CN107342427A - A kind of preparation method of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts - Google Patents
A kind of preparation method of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts Download PDFInfo
- Publication number
- CN107342427A CN107342427A CN201710724820.9A CN201710724820A CN107342427A CN 107342427 A CN107342427 A CN 107342427A CN 201710724820 A CN201710724820 A CN 201710724820A CN 107342427 A CN107342427 A CN 107342427A
- Authority
- CN
- China
- Prior art keywords
- preparation
- alloy catalysts
- nanometer alloy
- salt precursor
- ethanol
- 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.)
- Granted
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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of preparation method the invention discloses Direct Ethanol Fuel Cell with Pd/Ag nanometer alloy catalysts.This method is by volume 3~7:1 is added to the water alcohol, stirring, it is separately added into polyvinylpyrrolidone, metal palladium salt precursor, argent salt precursor body and sodium citrate, after 1.5~2.5 h being stirred at 20~25 DEG C, 1.8~12 h are reacted under illumination condition, centrifuge and collect sediment, washing can obtain Pd/Ag nanometer alloy catalysts after drying.The present invention is using polyvinylpyrrolidone as stabilizer and directed agents; by the reduction of alcohol and sodium citrate; one-step synthesis Pd/Ag nanometer alloy catalysts in a mild condition, combined coefficient and yield are not only increased, and the catalyst pattern has controllability; there is preferable catalytic activity to ethanol; it can be used as the catalyst of Direct Ethanol Fuel Cell, and preparation process is simple, it is with short production cycle; it is easy to large-scale production, there is good application prospect.
Description
Technical field
The invention belongs to catalyst technical field, more particularly, to a kind of Direct Ethanol Fuel Cell Pd/Ag nanometers
The preparation method of alloy catalyst.
Background technology
Direct alcohol fuel cell（Direct Alcohol Fuel Cell, DAFC）It is by fuel（Methanol, ethanol etc.）
Chemical energy be converted into a kind of electrochemical reaction appts of electric energy.Because DAFC has, fuel source is abundant, running temperature
It is low, specific energy density is high, storage it is easy to carry the features such as, at present turn into International Fuel Cell research and development new energy technology
One of.But this technology is always to hinder its business also there is no small technical bottleneck, the performance and cost of its catalyst
Two key factors of change process.DAFC belongs to low-temperature fuel cell, and its running temperature is usually no more than 100 DEG C, in this temperature
Under, most transition metal are all very low to the catalytic oxidation activity of hydrogen and organic molecule, thus generally use noble metal platinum（Pt）
As catalyst, however, Pt, as a kind of scarce resource, its price is sufficiently expensive, and is easily poisoned in catalytic reaction process, because
This limits its large-scale application to a certain extent.Palladium（Pd）Catalyst activity is excellent, can be compared favourably with Pt, and price is only
The 1/3 of the latter, this advantageously reduces the cost of catalyst；There are some researches show for organic molecule methanol and ethanol etc. in addition
Pd has more preferable electrocatalysis characteristic than Pt, therefore Pd is considered as one of important alternative materials of Pt.Grinding in monometallic Pd simultaneously
On the basis of studying carefully, another metal is introduced into system, forms Nanoalloy, not only reduces Pd dosage, and introduce
Second of metal is advantageous to the oxidation of strong absorption residue, shows certain cooperative effect, and the catalysis that can improve catalyst is lived
Property, anti-Poisoning, selectivity and stability.In recent years the section for the metallic catalyst of mono-/bis-containing Pd to organic molecule electro-catalysis
It is very active to learn research, especially Pd/Ag alloy nanos catalyst, extensive concern is received in the research of fuel cell.
For example, Chinese patent application 201510569877.7 discloses the preparation of a types of fuel cells nanometer palladium-silver
Method, it prepares PVP solution, AgNO respectively first using ethylene glycol as solvent3The ethylene glycol solution of solution and sodium chloride；To go
Ionized water is solvent, prepares saturated sodium-chloride water solution and PdCl respectively2Solution, by ethylene glycol and the ethylene glycol solution of sodium chloride
Mixing is after stirring 0.9~1.1 h at 155~165 DEG C, then by the AgNO of Part I3Solution is uniformly added dropwise to wherein simultaneously
It was added dropwise in two minutes, then starts simultaneously at the AgNO that Part II is added dropwise3Solution and PVP solution and in 5 min
It is even to be added dropwise；Obtained solution stirs 40~50 min at 155~165 DEG C, cools down at room temperature, obtains nano silver wire；
Deionized water will be added in the obtained solution containing nano silver wire, Fresh is then added dropwise thereto at room temperature
PdCl2Solution, after being added dropwise, continue the h of stirring 11.5~12.5 at room temperature；The solution separation of solid and liquid that will be obtained, is obtained
After product is washed with saturated sodium-chloride water solution, then washed with absolute ethyl alcohol, produce described Pd/Ag alloy nanotubes catalysis
Agent.Chinese patent application 201510194588.3 also discloses that a kind of DMFC palladium on carbon silver nanoparticle is compound to urge
The preparation method of agent, Vulcan XC-72R activated carbons, polyvinylpyrrolidone, PdCl are separately added into three-necked flask2Water
Solution and distilled water, then polyvinylpyrrolidone is set to be completely dissolved and uniformly divide activated carbon by 30 min ultrasonic disperse
It is dispersed in mixed solution；Under conditions of being stirred continuously, the NaOH aqueous solution is added；Continue after stirring 10 min, to three-necked flask
Middle addition AgNO3The aqueous solution；Continue after stirring 10 min, 20 ml are rapidly joined into three-necked flask by 128~256 mg
NaBH4The solution of preparation；Stop stirring after continuously stirring 24 h, and stand 24 h；Filtering, fully washing, and be dried in vacuo
After case dries 6 h at 80 DEG C, that is, obtain palladium on carbon silver nanoparticle composite catalyst.
But technology generally existing severe reaction conditions, the program of these synthesis Pd/Ag Nanoalloys are numerous and diverse at present,
Substantial amounts of reducing agent is added in preparation process, reaction condition is difficult to control in preparation process, or preparation process need to use high energy
The experimental conditions such as radiation, and cause cost higher, and product is uneven and the problems such as industrialized production difficulty, to a certain extent
Limit Pd/Ag Nanoalloys further applying in direct alcohol fuel cell.
Received in addition, having been reported that synthesize palladium-silver using photochemistry and light irradiation synthetic method as radiation source using energy beam in the recent period
Rice alloy catalyst, has the characteristics of simple and easy to do, product uniformity is good, and easily managed with the growth mechanism of the method synthetic material
Solution, thus a kind of new method for the nanocatalyst for being hopeful to control synthesis that there is sizes and pattern as pole.But by
Easily the body of operator is damaged in laser, ultraviolet light and γ radiation, and cost is higher, so having in application
Certain limitation.Therefore, it is necessary to find a kind of safety, cheap, easy-to-use method carrys out the conjunction of controlledly synthesis palladium-silver nanometer
Au catalyst.
The content of the invention
The technical problem to be solved in the present invention is in view of the shortcomings of the prior art, there is provided a kind of process conditions are gentle, pair set
Standby to require low, product uniformity is good, the preparation side of one-step synthesis Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts
Method, use common commercially available incandescent lamp or electricity-saving lamp as light source, in water-alcohol mixed solution system, using polyvinylpyrrolidone as
Stabilizer and directed agents, using alcohol and sodium citrate as reducing agent, Pd/Ag nanometer alloy catalysts are prepared in a mild condition, should
Preparation method is simple, and efficiency high, cost is low, is easy to large-scale production.
It is a further object of the present invention to provide a kind of Pd/Ag nanometer alloy catalysts obtained using the preparation method.
Another object of the present invention is to provide above-mentioned Pd/Ag Nanoalloys as Direct Ethanol Fuel Cell catalyst
The application of aspect.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of Direct Ethanol Fuel Cell preparation method of Pd/Ag nanometer alloy catalysts, comprises the following steps：By volume
3~7:1 is added to the water alcohol, stirring, is separately added into polyvinylpyrrolidone, metal palladium salt precursor, argent salt precursor body
And sodium citrate, after stirring 1.5~2.5 h at 20~25 DEG C, 1.8~12 h are reacted under illumination condition, centrifugation, collect precipitation
Thing, washing can obtain Pd/Ag nanometer alloy catalysts after drying；Wherein polyvinylpyrrolidone：Metal palladium salt precursor：Gold
Belong to silver salt presoma：The mass ratio of sodium citrate is 8~60:0.5~3.5:0.1~6:0~0.5.
Preferably, the polyvinylpyrrolidone：Metal Palladium salt precursor:Argent salt precursor body:The quality of sodium citrate
Than for 9.8~58.92:0.7~3:0.2~5.2:0.1~0.4.
It is highly preferred that the polyvinylpyrrolidone：Metal Palladium salt precursor:Argent salt precursor body:The matter of sodium citrate
Amount is than being 9.82:0.7:1.2:0.4.
Preferably, the volume ratio of alcohol and water is 5:1.
Preferably, the alcohol is ethanol or ethylene glycol.
Preferably, the Metal Palladium salt precursor body is palladium nitrate.
Preferably, the argent salt precursor body is silver nitrate.
Preferably, the illumination condition is radiation of visible light.
Preferably, the light source of the illumination is incandescent lamp or electricity-saving lamp.
It is highly preferred that the light source of the illumination is incandescent lamp, illumination condition is the h of 200 W illumination 2.
Preferably, is absolute ethyl alcohol and deionized water centrifuge washing 2 times is respectively adopted in wash conditions.
Preferably, the drying is vacuum drying, and drying temperature is 35~45 DEG C, and drying time is 12~48 h.
It is highly preferred that the drying is dried in vacuo 48 h under the conditions of being 35 DEG C.
The Pd/Ag nanometer alloy catalysts and Pd/Ag nanometer alloy catalysts being prepared by the above method are in conduct
Application in terms of Direct Ethanol Fuel Cell catalyst is also within protection scope of the present invention.
Compared with prior art, the present invention has advantage following prominent：
1st, present invention Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts obtained in normal temperature and pressure environment, technique
Mild condition, low for equipment requirements, with short production cycle, product uniformity is good；
2nd, the reduction of the invention by alcohol and sodium citrate, one-step synthesis Pd/Ag nanometer alloy catalysts, cost is cheap,
Environment-friendly, operating process is simple and easy to do；
3rd, the high-energy radiations such as laser, ultraviolet light and γ radiation compensate for operation as supplementary means using general visible source
The body of person damages the deficiency higher with cost, and it is higher to overcome instrument and equipment requirement, the limitation such as producing cost costliness；
4th, the present invention belongs to the Pd/Ag of the dosage of precursor concentration and reducing agent, one-step synthesis different-shape and size by changing
Nanometer alloy catalyst, realize pattern and the size regulation and control of the nanometer alloy catalyst；
5th, the Pd/Ag Nanoalloys modified electrode obtained by the present invention has good electro-catalysis to live to ethanol in the basic conditions
Property, it can be used as Direct Ethanol Fuel Cell catalyst, have a good application prospect；
6th, the yield of nano Pd particle/Ag nanometer alloy catalysts prepared by the present invention is high, is 90%~96%, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 1.
Fig. 2 is the EDS figures of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope photo of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope photo of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 2.
Fig. 5 is the transmission electron microscope photo of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 3.
Fig. 6 is the transmission electron microscope photo of the Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 4.
Fig. 7 illustrates Pd/Ag nanometer alloy catalysts prepared by the embodiment of the present invention 1,2,3,4 to oxidation of ethanol
Electro catalytic activity（Electrode surface nano Pd particle/μ the g/cm of Ag Nanoalloys carrying capacity 482, electrolyte is the 1 of 1 mol/L ethanol
Mol/L KOH solutions, the mV/s of sweep speed 50, three-electrode system：With drop coating nano Pd particle/Ag Nanoalloy modified glassy carbon electrodes
（Pd/GCE）For working electrode, saturated calomel electrode（SCE）For reference electrode, platinum electrode is auxiliary electrode）；In figure, a, b,
C, d represents the catalyst prepared by embodiment 1-4 respectively.
Embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment（Utilize the electro catalytic activity of ethanol
Evaluate the catalytic performance of Pd/Ag Nanoalloys）.Following examples are the preferable embodiment of the present invention, but not to the present invention
Protection domain limit in any form.The present invention mainly illustrates that the catalyst and the application based on the catalyst are thought
Think, in embodiment the replacement of simple parameter can not be repeated one by one in embodiment, but and be not so limited the present invention, it is other
Any Spirit Essence without departing from the present invention with made under principle change, modification, replacement, combine, simplification, should be considered as equivalent
Substitute mode, all should include within the scope of the present invention.
Unless stated otherwise, the reagent of the invention used, method and apparatus for the art conventional reagent, method and are set
It is standby.Unless stated otherwise, following examples agents useful for same and material are purchased in market.
Embodiment 1
1st, preparation method
A kind of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts, are prepared by following methods：
（1）Add 4 mL water and 20 mL ethanol successively in reaction vessel, stirring obtains water-ethanol mixed solution system；
（2）By 0.007 g Pd (NO3)2Powder, 0.012 g AgNO3, 0.004 g sodium citrates and 0.0982 g PVP add
Enter into water-ethanol mixed solution system, the solution prepared is placed on into constant temperature blender with magnetic force stirs 2 h in 20 DEG C；
（3）Reaction solution after stirring is placed in the illumination reaction case of designed, designed, is placed in the common commercially available white of 200 W
The h of parallel radiation 2 under vehement light；
（4）The black precipitate of gained is centrifuged, and is placed in 35 with absolute ethyl alcohol and deionized water centrifuge washing 2 times respectively
DEG C vacuum drying oven in dry 48 h, as Pd/Ag nanometer alloy catalysts material.
The yield of Pd/Ag nanometer alloy catalysts prepared by this method is 96%.
2nd, the product feature and physicochemical property of Pd/Ag nanometer alloy catalysts
Transmission electron microscope photo（TEM）With EDS by company of Jeol Ltd. JEOL-2010 type transmission electron microscopies
Mirror obtains；The X-ray diffraction of sample（XRD）Collection of illustrative plates is by Beijing Pu Xi all purpose instruments Co., Ltd XD-3 type X-ray diffraction analysis
Instrument determines（Cu targets, Ka radiation, the nm of λ=0.15406）, the kV of operating voltage 36, the mA of tube current 30, cyclic voltammetry curve（CV）By
Shanghai Chen Hua Instrument Ltd. electrochemical workstation CHI-660E is obtained.
（1）The X-ray diffraction structure of gained Pd/Ag nanometer alloy catalysts is face-centred cubic structure.As shown in figure 1, receive
There are 5 diffraction maximums respectively at 40.13 °, 46.44 °, 68.08 °, 81.98 ° and 86.30 ° in the rice Pd θ of the angle of diffraction 2, mutually should be
Metal Pd simple substance diffraction crystal face（111）、（200）、（220）、（311）With（222）Characteristic peak.Pd/Ag Nanoalloys are due to having
Ag presence, the position of its diffraction maximum is set between Pd and Ag diffraction maximum, to show the life of alloy there occurs some movement
Into.
（2）As shown in Fig. 2 the EDX spectrograms of the catalyst show the presence of two kinds of elements of Pd and Ag in alloy.
（3）The microscopic appearance of the catalyst is as shown in figure 3, be in nano thread structure.
（4）The electro catalytic activity such as Fig. 7 of the Pd/Ag nanometer alloy catalysts of preparation to oxidation of ethanol（a）It is shown：To ethanol
The initial oxidation potential of oxidation is -0.68V, and in forward potential scanning, nano Pd particle modified glassy carbon electrode is in ethanol solution
Electric current gradually increases, and occurs first oxidation peak I near -0.20 V；When negative sense scans, electric current is being gradually reduced, until
Occur second oxidation peak II near -0.38 V；The electric current of oxidation peak I is 1.22 × 10-3 A。
Embodiment 2
1st, preparation method
A kind of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts, are prepared by following methods：
（1）Add 4 mL water and 20 mL ethanol successively in reaction vessel, stirring obtains water-ethanol mixed solution system；
（2）By 0.007 g Pd (NO3)2Powder, 0.005 g AgNO3, 0.001 g sodium citrates and 0.098 g PVP add
Into water-ethanol mixed solution system, the solution prepared is placed on constant temperature blender with magnetic force and stirs 2 h in 23 DEG C；
（3）Reaction solution after stirring is placed in the illumination reaction case of designed, designed, is placed in the common commercially available white of 200 W
The h of parallel radiation 2 under vehement light；
（4）The black precipitate of gained is centrifuged, and is placed in 45 with absolute ethyl alcohol and deionized water centrifuge washing 2 times respectively
DEG C vacuum drying oven in dry 12 h, as Pd/Ag nanometer alloy catalysts material.
The yield of Pd/Ag nanometer alloy catalysts prepared by this method is 93%.
2nd, the product feature and physicochemical property of Pd/Ag nanometer alloy catalysts
The experiment material of product feature and physicochemical property is with experimental method with embodiment 1.
（1）The microscopic appearance of gained Pd/Ag nanometer alloy catalysts is as shown in figure 4, be in nano wire pattern.
（2）The electro catalytic activity such as Fig. 7 of the Pd/Ag nanometer alloy catalysts of preparation to oxidation of ethanol（b）It is shown：To ethanol
The initial oxidation potential of oxidation is -0.65V, and in forward potential scanning, nano Pd particle modified glassy carbon electrode is in ethanol solution
Electric current gradually increases, and occurs first oxidation peak I near -0.28 V；When negative sense scans, electric current is being gradually reduced, until
Occur second oxidation peak II near -0.41 V；The electric current of oxidation peak I is 4.56 × 10-4 A。
Embodiment 3
1st, preparation method
A kind of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts, are prepared by following methods：
（1）Add 6 mL water and 12 mL ethylene glycol successively in reaction vessel, stirring obtains water-alcohol mixed solution system；
（2）By 0.007 g Pd (NO3)2、0.002 g AgNO3, 0.004 g sodium citrates and 0.098 g PVP be added to
In water-ethanol mixed solution system, the solution prepared is placed on constant temperature blender with magnetic force and stirs 2 h in 25 DEG C；
（3）Reaction solution after stirring is placed in the illumination reaction case of designed, designed, is placed in 15 W common commercially available section
The h of parallel radiation 12 under energy light；
（4）The black precipitate of gained is centrifuged, and is placed in 40 with absolute ethyl alcohol and deionized water centrifuge washing 2 times respectively
DEG C vacuum drying oven in dry 24 h, as Pd/Ag nanometer alloy catalysts material.
The yield of Pd/Ag nanometer alloy catalysts prepared by this method is 93%.
2nd, the product feature and physicochemical property of Pd/Ag nanometer alloy catalysts
The experiment material of product feature and physicochemical property is with experimental method with embodiment 1.
（1）The microscopic appearance of gained Pd/Ag nanometer alloy catalysts is as shown in figure 5, be in granular form pattern.
（2）The electro catalytic activity such as Fig. 7 of the Pd/Ag nanometer alloy catalysts of preparation to oxidation of ethanol（c）It is shown：To ethanol
The initial oxidation potential of oxidation is -0.67V, and in forward potential scanning, nano Pd particle/Ag modified glassy carbon electrodes are in ethanol solution
Electric current gradually increase, occur first oxidation peak I near -0.20 V；When negative sense scans, electric current is being gradually reduced, directly
Extremely occur second oxidation peak II near -0.36 V；The electric current of oxidation peak I is 9.43 × 10-4 A。
Embodiment 4
1st, preparation method
A kind of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts, are prepared by following methods：
（1）Add 8 mL water and 40 mL ethanol successively in reaction vessel, stirring obtains water-ethanol mixed solution system；
（2）By 0.030 g Pd (NO3)2Powder, 0.052 g AgNO3It is molten that water-ethanol mixing is added to 0.5892 g PVP
In liquid system, the solution prepared is placed on constant temperature blender with magnetic force and stirs 2 h in 25 DEG C；
（3）Reaction solution after stirring is placed in the illumination reaction case of designed, designed, is placed in the common commercially available white of 200 W
The h of parallel radiation 2 under vehement light；
（4）The black precipitate of gained is centrifuged, and is washed with ethanol and deionized water and repeatedly, is placed in 40 DEG C of vacuum drying oven
The middle h of drying 24, as Pd/Ag nanometer alloy catalysts material.
The yield of Pd/Ag nanometer alloy catalysts prepared by this method is 90%.
2nd, the product feature and physicochemical property of Pd/Ag nanometer alloy catalysts
The experiment material of product feature and physicochemical property is with experimental method with embodiment 1.
（1）The microscopic appearance of gained Pd/Ag nanometer alloy catalysts is as shown in fig. 6, be in cluster-shaped.
（2）The electro catalytic activity such as Fig. 7 of the Pd/Ag nanometer alloy catalysts of preparation to oxidation of ethanol（d）It is shown：To ethanol
The initial oxidation potential of oxidation is -0.56 V, and in forward potential scanning, nano Pd particle modified glassy carbon electrode is in ethanol solution
Electric current gradually increases, and occurs first oxidation peak I near -0.28 V；When negative sense scans, electric current is being gradually reduced, until
Occur second oxidation peak II near -0.39 V；The electric current of oxidation peak I is 4.06 × 10-4 A。
To sum up, the Pd/Ag nanometer alloy catalysts of the present embodiment are closed with embodiment 1, embodiment 2 and embodiment 3 respectively
Into Pd/Ag nanometer alloy catalysts the electrocatalysis characteristic of ethanol is contrasted, test result indicates that：With embodiment 1-3 systems
Standby nano wire is compared with nano particle, and cluster-shaped Pd/Ag nanometer alloy catalysts substantially reduce to the electro catalytic activity of ethanol,
Catalysis of the Pd/Ag nanometer alloy catalysts for illustrating to be prepared under conditions of no addition reducing agent sodium citrate to ethanol
Active obvious reduction.
Optimization of process conditions prepared by the Pd/Ag nanometer alloy catalysts of embodiment 5
1st, the water-ethanol mixed solution of different proportion is to preparing the influences of Pd/Ag nanometer alloy catalysts
By ethanol and water respectively by volume 1:10、1:7、1:5、1:3、1:1、3:1、5:1、7:1、10:1 adds reaction vessel
In, stirring obtains the water-ethanol mixed solution system of different proportion, and other steps are same as Example 1, investigate different proportion
Water-ethanol mixed solution is to preparing the influences of Pd/Ag nanometer alloy catalysts.
Test result indicates that the volume ratio of ethanol and water is 3~7:When 1, prepared Pd/Ag nanometer alloy catalysts
Yield and catalytic activity are higher, and wherein the volume ratio of ethanol and water is 5:When 1, prepared Pd/Ag nanometer alloy catalysts
Efficiency and catalytic activity highest, and when the volume ratio of ethanol and water is 1:When 1~10, by test result indicates that, Pd/Ag receives
The yield of rice alloy catalyst only has 40% or so.
2nd, different illumination conditions are to preparing the influences of Pd/Ag nanometer alloy catalysts
Common commercially available incandescent light is used as light source, by step in embodiment 1（3）Reaction solution be respectively placed in 15W 1h, 15W
2h、15W 4h、15W 8h、15W 12h、15W 16h、100W 1h、100W 2h、100W 4h、100W 5h、200W 1h、200W
2h, 200W 4h illumination condition are reacted, and other steps are same as Example 1, investigate different illumination conditions to preparing Pd/
The influence of Ag nanometer alloy catalysts.
Test result indicates that under conditions of 200W illumination 2h Pd/Ag nanometer alloy catalysts yield highest, acquisition
Product is best to the electrocatalysis characteristic of ethanol.
Claims (10)
1. a kind of Direct Ethanol Fuel Cell preparation method of Pd/Ag nanometer alloy catalysts, it is characterised in that by volume
3~7:1 is added to the water alcohol, stirring, is separately added into polyvinylpyrrolidone, metal palladium salt precursor, argent salt precursor body
And sodium citrate, after stirring 1.5~2.5 h at 20~25 DEG C, 1.8~12 h are reacted under illumination condition, centrifugation, collect precipitation
Thing, washing obtain Pd/Ag nanometer alloy catalysts after drying；Wherein polyvinylpyrrolidone：Metal palladium salt precursor：Argent
Salt precursor body：The mass ratio of sodium citrate is 8~60:0.5~3.5:0.1~6:0~0.5.
2. preparation method according to claim 1, it is characterised in that the polyvinylpyrrolidone：Metal Palladium salt precursor：
Argent salt precursor body：The mass ratio of sodium citrate is 9.8~58.92:0.7~3:0.2~5.2:0.1~0.4.
3. preparation method according to claim 1, it is characterised in that the volume ratio of alcohol and water is 5:1.
4. preparation method according to claim 1, it is characterised in that the alcohol is ethanol or ethylene glycol.
5. preparation method according to claim 1, it is characterised in that the Metal Palladium salt precursor body is palladium nitrate；It is described
Argent salt precursor body is silver nitrate.
6. preparation method according to claim 1, it is characterised in that the illumination condition is radiation of visible light.
7. preparation method according to claim 6, it is characterised in that the light source of the illumination is incandescent lamp or electricity-saving lamp.
8. preparation method according to claim 1, it is characterised in that the condition of the drying is 35~45 DEG C of vacuum drying
12~48 h.
9. the Pd/Ag nanometer alloy catalysts that the preparation method described in any one of claim 1~8 obtains.
10. the Pd/Ag nanometer alloy catalysts described in claim 9 are in terms of as Direct Ethanol Fuel Cell catalyst
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710724820.9A CN107342427B (en) | 2017-08-22 | 2017-08-22 | Preparation method of Pd/Ag nano alloy catalyst for direct ethanol fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710724820.9A CN107342427B (en) | 2017-08-22 | 2017-08-22 | Preparation method of Pd/Ag nano alloy catalyst for direct ethanol fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107342427A true CN107342427A (en) | 2017-11-10 |
| CN107342427B CN107342427B (en) | 2020-04-28 |
Family
ID=60215523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710724820.9A Active CN107342427B (en) | 2017-08-22 | 2017-08-22 | Preparation method of Pd/Ag nano alloy catalyst for direct ethanol fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107342427B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598508A (en) * | 2018-05-24 | 2018-09-28 | 西北工业大学 | The processing method of AgPd Nanoalloy formates oxidation catalysts and the surfactant-free of raising catalytic activity |
| CN108666590A (en) * | 2018-04-27 | 2018-10-16 | 南京师范大学 | The preparation method and its resulting materials of a kind of tree crown shape multistage PdAg nanodendrites and application |
| CN108736022A (en) * | 2018-05-07 | 2018-11-02 | 南京师范大学 | The preparation method and its resulting materials of a kind of hetero-junctions PdAg nano wires and application |
| CN109971172A (en) * | 2019-03-18 | 2019-07-05 | 岭南师范学院 | A kind of one one step preparation method of palladium-silver/polyaniline nano-composite material and application |
| CN112421058A (en) * | 2020-11-26 | 2021-02-26 | 西北工业大学 | PdAgF nano alloy formate oxidation catalyst and preparation and use methods thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682040A (en) * | 2007-06-12 | 2010-03-24 | 佳能株式会社 | Method of producing fuel cell catalyst layer |
| CN102794172A (en) * | 2012-07-26 | 2012-11-28 | 安徽理工大学 | Photosynthesis preparation method of nano palladium catalyst |
| CN105073254A (en) * | 2013-02-25 | 2015-11-18 | 日产自动车株式会社 | Catalyst particles for fuel cells and method for producing same |
| CN105594035A (en) * | 2013-08-09 | 2016-05-18 | 日产自动车株式会社 | Catalyst particles, electrocatalyst using the same, electrolyte membrane-electrode assembly, and fuel cell using the catalyst particles |
-
2017
- 2017-08-22 CN CN201710724820.9A patent/CN107342427B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682040A (en) * | 2007-06-12 | 2010-03-24 | 佳能株式会社 | Method of producing fuel cell catalyst layer |
| CN102794172A (en) * | 2012-07-26 | 2012-11-28 | 安徽理工大学 | Photosynthesis preparation method of nano palladium catalyst |
| CN105073254A (en) * | 2013-02-25 | 2015-11-18 | 日产自动车株式会社 | Catalyst particles for fuel cells and method for producing same |
| CN105594035A (en) * | 2013-08-09 | 2016-05-18 | 日产自动车株式会社 | Catalyst particles, electrocatalyst using the same, electrolyte membrane-electrode assembly, and fuel cell using the catalyst particles |
Non-Patent Citations (3)
| Title |
|---|
| SHAOFANG FU，ET AL.: "Facile One-Step Synthesis of Three-Dimensional Pd-Ag Bimetallic Alloy Networks and Their Electrocatalytic Activity toward Ethanol Oxidation", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 刘时杰: "《铂族金属冶金学 第1版》", 30 June 2013 * |
| 谭德新，等: "多重栾晶钯颗粒的可见光简易合成及对乙醇的电催化氧化", 《无机化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666590A (en) * | 2018-04-27 | 2018-10-16 | 南京师范大学 | The preparation method and its resulting materials of a kind of tree crown shape multistage PdAg nanodendrites and application |
| CN108666590B (en) * | 2018-04-27 | 2020-05-05 | 南京师范大学 | Preparation method of crown-shaped multistage PdAg nano dendrites, obtained material and application thereof |
| CN108736022A (en) * | 2018-05-07 | 2018-11-02 | 南京师范大学 | The preparation method and its resulting materials of a kind of hetero-junctions PdAg nano wires and application |
| CN108736022B (en) * | 2018-05-07 | 2020-04-03 | 南京师范大学 | Preparation method of heterojunction PdAg nanowire, material obtained by preparation method and application of heterojunction PdAg nanowire |
| CN108598508A (en) * | 2018-05-24 | 2018-09-28 | 西北工业大学 | The processing method of AgPd Nanoalloy formates oxidation catalysts and the surfactant-free of raising catalytic activity |
| CN108598508B (en) * | 2018-05-24 | 2020-09-22 | 西北工业大学 | AgPd nano-alloy formate oxidation catalyst and surfactant-free treatment method for improving catalytic activity |
| CN109971172A (en) * | 2019-03-18 | 2019-07-05 | 岭南师范学院 | A kind of one one step preparation method of palladium-silver/polyaniline nano-composite material and application |
| CN109971172B (en) * | 2019-03-18 | 2021-04-02 | 岭南师范学院 | One-step preparation method and application of palladium-silver alloy/polyaniline nanocomposite |
| CN112421058A (en) * | 2020-11-26 | 2021-02-26 | 西北工业大学 | PdAgF nano alloy formate oxidation catalyst and preparation and use methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107342427B (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Ultrasonic-assisted synthesis of N-doped graphene-supported binary PdAu nanoflowers for enhanced electro-oxidation of ethylene glycol and glycerol | |
| CN107342427A (en) | A kind of preparation method of Direct Ethanol Fuel Cell Pd/Ag nanometer alloy catalysts | |
| Hu et al. | Photo-responsive metal/semiconductor hybrid nanostructure: a promising electrocatalyst for solar light enhanced fuel cell reaction | |
| Jiang et al. | Trimetallic PtSnRh wavy nanowires as efficient nanoelectrocatalysts for alcohol electrooxidation | |
| Hu et al. | 2D/1D heterostructure of g-C3N4 nanosheets/CdS nanowires as effective photo-activated support for photoelectrocatalytic oxidation of methanol | |
| Lan et al. | Efficient electrochemical ethanol-to-CO2 conversion at rhodium and bismuth hydroxide interfaces | |
| CN109449466A (en) | Preparation method, the preparation method of membrane electrode anode catalyst layer of membrane electrode | |
| CN108745340A (en) | A kind of preparation method and application of carbon load bismuth nanoparticle catalyst | |
| Zhang et al. | Novel synthesis of PtPd nanoparticles with good electrocatalytic activity and durability | |
| CN102847534B (en) | Light-driven regulation preparation method and electrocatalysis activity of nanometer material | |
| CN105845948B (en) | A kind of preparation method of flower-shaped copper/cupric oxide Micron-nano composites carried noble metal fuel-cell catalyst | |
| Xiong et al. | Concave Pd–Ru nanocubes bounded with high active area for boosting ethylene glycol electrooxidation | |
| Hernández et al. | Formic acid oxidation on AuPd core-shell electrocatalysts: Effect of surface electronic structure | |
| CN105789639A (en) | Method for preparing Au-cluster/carbon nano tube composite catalyst | |
| Xu et al. | Surface plasmon enhanced ethylene glycol electrooxidation based on hollow platinum-silver nanodendrites structures | |
| Han et al. | Polyoxometallate-stabilized Pt–Ru catalysts on multiwalled carbon nanotubes: influence of preparation conditions on the performance of direct methanol fuel cells | |
| CN109935840A (en) | A kind of preparation method of fuel cell Pt base catalyst | |
| Shi et al. | Electrocatalytic activity and stability of carbon nanotubes-supported Pt-on-Au, Pd-on-Au, Pt-on-Pd-on-Au, Pt-on-Pd, and Pd-on-Pt catalysts for methanol oxidation reaction | |
| Jin et al. | Modification of Ag nanoparticles/reduced graphene oxide nanocomposites with a small amount of Au for glycerol oxidation | |
| Wang et al. | Electrochemical synthesis of Pt nanoparticles on ZrO2/MWCNTs hybrid with high electrocatalytic performance for methanol oxidation | |
| Beydaghi et al. | Preparation and Characterization of Electrocatalyst Nanoparticles for Direct Methanol Fuel Cell Applications Using β-D-glucose as Protection Agent | |
| Duan et al. | Bowl-like carbon supported AuPd and phosphotungstic acid composite for electrooxidation of ethylene glycol and glycerol | |
| Mao et al. | Facile preparation of Cu@ Pt/rGO hybrids and their electrocatalytic activities for methanol oxidation | |
| Altuner et al. | Ternary/quaternary nanomaterials for direct alcohol fuel cells | |
| Song et al. | Visible-light-driven trimetallic Pt-Ag-Ni alloy nanoparticles for efficient nanoelectrocatalytic oxidation of alcohols |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |