1%；In step 3, the concentration of sodium hydrate aqueous solution is 3 moles, and reaction temperature is
60 DEG C, reaction time 48h.
4. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atom percentage content
Atomic percentage conc for 83%, Cu is 2%；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, and reaction temperature is
60 DEG C, reaction time 48h.
5. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atom percentage content
Atomic percentage conc for 83%, Cu is 2%；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, and reaction temperature is
50 DEG C, reaction time 36h.
6. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atom percentage content
Atomic percentage conc for 81%, Cu is 4%；In step 3, the concentration of sodium hydrate aqueous solution is 5 moles, and reaction temperature is
40 DEG C, reaction time 24h.
7. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 10%, Pd atom percentage content 5%, Al atom percentage content
Atomic percentage conc for 82%, Cu is 3%；In step 3, the concentration of sodium hydrate aqueous solution is 5 moles, and reaction temperature is
60 DEG C, reaction time 48h.
8. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 12%, Pd atom percentage content 3%, Al atom percentage content
Atomic percentage conc for 83%, Cu is 2%；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, and reaction temperature is
60 DEG C, reaction time 48h.
9. the preparation method of the PdSn-CuO composites of nano-porous structure according to claim 2, wherein,
In step 1, Sn atom percentage content 8%, Pd atom percentage content 7%, Al atom percentage content is
83%, Cu atomic percentage conc are 2%；In step 3, the concentration of sodium hydrate aqueous solution is 1 mole, reaction temperature 60
DEG C, reaction time 48h.
10. prepared according to the preparation method of the PdSn-CuO composites of any nano-porous structure in claim 2-9
Nano-porous structure PdSn-CuO composites methanol fuel cell anode catalyst catalytic performance application, it is special
Sign is, the PdSn-CuO composites are as working electrode material, and the mixed solution of sodium hydroxide and methanol is as work
Electrolyte, using three-electrode system, structure methanol fuel cell system carries out anode catalyst catalytic performance application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710777031.1A CN107507986A (en) | 2017-08-31 | 2017-08-31 | A kind of PdSn CuO composites of nano-porous structure prepare and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710777031.1A CN107507986A (en) | 2017-08-31 | 2017-08-31 | A kind of PdSn CuO composites of nano-porous structure prepare and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107507986A true CN107507986A (en) | 2017-12-22 |
Family
ID=60694657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710777031.1A Pending CN107507986A (en) | 2017-08-31 | 2017-08-31 | A kind of PdSn CuO composites of nano-porous structure prepare and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107507986A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923737A (en) * | 2018-09-20 | 2020-03-27 | 天津大学 | Nano porous hydrogen production catalyst and preparation method thereof |
| CN112169809A (en) * | 2020-11-03 | 2021-01-05 | 西安工程大学 | Preparation method of flexible nano Pd/CuO particle @ foam Cu catalyst |
| CN114192132A (en) * | 2021-12-15 | 2022-03-18 | 合肥工业大学 | Method for simultaneously obtaining nano-porous strip and nano-fiber powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406128A (en) * | 2013-08-13 | 2013-11-27 | 山东大学 | Preparation method of nano-particles with nano-grade porous structure |
| CN104475125A (en) * | 2014-11-06 | 2015-04-01 | 天津大学 | Method for preparing Pd/CuO composite nanometer porous material by using amorphous alloy for dealloying |
| CN106571473A (en) * | 2016-10-26 | 2017-04-19 | 济南大学 | Preparation method of Cu/Cu2O/CuO three-dimensional composite material having hierarchical pore structure |
| CN106890640A (en) * | 2017-01-22 | 2017-06-27 | 南昌大学 | A kind of core shell structure Pd Sn@SiO2Catalyst and preparation method |
-
2017
- 2017-08-31 CN CN201710777031.1A patent/CN107507986A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406128A (en) * | 2013-08-13 | 2013-11-27 | 山东大学 | Preparation method of nano-particles with nano-grade porous structure |
| CN104475125A (en) * | 2014-11-06 | 2015-04-01 | 天津大学 | Method for preparing Pd/CuO composite nanometer porous material by using amorphous alloy for dealloying |
| CN106571473A (en) * | 2016-10-26 | 2017-04-19 | 济南大学 | Preparation method of Cu/Cu2O/CuO three-dimensional composite material having hierarchical pore structure |
| CN106890640A (en) * | 2017-01-22 | 2017-06-27 | 南昌大学 | A kind of core shell structure Pd Sn@SiO2Catalyst and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| ANNA ZALINEEVA等: "Nano-structured Pd-Sn catalysts for alcohol electro-oxidation in alkaline medium", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| WENCE XU等: "Preparation of Nanoporous Pd/CuO by Dealloying and Their Electrocatalysis for Methanol in Alkaline Condition", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923737A (en) * | 2018-09-20 | 2020-03-27 | 天津大学 | Nano porous hydrogen production catalyst and preparation method thereof |
| CN112169809A (en) * | 2020-11-03 | 2021-01-05 | 西安工程大学 | Preparation method of flexible nano Pd/CuO particle @ foam Cu catalyst |
| CN112169809B (en) * | 2020-11-03 | 2024-01-19 | 深圳万知达科技有限公司 | Preparation method of flexible nano Pd/CuO particle@foam Cu catalyst |
| CN114192132A (en) * | 2021-12-15 | 2022-03-18 | 合肥工业大学 | Method for simultaneously obtaining nano-porous strip and nano-fiber powder |
| CN114192132B (en) * | 2021-12-15 | 2024-03-05 | 合肥工业大学 | Method for simultaneously obtaining nano porous strip and nano fiber powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Highly porous nickel@ carbon sponge as a novel type of three-dimensional anode with low cost for high catalytic performance of urea electro-oxidation in alkaline medium | |
| CN102881916B (en) | Gas diffusion electrode carried with double-shell core-shell catalyst and preparation and application thereof | |
| Xu et al. | Pd/C promoted by Au for 2-propanol electrooxidation in alkaline media | |
| CN101332438B (en) | Method for coating noble metal on nano porous gold and prepared catalyst | |
| CN104393307B (en) | Air electrode based on carbon-free Ag-Cu catalyst layer and preparation method thereof | |
| CN107507986A (en) | A kind of PdSn CuO composites of nano-porous structure prepare and application | |
| Miao et al. | Preparation and electrochemistry of Pd–Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell | |
| Niu et al. | A novel nanoporous palladium catalyst for formaldehyde electro-oxidation in alkaline media | |
| CN101997123B (en) | Nano porous alloy fuel battery catalyst and preparation method thereof | |
| CN103165914A (en) | Pt/Au/PdCo/C catalyst, and preparation and application thereof | |
| Hosseini et al. | Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media | |
| Norouzi et al. | Methanol electrooxidation on novel modified carbon paste electrodes with supported poly (isonicotinic acid)(sodium dodecyl sulfate)/Ni-Co electrocatalysts | |
| CN107644999B (en) | Preparation and application of Pd-Sn composite material with nano-porous structure | |
| CN106328963A (en) | Preparation method and application of self-supporting Pd-Ag-Ni ternary metal catalyst | |
| CN100353599C (en) | Carbon carried Pd/oxide composite electric catalyst and preparing process thereof | |
| CN105013483A (en) | Platinum-palladium-platinum/manganese dioxide/graphene laminated catalyst and preparation method therefor | |
| Xu et al. | Electrosynthesis of dendritic palladium supported on Ti/TiO2NTs/Ni/CeO2 as high-performing and stable anode electrocatalyst for methanol electrooxidation | |
| Mert et al. | Ag decorated NiCo catalyst on Ni foam electrodes for electrocatalytic oxidation of methanol | |
| CN109301269A (en) | A kind of PtAgCo/C nanometer flower structure catalysis material and preparation method thereof and application as fuel-cell catalyst | |
| Yang et al. | Preparation of nanoporous Cu/Cu2O composites by anodic oxidation and their electrocatalytic performance towards methanol oxidation | |
| Hosseini et al. | Electro-oxidation of methanol catalysed by porous nanostructured Fe/Pd-Fe electrode in alkaline medium | |
| CN105289591A (en) | Preparation method of nano carbon based loaded two-dimensional noble metal cluster composite material | |
| WO2012004639A1 (en) | Palladium alloy catalysts for fuel cell cathodes and a method of preparing the same | |
| Qiu et al. | Bimetallic Pt–Au thin film electrocatalysts with hierarchical structures for the oxidation of formic acid | |
| CN113130913B (en) | PtNPs/NiNPs/AgNWs/PET plastic electrode and application thereof in construction of fructose fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Applicant after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Applicant before: Tianjin University |
|
| CB02 | Change of applicant information | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171222 |
|
| WD01 | Invention patent application deemed withdrawn after publication |