CN104600326B - Preparation method of carbon-supported nano platinum alloy catalyst - Google Patents
Preparation method of carbon-supported nano platinum alloy catalyst Download PDFInfo
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- CN104600326B CN104600326B CN201410820921.2A CN201410820921A CN104600326B CN 104600326 B CN104600326 B CN 104600326B CN 201410820921 A CN201410820921 A CN 201410820921A CN 104600326 B CN104600326 B CN 104600326B
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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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 provides a preparation method of a carbon-supported nano platinum alloy catalyst. The method comprises the following steps: I. depositing Cu on the surfaces of Pt/C carbon-supported nano platinum catalyst particles by utilizing an underpotential deposition method to obtain Cu-Pt/C; II. dispersing Cu-Pt/C in a solution containing 3d transition metal ions uniformly to obtain Cu-Pt/C suspension, and drying the Cu-Pt/C suspension to obtain a dried sample; III. ball-milling the dried sample, and putting the dried sample in a reducing atmosphere to be reduced and alloyed; IV. dealloying the sample obtained in the step III, and washing and drying to obtain the carbon-supported nano alloy catalyst. The preparation method provided by the invention has the beneficial effects that the losses caused because carbon support materials undergo high temperature can be effectively reduced, thus relieving the problem of severe fused growth of carbon-supported Pt alloy nanoparticles at high temperature; the nano platinum alloy catalyst prepared by the method has the advantages of small platinum alloy particle size, good dispersibility and high catalytic oxygen reduction property.
Description
Technical field
The present invention relates to a kind of preparation method of carbon-supported nano platinum alloy catalyst (Pt-alloy/C), belongs to materials synthesis
And technical field of electrochemistry.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) because its running temperature low (80 DEG C or so), power density is high, it is fast to start,
The advantages of power match speed is fast receives significant attention.In all eurypalynous fuel cells, H2/ air PEMFC is light vapor
Car and the first-selection of building energy supply.Recently, Thomas et al. is to pure electronic fuel battery car and secondary cell pure electric automobile
Compare.The research is to weight, volume, cost, CO2Discharge, fuel make up or charging interval, efficient energy conversion, use
The factors such as life-span carry out being found after Integrated comparative, when the course continuation mileage of automobile is in more than 160km (100miles), fuel cell
Advantage is had more than secondary cell.
At present, PEMFC wide variety of principal element on automobile is hindered to be that catalyst Pt supports demand too
Height, so as to cause fuel cell car high expensive, compares with vapour/diesel vehicle and lacks competitiveness.Wherein solve Pt loadings to ask
Topic, mainly sets about from reduction negative electrode platinum demand, because current negative electrode platinum supports demand accounting and is about 90%.Reduce negative electrode platinum
Carrying capacity, inevitable requirement exploitation has high activity, the catalyst of high stability and improves the utilization rate of catalyst.
At present, it is believed to be expected to realize that one of approach that negative electrode platinum carrying capacity is reduced is by Pt and 3d transition metal alloys
Change, alloying rear catalyst activity can improve more than 2 times.A lot of about the preparation method of the alloy catalyst, low temperature is organic
Liquid phase reduction, microemulsion method, vapour deposition process, electrochemical deposition method and dipping high temperature reduction method etc., it is by contrast, relevant
The Patents of dipping high temperature reduction method are more, and the equipment and raw material required for the method is relatively conventional, and whole process is easy
Manipulation, is more hopeful to realize amplifying the production cost for producing and reducing alloy catalyst.But at present the method is faced with one urgently
Problem to be solved：When carrier carbon is under conditions of platinum, transistion metal compound, reducing atmosphere and high temperature has both, its
Quality can be substantially reduced, and this causes the nano particle on carrier that migration occurs, merges and grow up, and finally affects catalyst component
And performance uniformity.By introducing Cu layers on Pt surfaces in the present invention, to weaken catalytic action of the Pt in whole process, from
And carbon loss is reduced, improve the purpose of catalyst performance.
The content of the invention
The purpose of the present invention is the problem for overcoming prior art to exist, there is provided a kind of carbon-supported nano platinum alloy catalyst (Pt-
Alloy/C preparation method), specifically a kind of method of the stability in whole preparation process that can improve carbon carrier, adopts
The nanometer platinum alloy catalyst (Pt-alloy/C) prepared with the method has little platinum particle size, good dispersion and catalysis
The high advantage of hydrogen reduction performance.
The present invention is achieved by the following technical solutions：
The present invention relates to a kind of preparation method of carbon-supported nano platinum alloy catalyst (Pt-alloy/C), the preparation method
Comprise the steps：
Step one, utilization are owed potential sedimentation and Cu are deposited on into Pt/C carbon-supported nano Pt catalyst granules surface, obtain Cu-
Pt/C；
Step 2, by above-mentioned Cu-Pt/C be dispersed in the solution containing 3d transition metal ions Cu-Pt/C suspends
Liquid, dry drying sample；
Step 3, by above-mentioned drying sample ball milling, be placed in reducing atmosphere reduction, alloying；
Step 4, the sample obtained in step 3 is carried out de- alloy treatment, washing, be dried after obtain carbon-supported nano conjunction
Au catalyst (Pt-alloy/C).
Preferably, in step one, the carbon carrier in the carbon load Pt nano particles is carbon black, activated carbon, graphitic carbon, carbon are received
Mitron, carbon nano-fiber or mesoporous carbon.
Preferably, in step one, the underpotential deposition method refers under inert gas shielding, by Pt/C carbon-supported nano platinum
Catalyst granules is scattered in acid copper solutions, and sets up three-electrode system, working electrode potential is controlled in copper ion
Occur to owe the current potential of potential deposition in Pt surfaces, maintain constant potential 10s～10mins, obtain final product Cu and cover preferable Cu-Pt/C.
Preferably, cathode and anode material and for electric conductivity is high and the good material of corrosion resistance in the three-electrode system, including
Platinum, gold, graphite etc., reference electrode includes saturated calomel electrode, Mercurous sulfate electrode, silver chloride electrode or hydrogen electrode.
Preferably, the inert gas refers specifically to nitrogen or argon gas.
Preferably, 0.05～0.3M CuSO are contained in the acid copper solutions4, 0.05～0.1M H2SO4。
Preferably, the Pt/C carbon-supported nanos Pt catalyst granule and the quality amount ratio of acid copper solutions are 1：(50～
500)。
Preferably, in step 2, the 3d transition metal ions derives from iron, cobalt, the nitrate of nickel, chlorate, acetic acid
Salt or formates.
Preferably, the concentration of the 3d transition metal ions is 0.20mmol/L～1.0mol/L.
Preferably, the solvent of solution described in step 2 be water, isopropanol, ethanol, methyl alcohol, ether, acetone, N, N- diformazans
The mixed solution of one or more in base formamide, ethylene glycol, glycerine.
Preferably, in step 2, the Cu-Pt/C is 1 with the quality amount ratio of the solution containing 3d transition metal ions：
(5～50).
Preferably, in step 3, the alloying temperature is 600～1000 DEG C.
Preferably, in step 3, the reducing atmosphere is specially H2H of the volume fraction in 5～10% scopes2/N2Or
H2/ Ar mixed gas.
Preferably, in step 4, the de- alloy approach is selected from the de- alloy of acidleach or the de- alloy of electrochemistry；Mode of washing bag
Include filter membrane dialysis or filter type；Drying mode includes that vacuum drying, spray drying, freeze-drying or common heating are dry
It is dry.
Preferably, the de- alloy of the acidleach adopts the sulfuric acid or nitric acid of 1M, and condition is 60～80 DEG C, 12～48h.
Compared with prior art, the present invention has following beneficial effect：
1st, carbon carrier loss can be significantly reduced, the Pt-al loy/C alloying pellet sizes obtained from are little and dispersion ratio
It is more uniform；
2nd, Cu has double effects, can not only reduce carbon loss, but also can significantly change Pt in Pt-alloy/C
Geometry electronic structure, to improve Pt area specific activity there is good effect.
3rd, single battery voltage is that the quality specific activity of Pt-alloy/C catalyst can reach 0.45A mg under 0.9VPt -1It is (single
Cell cathode carrying capacity：0.18～0.20mgPt cm-2；Anode：64μgPt cm-2；Electrode area：5*5cm2.Test condition：80 DEG C,
Hydrogen:Oxygen stoichiometry ratio=2:9.5, back pressure is 150KPa, and relative humidity is 100%.).
Description of the drawings
The detailed description by reading non-limiting example made with reference to the following drawings, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is Pt-al loy/C TEM photos in embodiment 1；
Fig. 2 is the Pt mass specific activity and single battery voltage that Pt-al loy/C Jing fuel cell tests are obtained in embodiment 1
(V) graph of a relation；
Fig. 3 is Pt-al loy/C TEM photos in comparative example 1；
Fig. 4 is the Pt mass specific activity and single battery voltage that Pt-al loy/C Jing fuel cell tests are obtained in comparative example 1
(V) graph of a relation.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to this
Bright protection domain.
Embodiment 1
The present embodiment is related to a kind of preparation method of carbon-supported nano platinum alloy catalyst (Pt-alloy/C), methods described bag
Include following steps：
Step 1,200ml acid copper sulfates are added under stirring condition by 1g Pt/C catalyst (platinum content is 30wt%)
Solution (0.05M CuSO4, 0.05MH2SO4) in, and ultrasonic disperse 30mins, deoxygenation 30mins；It is stone that cathode and anode material is simultaneous
Ink, reference electrode is saturated calomel electrode, with mechanical stirring device in the three-electrode system；Negative electrode is arranged on into the deficient electricity of Cu
Near the sedimentation potential of position, constant potential 2mins is maintained, obtain Cu-Pt/C.
Step 2, Cu-Pt/C impregnated in containing Co (NO3)2·6H2It is follow-up using super in the 20ml aqueous solution of O 2.695g
Sound mode in combination with standard machinery stirring, ultrasonic 30mins, standard machinery stirring 30mins, is repeated twice, and obtains Cu-Pt/C
Suspension；
Step 3, by the suspension freeze-drying 12h in step 2；
Step 4, the drying sample in step 3 is ground, and is subsequently placed in 10%H2/N2In gaseous mixture, 900 DEG C are heated to, perseverance
Warm 12h；
Step 5, by the sample obtained in step 4 80 DEG C of 1M HNO are placed in3Alloy treatment 48h is taken off in solution, it is washed
Filter and 80 DEG C of vacuum drying 8h.
Effect：The TEM photos of the prepared catalyst of embodiment 1 are as shown in figure 1, distribution ratio of the alloy nanoparticle on carbon
It is more uniform.Single battery voltage is the quality specific activity measured under 0.9V as shown in Fig. 2 its value is 0.45A mgPt -1(monocell is cloudy
Pole carrying capacity：0.18mgPt cm-2；Anode：64μgPt cm-2；Electrode area：5*5cm2；Test condition：80℃；Hydrogen:Oxymeter
Amount ratio=2:9.5；Back pressure is 150KPa；Relative humidity is 100%.).
In the present embodiment, the cathode and anode material in step 1 is capable of achieving the present embodiment selected from platinum, gold or graphite；Reference
Electrode is capable of achieving the present embodiment selected from saturated calomel electrode, Mercurous sulfate electrode, silver chloride electrode or hydrogen electrode.
Embodiment 2
The present embodiment is the change case of embodiment 1, and change part is only that：In step 2,3d transition metal ions is derived from
Nickel nitrate.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.48A mg than activity valuePt -1。
Embodiment 3
The present embodiment is the change case of embodiment 1, and change part is only that：In step 2, Co (NO3)2·6H2The concentration of O
For 0.20mmol/L.
Effect：Catalyst manufactured in the present embodiment quality for measuring in the case where single battery voltage is 0.9V is than activity value
0.45AmgPt -1。
Embodiment 4
The present embodiment is the change case of embodiment 1, and change part is only that：In step 2, Co (NO3)2·6H2The concentration of O
For 1.0mol/L.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.47A mg than activity valuePt -1。
Embodiment 5
The present embodiment is the change case of embodiment 1, and change part is only that：In step 1, contain in acid copper solutions
0.05M CuSO4、0.1M H2SO4。
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.44A mg than activity valuePt -1。
Embodiment 6
The present embodiment is the change case of embodiment 1, and change part is only that：In step 1,0.3M is contained in acid copper solutions
CuSO4、0.05M H2SO4。
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.47A mg than activity valuePt -1。
Embodiment 7
The present embodiment is the change case of embodiment 1, and change part is only that：In step 4, alloying temperature is 600 DEG C.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.40Amg than activity valuePt -1。
Embodiment 8
The present embodiment is the change case of embodiment 1, and change part is only that：In step 4, alloying temperature is 1000 DEG C.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.48Amg than activity valuePt -1。
Embodiment 9
The present embodiment is the change case of embodiment 1, and change part is only that：In step 5, the de- alloy of the acidleach adopts 1M
Sulfuric acid, condition be 60 DEG C, 12h.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.45A mg than activity valuePt -1。
Embodiment 10
The present embodiment is the change case of embodiment 1, and change part is only that：In step 5, the de- alloy of the acidleach adopts 1M
Sulfuric acid, condition be 70 DEG C, 30h.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.40A mg than activity valuePt -1。
Embodiment 11
The present embodiment is the change case of embodiment 1, and change part is only that：In step 1, the quality of Pt/C catalyst is
1g, acid copper sulfate solution (0.05M CuSO4, 0.05MH2SO4) volume be 50mL.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.42Amg than activity valuePt -1。
Embodiment 12
The present embodiment is the change case of embodiment 1, and change part is only that：In step 1, the quality of Pt/C catalyst is
1g, acid copper sulfate solution (0.05M CuSO4, 0.05MH2SO4) volume be 500mL.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V voltages is 0.46A mg than activity valuePt -1。
Embodiment 13
The present embodiment is the change case of embodiment 1, and change part is only that：In step 2, the quality of the Cu-Pt/C is
(concentration is the solution of 1g, 3d transition metal ions：(the NO containing Co in the 20ml aqueous solution3)2·6H2O 2.695g) volume be
5mL。
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V vs.RHE is 0.50Amg than activity valuePt -1。
Embodiment 14
The present embodiment is the change case of embodiment 13, and change part is only that：In step 2, the quality of the Cu-Pt/C is
(concentration is the solution of 1g, 3d transition metal ions：(the NO containing Co in the 20ml aqueous solution3)2·6H2O 2.695g) volume be
50mL。
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V vs.RHE is 0.40Amg than activity valuePt -1。
Embodiment 15
The present embodiment is the change case of embodiment 1, and change part is only that：In step 2, the solution of 3d transition metal ions
In solvent be water and ethanol volume ratio be 2:1 mixed solution.
Effect：The quality that catalyst manufactured in the present embodiment is measured under 0.9V vs.RHE is 0.48Amg than activity valuePt -1。
Comparative example 1
This comparative example is the comparative example of embodiment 1, is related to a kind of catalyst, and preparation method is as follows：
Step 1, is added to 1g Pt/C catalyst (platinum content is 30wt%) containing Co under standard machinery stirring condition
(NO3)2·6H2It is follow-up using the ultrasonic mode in combination with standard machinery is stirred, ultrasound in the 20ml aqueous solution of O 2.695g
30mins, standard machinery stirring 30mins, is repeated twice, and obtains Pt/C suspension；
Step 2, by the 80 DEG C of vacuum drying 12h of suspension in step 1；
Step 3, the drying sample in step 2 is ground, and is subsequently placed in 10%H2/N2In gaseous mixture, 900 DEG C are heated to, perseverance
Warm 12h；
Step 4, by the sample obtained in step 3 80 DEG C of 1M HNO are placed in3Alloy treatment 48h is taken off in solution, it is washed
Filter and 80 DEG C of vacuum drying 8h, obtain final product.
Effect：The TEM photos of the prepared catalyst of comparative example 1 are as shown in Figure 3.The mass ratio measured under 0.9V voltages is lived
Property as shown in figure 4, its value be 0.25A mgPt -1(monocell negative electrode carrying capacity：0.18～0.20mgPt cm-2；Anode：64μgPt cm-2；Electrode area：5*5cm2.Test condition：80 DEG C, hydrogen:Oxygen stoichiometry ratio=2:9.5, back pressure is 150KPa, relative humidity
For 100%.).
Comparative example 2
This comparative example is the comparative example of embodiment 1, and other conditions are same as Example 1, the difference is that only：Step 1
CuSO containing 0.5M in middle acid copper sulfate solution4, 0.15MH2SO4。
Effect：The quality that the catalyst of this comparative example is measured under 0.9V voltages is 0.22A mg than activity valuePt -1。
Comparative example 3
This comparative example is the comparative example of embodiment 1, and other conditions are same as Example 1, the difference is that only：Step 2
In, (concentration is for the solution of 3d transition metal ions：(the NO containing Co in the 20ml aqueous solution3)2·6H2O 2.695g) volume be
80mL。
Effect：The quality that the catalyst of this comparative example is measured under 0.9V voltages is 0.21A mg than activity valuePt -1。
Comparative example 4
This comparative example is the comparative example of embodiment 1, and other conditions are same as Example 1, the difference is that only：Step 4
In, the temperature for taking off alloy treatment is 95 DEG C, and the time is 50h.
Effect：The quality that the catalyst of this comparative example is measured under 0.9V voltages is 0.20A mg than activity valuePt -1。
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various modifications or modification, this not shadow
Ring the flesh and blood of the present invention.
Claims (7)
1. a kind of preparation method of carbon-supported nano platinum alloy catalyst, it is characterised in that the preparation method comprises the steps：
Step one, utilization are owed potential sedimentation and Cu are deposited on into Pt/C carbon-supported nano Pt catalyst granules surface, obtain Cu-Pt/
C；
Step 2, the Cu-Pt/C is dispersed in in the solution containing 3d transition metal ions to obtain Cu-Pt/C suspension,
Dry drying sample；
Step 3, by the drying sample ball milling, be placed in reducing atmosphere reduction, alloying；
Step 4, the sample obtained in step 3 is carried out de- alloy treatment, washing, be dried after obtain carbon-supported nano alloy and urge
Agent；
In step one, the underpotential deposition method is referred specifically under inert gas shielding, by Pt/C carbon-supported nano platinum catalysts
Particle is scattered in acid copper solutions, and sets up three-electrode system, enables working electrode potential control in copper ion in Pt tables
There is the current potential for owing potential deposition in face, maintain constant potential 10s～10mins；
Contain 0.05～0.3M CuSO in the acid copper solutions4, 0.05～0.1M H2SO4；
In step 2, the concentration of the 3d transition metal ions is 0.20mmol/L～1.0mol/L；
In step 4, the de- alloy approach is selected from the de- alloy of acidleach or the de- alloy of electrochemistry；
The de- alloy of the acidleach adopts the sulfuric acid or nitric acid of 1M, and condition is 60～80 DEG C, 12～48h.
2. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step one,
Carbon in the Pt/C carbon-supported nanos platinum catalyst is selected from carbon black, activated carbon, graphitic carbon, CNT, carbon nano-fiber or Jie
Hole carbon.
3. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step 2,
The 3d transition metal ions derives from iron, cobalt, the nitrate of nickel, chlorate, acetate or formates.
4. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step 2,
The solvent of the solution is in water and isopropanol, ethanol, methyl alcohol, ether, acetone, DMF, ethylene glycol, glycerine
The mixed solution of one or more.
5. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step 3,
The alloying temperature is 600～1000 DEG C.
6. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step 3,
The reducing atmosphere is specially H2H of the volume fraction 5～10%2/N2Or H2The mixed gas of/Ar.
7. the preparation method of carbon-supported nano platinum alloy catalyst according to claim 1, it is characterised in that in step 4,
The mode of washing includes filter membrane dialysis or filter type；Drying mode include vacuum drying, be spray-dried, freeze-drying or
Common heating is dried.
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| CN105633422B (en) * | 2016-03-21 | 2018-02-13 | 北京化工大学 | A kind of mass prepares the method that fuel battery negative pole takes off alloy elctro-catalyst with platinum base |
| CN106960962B (en) * | 2017-04-26 | 2019-11-15 | 北京化工大学 | A kind of platinum base of polyaniline-coated carbon carrier takes off alloy fuel cell catalyst and preparation method thereof |
| CN108607576A (en) * | 2018-04-23 | 2018-10-02 | 北京化工大学 | A method of simply preparing monodisperse platinoid duplex metal nano granule |
| CN110112430A (en) * | 2019-04-19 | 2019-08-09 | 贵研铂业股份有限公司 | A kind of platinum alloy carbon-supported powder and preparation method thereof |
| CN110518257B (en) * | 2019-09-03 | 2022-07-22 | 上海电气集团股份有限公司 | Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst |
| CN110783577B (en) * | 2019-10-08 | 2021-05-18 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| CN111725525B (en) * | 2020-06-18 | 2022-03-15 | 上海交通大学 | Carbon-supported monodisperse Pt-Ni nanoparticle catalyst prepared by electrodeposition and preparation and application thereof |
| CN111916775B (en) * | 2020-08-12 | 2022-03-22 | 贵州梅岭电源有限公司 | Platinum-based alloy catalyst for fuel cell and preparation method thereof |
| CN115020719A (en) * | 2022-06-21 | 2022-09-06 | 北京化工大学 | Preparation method of dual-site catalyst for direct formate fuel cell anode |
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