CN107482234A - A kind of preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope - Google Patents
A kind of preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope Download PDFInfo
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- CN107482234A CN107482234A CN201710740603.9A CN201710740603A CN107482234A CN 107482234 A CN107482234 A CN 107482234A CN 201710740603 A CN201710740603 A CN 201710740603A CN 107482234 A CN107482234 A CN 107482234A
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- 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
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- 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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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]
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- 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 sulphur, nitrogen, the carbon material supported palladium-copper alloy fuel-cell catalyst of cobalt codope preparation method, belong to the preparing technical field of fuel battery nano composite catalyst, specifically include and prepare sulphur, nitrogen, the preparation of cobalt codope carbon material carrier and grade step in supported on carriers palladium-copper alloy activearm, there is good synergy between carrier and alloy active component.Sulphur, nitrogen, cobalt codope carbon material play an important roll as fuel-cell catalyst carrier to improving catalyst activity, on the one hand copper has played promoting catalysis as transition metal, improve the activity of noble metal catalyst, on the other hand the dosage of noble metal catalyst is reduced, the cost of fuel-cell catalyst is reduced, therefore is had broad application prospects.
Description
Technical field
The invention belongs to the preparing technical field of fuel battery nano composite catalyst, and in particular to a kind of sulphur, nitrogen, cobalt are common
Adulterate the preparation method of carbon material supported palladium-copper alloy fuel-cell catalyst.
Background technology
It is excellent that DMFC has that operating temperature is moderate, energy density is high and liquid fuel supply mode is simple etc.
Point, it is the electrical source of power for most holding promise for electric automobile and various movable equipments.The property of DMFC at present
Can and cost can not still fully meet the requirements of commercial applications, a big chunk reason be insufficient catalytic activity and it is high into
This anode catalyst.Therefore, the catalyst for finding high activity, high stability and low cost is necessity of commercializing fuel cells
Selection.
According to the skin effect of catalyst, it is desirable to meet the requirement of low-cost high-efficiency, first have to make active component abundant
Micronized is realized, on this basis, catalyst particle, which is fixed on suitable carrier, can make catalyst utilization reach maximum
Change.Therefore, it is the key factor for influenceing catalyst activity to select appropriate carrier, and carrier also just turns into crucial group in catalyst
/ mono-.Domestic and international recent study finds that the carbon material of metal and N codopes has good chemical property, enriches hair
Such material system is opened up, is expected to obtain preferable electrochemistry carbon material carrier.
Using carbon material as carrier, generally require to introduce dressing agent in carrier surface, play to catalyst-loaded activearm
The anchorage effect divided, so as to improve dispersiveness of the catalyst activity component in carrier surface, but this physical modification acts on
It is easy to decay in cell operations so that carrier interface absorption stability declines, and causes battery life to decline, and
This method for introducing dressing agent will also increase process complexity and material cost.
Nano material with shell structurre shows that huge application potential, such as Shell Materials have in every field
Higher specific surface area, its abundant hole can also promote mass transfer and electronics to shift, and be advantageous to improve catalyst
Activity.
The content of the invention
Present invention solves the technical problem that it there is provided the carbon material supported palladium-copper alloy fuel of a kind of sulphur, nitrogen, cobalt codope
The preparation method of cell catalyst, so as to effectively improve the performance of anode catalysts for direct methanol fuel cell.
The present invention adopts the following technical scheme that a kind of sulphur, nitrogen, cobalt codope are carbon material supported to solve above-mentioned technical problem
The preparation method of palladium-copper alloy fuel-cell catalyst, it is characterised in that concretely comprise the following steps：
（1）The mercaptan of 2- amino -1,3,5- triazines -4,6- two and mass concentration is super for 37% formalin and deionized water warp
The uniform wiring solution-forming of sound dispersion mixing, adds Co (CH3COO)4·H2O simultaneously is uniformly mixed to obtain suspension, by what is obtained
Suspension is transferred in autoclave and sealed, and 8h is reacted in 190 DEG C, reaction naturally cools to room temperature after terminating, by what is obtained
Product be washed with deionized until filtrate become colorless, put into vacuum drying chamber in 80 DEG C dry to constant weight, then in N2
3h is calcined in 750 DEG C obtain double-deck ghost spherical structure sulphur, nitrogen, cobalt codope carbon material under atmosphere；
（2）By step（1）Obtained sulphur, nitrogen, cobalt codope carbon material are scattered in ethylene glycol, and ultrasonic agitation 2h is disperseed
Liquid, PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and CuSO4·5H2O, stir to well mixed and obtain mixed liquor,
Obtained mixed liquor is transferred in autoclave and sealed, 6h is reacted in 160 DEG C, reaction naturally cools to room temperature after terminating,
Then product is centrifuged, and be washed with deionized, put into vacuum drying chamber drying to constant weight and obtain sulphur, nitrogen, cobalt codope
Carbon material supported ghost spherical structure palladium-copper alloy fuel-cell catalyst.
Further preferably, step（1）Described in 2- amino -1,3,5- triazines -4,6- two mercaptan, mass concentration be 37%
Formalin and Co (CH3COO)4·H2The O mass ratio that feeds intake is 1:6:10.
Further preferably, step（2）Described in sulphur, nitrogen, cobalt codope carbon material and CuSO4·5H2The O mass ratio that feeds intake
For 2:1, PdCl2With CuSO4·5H2O molar ratio is 5:8.
The present invention has the advantages that compared with prior art：
1st, the present invention innovates based on the appearance structure of fuel-cell catalyst carrier, has synthesized first spherical with double-deck ghost
Sulphur, nitrogen, the cobalt codope carbon material of structure, and as fuel-cell catalyst carrier, the sulphur of double-deck ghost spherical structure,
Nitrogen, cobalt codope carbon material carrier can provide three-phase for electrode reaction（Solid-liquid-gas）Area, passage is provided for electrolyte transmission,
And then the specific surface area of catalyst is improved, increase the catalytic activity of catalyst；
2nd, sulphur, nitrogen, cobalt codope, which act on, causes carbon material to have more catalytic active sites, is risen with the copper one in palladium-copper alloy
Wave the good cooperative effect to noble metal, effectively increase the electrocatalysis characteristic of noble metal, reduce noble metal catalyst into
This, improves the utilization rate of noble metal, has good prospect in the anode catalysis material application of fuel cell；
3rd, sulphur, nitrogen, cobalt codope, which act on, causes carbon material carrier surface property to vary widely, to the anchor of metal catalytic component
Gu effect enhancing, in the case of no added dressing agent, it is possible to achieve to the uniform load of metal catalytic component, substantially increase
The activity and stability of catalyst.
Brief description of the drawings
Fig. 1 is the SEM figures that sulphur, nitrogen, cobalt codope carbon material is made in embodiment 1；
Fig. 2 is the TEM figures that load palladium-copper alloy fuel-cell catalyst is made in embodiment 1；
Fig. 3 is the XRD that palladium-copper alloy is made in embodiment 1；
Fig. 4 is that the electrochemistry of catalyst in embodiment 1 and comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 is followed
Ring volt-ampere test curve.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
By the formalin and 40mL of the mercaptan of 0.01g 2- amino -1,3,5- triazines -4,6- two and 0.06g mass concentrations for 37%
Deionized water is well mixed wiring solution-forming through ultrasonic disperse, adds 0.1g Co (CH3COO)4·H2O is simultaneously uniformly mixed
To suspension；Obtained suspension is transferred in autoclave and sealed, 8h is reacted in 190 DEG C, reaction is naturally cold after terminating
But to room temperature；Obtained product is washed with deionized until filtrate becomes colorless, put into vacuum drying chamber dry in 80 DEG C
It is dry to constant weight, then in N23h is calcined in 750 DEG C obtain sulphur, nitrogen, cobalt codope carbon material under atmosphere；By obtained sulphur, nitrogen, cobalt
Codope carbon material 40mg is scattered in 20mL ethylene glycol, and ultrasonic agitation 2h obtains dispersion liquid；By in obtained dispersion liquid successively
Add 2.5mL 20mM PdCl2The aqueous solution and 20mg CuSO4·5H2O, stir to well mixed and obtain mixed liquor, by made from
Mixed liquor is transferred in autoclave and sealed, and 6h is reacted in 160 DEG C, and reaction naturally cools to room temperature after terminating, then will production
Thing centrifuges, and is washed with deionized, and puts into vacuum drying chamber to dry and obtains sulphur, nitrogen, cobalt codope carbon material to constant weight and bear
Carry palladium-copper alloy fuel-cell catalyst.
Obtained sulphur, nitrogen, cobalt codope carbon material are double-deck ghost spherical structure as shown in Figure 1, this special material
Composition and appearance structure provide passage for the transmission of electrolyte, and then improve the specific surface area of catalyst, are effectively increased electro-catalysis
The catalytic activity of agent.
As shown in Figure 2 it is obtained load palladium-copper alloy fuel-cell catalyst in PdCu alloy hollows nano particle well
It is dispersed in sulphur, nitrogen, on cobalt codope carbon material carrier, this is due to the electronics that Co-S-N-C avtive spots change carrier surface
Structure, the surface nature of carrier is further have adjusted, so as to optimize anchorage effect of the carrier to noble metal nano particles, in nothing
In the case of modification, be still advantageous to the nucleation of noble metal nano particles and disperse, be advantageous to the raising of catalyst performance.
Fig. 3 XRD spectrum illustrates the formation of PdCu alloys.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
Comparative example 1
0.01g melamines and 0.05g mass concentrations are mixed for 37% formalin with 40mL deionized waters through ultrasonic disperse
Uniform wiring solution-forming, then add 0.1g Co (CH3COO)4·H2O simultaneously is uniformly mixed to obtain suspension；It is outstanding by what is obtained
Turbid is transferred in autoclave and sealed, and 6h is reacted in 180 DEG C, and reaction naturally cools to room temperature after terminating；The production that will be obtained
Thing is washed with deionized until filtrate becomes colorless, and is put into vacuum drying chamber and is dried in 80 DEG C to constant weight, then in N2Gas
2h is calcined in 800 DEG C obtain nitrogen, cobalt codope carbon material under atmosphere；Obtained nitrogen, cobalt codope carbon material 40mg are scattered in
In 20mL ethylene glycol, add 50mg sodium glutamates and obtain dispersion liquid as dressing agent, ultrasonic agitation 2h；By in obtained dispersion liquid
Sequentially add 2.5mL 20mM PdCl2The aqueous solution and 20mg CuSO4·5H2O, stir to well mixed and obtain mixed liquor, will
To mixed liquor be transferred in autoclave and seal, 6h are reacted in 160 DEG C, reaction naturally cools to room temperature after terminating, then
Product is centrifuged, and is washed with deionized, puts into vacuum drying chamber and dries to constant weight obtains nitrogen, cobalt codope carbon material is born
Carry palladium-copper alloy fuel-cell catalyst.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
Comparative example 2
Main preparation flow is identical with comparative example 1, is not add sodium glutamate as modification with the difference of comparative example 1
Agent.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
Comparative example 3
Take Xc-72 carbon materials to be scattered in for carrier 40mg in 20mL ethylene glycol, add 50mg sodium glutamates as dressing agent, ultrasound
Stirring 2h obtains dispersion liquid；2.5mL 20mM PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and 20mg CuSO4·
5H2O, stir to well mixed and obtain mixed liquor, obtained mixed liquor is transferred in autoclave and sealed, it is anti-in 160 DEG C
Answer 6h, reaction to naturally cool to room temperature after terminating, then centrifuge product, and be washed with deionized, put to vacuum drying chamber
Middle drying to constant weight obtains the carbon material supported palladium-copper alloy fuel-cell catalysts of Xc-72.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
Comparative example 4
By the formalin and 40mL of the mercaptan of 0.01g 2- amino -1,3,5- triazines -4,6- two and 0.06g mass concentrations for 37%
Deionized water is well mixed wiring solution-forming through ultrasonic disperse, adds 0.1g Co (CH3COO)4·H2O is simultaneously uniformly mixed
To suspension；Obtained suspension is transferred in autoclave and sealed, 8h is reacted in 190 DEG C, reaction is naturally cold after terminating
But to room temperature；Obtained product is washed with deionized until filtrate becomes colorless, put into vacuum drying chamber dry in 80 DEG C
It is dry to constant weight, then in N23h is calcined in 750 DEG C obtain sulphur, nitrogen, cobalt codope carbon material under atmosphere；By obtained sulphur, nitrogen, cobalt
Codope carbon material 40mg is scattered in 20mL ethylene glycol, and ultrasonic agitation 2h obtains dispersion liquid；It will be added in obtained dispersion liquid
2.5mL 20mM PdCl2The aqueous solution, stir to well mixed and obtain mixed liquor, obtained mixed liquor is transferred to reaction under high pressure
Sealed in kettle, 6h is reacted in 160 DEG C, reaction naturally cools to room temperature after terminating, then centrifuged product, and be washed with deionized water
Wash, put into vacuum drying chamber drying to constant weight and obtain the carbon material supported palladium fuel-cell catalyst of sulphur, nitrogen, cobalt codope.
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
Comparative example 5
Take the 20%Pt/Xc-72 of JM companies of the business platinum catalyst U.S..
Electro-chemical test uses Solartron 1287（Solartron Analytical, England）The electrode body of type three
The half-cell of system is carried out.To scribble the glass-carbon electrode of catalyst（3mm external diameters）For working electrode.Electrode and reference electrode are distinguished
For 1cm2Platinized platinum and Ag/AgCl saturated calomel electrode.Electrolyte is the 1M methanol+1M KOH aqueous solution, to make catalyst attached
On glass-carbon electrode, clean glass-carbon electrode using secondary water and be dried at room temperature for.The preparation step of thin layer catalyst on electrode
It is rapid as follows：Take the perfluorinated sulfonic acid that 5mg catalyst adds 0.5mL ethanol and 50 μ L mass concentrations are 5%（PFSA）Solution, ultrasonic disperse
About 10min, 15 μ L are taken to be coated onto through the uniform suspension of ultrasonic disperse on bright and clean glass-carbon electrode with microsyringe, at room temperature
It can be tested after drying, electric performance test result is as shown in Figure 4.
The carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope obtained by the present invention is applied to first
The catalysis oxidation of alcohol, and there is good electro catalytic activity.Integrated embodiment 1 and comparative example 1-5, it can be seen that supported palladium copper closes
PdCu ghosts ball in golden fuel-cell catalyst is formed by the accumulation of PdCu little particles, and wherein PdCu ghosts spherolite footpath exists
The short grained particle diameter of 50nm or so, PdCu is in 5nm or so, and PdCu ghost balls are uniformly dispersed on carrier；Electrical property is surveyed
In test result, curve a is catalyst electrical property prepared by embodiment 1, and b, c, d, e and f correspond respectively to comparative example 4, comparative example
5th, the catalyst electrical property of comparative example 1, comparative example 2 and comparative example 3, compared with comparative example 1-5, sulphur made from embodiment 1, nitrogen,
Current density of the carbon material supported palladium-copper alloy fuel-cell catalyst of cobalt codope in methanol electrolysis matter solution can reach
140mA·cm-2, peak area corresponding to curve is also maximum, shows that catalyst goes out electrification to methanol oxidation performance made from embodiment 1
Active highest is learned, we think, as catalyst carrier, the dispersiveness nanocrystalline PdCu that is supported is changed Co-S-N-C
It is apt to, improves the utilization ratio of metal, and enhances the cooperative effect between carrier and metal, therefore final obtained catalysis
Agent electro catalytic activity excellent performance, it is expected to turn into a kind of fuel-cell catalyst with broad prospect of application.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
- A kind of 1. preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope, it is characterised in that Concretely comprise the following steps：（1）The mercaptan of 2- amino -1,3,5- triazines -4,6- two and mass concentration is super for 37% formalin and deionized water warp The uniform wiring solution-forming of sound dispersion mixing, adds Co (CH3COO)4·H2O simultaneously is uniformly mixed to obtain suspension, by what is obtained Suspension is transferred in autoclave and sealed, and 8h is reacted in 190 DEG C, reaction naturally cools to room temperature after terminating, by what is obtained Product be washed with deionized until filtrate become colorless, put into vacuum drying chamber in 80 DEG C dry to constant weight, then in N2 3h is calcined in 750 DEG C obtain double-deck ghost spherical structure sulphur, nitrogen, cobalt codope carbon material under atmosphere；（2）By step（1）Obtained sulphur, nitrogen, cobalt codope carbon material are scattered in ethylene glycol, and ultrasonic agitation 2h is disperseed Liquid, PdCl will be sequentially added in obtained dispersion liquid2The aqueous solution and CuSO4·5H2O, stir to well mixed and obtain mixed liquor, Obtained mixed liquor is transferred in autoclave and sealed, 6h is reacted in 160 DEG C, reaction naturally cools to room temperature after terminating, Then product is centrifuged, and be washed with deionized, put into vacuum drying chamber drying to constant weight and obtain sulphur, nitrogen, cobalt codope Carbon material supported ghost spherical structure palladium-copper alloy fuel-cell catalyst.
- 2. the preparation of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur according to claim 1, nitrogen, cobalt codope Method, it is characterised in that：Step（1）Described in the mercaptan of 2- amino -1,3,5- triazines -4,6- two, mass concentration be 37% formaldehyde Solution and Co (CH3COO)4·H2The O mass ratio that feeds intake is 1:6:10.
- 3. the preparation of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur according to claim 1, nitrogen, cobalt codope Method, it is characterised in that：Step（2）Described in sulphur, nitrogen, cobalt codope carbon material and CuSO4·5H2The O mass ratio that feeds intake is 2: 1, PdCl2With CuSO4·5H2O molar ratio is 5:8.
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| CN110112429A (en) * | 2019-05-14 | 2019-08-09 | 长沙锦锋新能源科技有限公司 | A kind of preparation method of magnesium air fuel cell catalyst |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN112436159A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
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| CN108448116A (en) * | 2018-03-05 | 2018-08-24 | 山东旭晟东阳新材料科技有限公司 | A kind of preparation method of the porous carbon aerogels fuel battery cathode with proton exchange film catalyst of the nitrogen with defect sturcture/sulphur codope |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
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| CN110112429A (en) * | 2019-05-14 | 2019-08-09 | 长沙锦锋新能源科技有限公司 | A kind of preparation method of magnesium air fuel cell catalyst |
| CN112436159A (en) * | 2020-11-06 | 2021-03-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
| CN112436159B (en) * | 2020-11-06 | 2022-09-02 | 扬州大学 | Alcohol fuel cell anode catalyst, preparation method and application thereof |
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