CN108075143A - A kind of preparation method and application of loaded PtCu nano hollow structures catalyst - Google Patents
A kind of preparation method and application of loaded PtCu nano hollow structures catalyst Download PDFInfo
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- CN108075143A CN108075143A CN201611014867.8A CN201611014867A CN108075143A CN 108075143 A CN108075143 A CN 108075143A CN 201611014867 A CN201611014867 A CN 201611014867A CN 108075143 A CN108075143 A CN 108075143A
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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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- 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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- 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
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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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- 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 present invention provides a kind of preparation method and application of loaded PtCu nano hollow structures catalyst.In the ethylene glycol of carrier and the mixed solution of water in the case of surfactant-free, add the aqueous solution of Pt and Cu transition metal salts successively, under 0 10 DEG C of cryogenic conditions, reducing agent is added in, then is warming up to 20 70 DEG C the reaction was continued 1 3h, it is washed, dry, obtain PtCu hollow-core construction catalyst.This method is easy to operate, is swift in response, and is easy to amplification synthesis, and prepared hollow-core construction nanocatalyst can be applied to the fields such as fuel cell.
Description
Technical field
The invention belongs to noble metal electrocatalyst fields, are related to a kind of system of loaded PtCu nano hollow structures catalyst
Preparation Method and application.
Background technology
Fuel cell is the power generator that the chemical energy with fuel is directly translated into electric energy, since it is followed from Kano
The limitation of ring makes it have the advantages of energy conversion efficiency is high, and fuel cell also has environmental-friendly, sustainable power generation, combustion
The advantages that material is diversified and higher than energy, therefore it is subject to the extensive concern in the world.Elctro-catalyst is one of fuel cell important
Component, at present, the catalyst that Proton Exchange Membrane Fuel Cells uses is mainly platinum and its alloy catalyst, but the valency of platinum
Lattice are expensive and reserves in China are relatively low, limit its application in a fuel cell.Therefore, how platinum utilization is improved,
The platinum-based electrocatalyst for preparing high activity is the main problem that we study.
Compared with solid metal catalyst, hollow-core construction shows low-density, high-specific surface area, saves material and low cost
The advantages of.Therefore, it is one of effective ways for improving unit mass Pt catalytic activity to prepare hollow-core construction catalyst.With non-Pt gold
Belong to for template, prepare the hollow-core construction using Pt alloys as shell, the utilization rate of Pt can be improved.In addition, two kinds that pass through shell
Or the interaction between three kinds of metals, the electronic structure and geometry mechanism of Pt can be regulated and controled, and then improve the catalysis of catalyst
Activity and selectivity；Meanwhile the surfaces externally and internally of the hollow shell structure with hole is respectively provided with catalytic action, can improve catalytic action
Ratios of the Pt in total Pt loads amount, so as to improve the utilization rate of Pt.
At present, liquid phase synthesis prepares metal nanoparticle mostly in various protective agents (polyvinylpyrrolidone, polypropylene
Acid, ammonium salt cationoid surfactant, sulfonic acid and sulfuric acid analog anion surfactants etc.) in the presence of carry out, so as to effectively
Control the size and pattern of metal nanoparticle.
It is mould that Chinese patent CN200910023865.9, which discloses a kind of method with the cuprous oxide particle of 50-1000nm,
Plate, cetyl trimethylammonium bromide prepare Pt nano hollow structures for protective agent.Chinese patent CN200310114338.1 is public
It is protective agent that a kind of method, which has been opened, with citric acid, and cobalt is the Pt nano hollow structures that template prepares that grain size is 15-50nm.It is Chinese special
It is carrier that sharp CN201110298886.9, which discloses a kind of method with graphene, and polyvinylpyrrolidone is protective agent, and nickel is mould
Plate prepares the Pt nano hollow structures that the grain size that graphene supports is 10-50nm.United States Patent (USP) 2012/0003563A1 is disclosed
A kind of method is template with Al or Mg or Zn powder, uses AgNO3Displacement obtains the silver nano-grain of racemosus shape, then replaces Ag with platinum salt
Obtain the Pt nanoparticle of racemosus shape.2013/0344421 A1 of United States Patent (USP) discloses a kind of method reducing agent reduction transition
Metal is simultaneously as template, then is replaced with platinum salt to obtain hollow-core construction elctro-catalyst.The grain size of obtained Pt nanoparticle is 3-
20nm。
The content of the invention
Present invention aims at propose a kind of preparation method of loaded PtCu nano hollow structures catalyst, this method behaviour
Make simply, to be swift in response, reaction temperature is low, of low cost, suitable for large-scale production.Prepared loaded PtCu nano-hollows
Structure catalyst PtCu size adjustables.
The present invention provides a kind of preparation method of loaded PtCu nano hollow structures catalyst, specific synthesis steps
For：In the ethylene glycol of carrier and the mixed solution of water, the aqueous solution of the metallic compound of Pt and Cu is separately added into, at 0-10 DEG C
It is lower stirring 30 minutes or more, then under conditions of stirring, be passed through inert atmosphere gases, then add in water-soluble reducing agent or its
Aqueous solution reacts 1-10 minutes；20-70 DEG C is warming up to again the reaction was continued 1-3h, loaded PtCu is obtained after washed, dry
Nano hollow structure catalyst.
The preparation method of loaded PtCu nano hollow structures catalyst of the present invention, the mixing of ethylene glycol and water are molten
In liquid, the volume ratio of ethylene glycol and water is 2:1.
The preparation method of loaded PtCu nano hollow structures catalyst of the present invention, the carrier are activity
Carbon, carbon nanotubes, graphene, tungsten carbide or indium tin oxide.
The preparation method of loaded PtCu nano hollow structures catalyst of the present invention, the Pt compounds are chlorine
Platinic acid, chloroplatinous acid, potassium chloroplatinate, platinic sodium chloride, ammonium chloroplatinate, chloroplatinic acid lithium, potassium chloroplatinite, sodium chloroplatinite, chlorine are sub-
One or two or more kinds of mixtures in platinic acid ammonium, chloroplatinous acid lithium；Cu compounds are copper chloride, in copper nitrate, copper sulphate
One or more kinds of mixtures, the concentration of Cu compound water solutions is 1-500mmol/L, Pt and Cu in mixed solution
Atomic ratio is 1：1~4.
The preparation method of loaded PtCu nano hollow structures catalyst of the present invention, the reducing agent aqueous solution
For sodium borohydride aqueous solution, molar concentration 0.5-5000mmol/L, sodium borohydride and the compound of Pt and Cu mole and ratio
Example is 10-1:1；The water-soluble reducing agent be the compound of hydrazine hydrate, hydrazine hydrate and Pt and Cu mole and ratio be 13:
1.；Inert atmosphere gases are Ar or N2。
The loaded PtCu nano hollow structures catalyst that the method for the invention is prepared is led applied to fuel cell
Domain.
The macromolecule organics such as surfactant are not used in preparation process of the present invention, reduce using synthesis of surfactant
It needs repeatedly washing, high speed centrifugation that can just obtain the tedious steps of more clean catalyst in the process, is further simplified production
Technological process reduces production cost；Preparation process carries out at a lower temperature, reduces to equipment corrosion resistance and heating unit
Requirement.The preparation method that the present invention uses is simple and effective, by being previously added carrier, and strictly controls reactant concentration, anti-
Temperature and reaction time are answered, the loaded PtCu catalyst being prepared has smaller grain size and smaller particle diameter distribution, simultaneously
There is preferable dispersiveness on carrier.In addition, prepared catalyst can effectively improve platinum utilization, the use of platinum is reduced
Amount, shows oxygen reduction reaction higher catalytic activity and stability.
Description of the drawings
Fig. 1 embodiments 1 prepare transmission electron microscope (TEM) photo of sample；
Fig. 2 embodiments 6 prepare transmission electron microscope (TEM) photo of sample；
Fig. 3 embodiments 7 prepare transmission electron microscope (TEM) photo of sample；
Fig. 4 embodiments 1 prepare the cyclic voltammetric of sample and hydrogen reduction test curve.
Specific embodiment
Test method in embodiment includes：
Cyclic voltammetry：
Electrolyte：N at room temperature2The 0.1M HClO of gas saturation4Aqueous solution, sweep speed 50mV/s, voltage scan range
0.05~1.2V (compared with reversible hydrogen electrode) is taken off using hydrogen and pays areal calculation ECA, and test equipment is collocation rotating disk electrode (r.d.e)
System (Pine Instruments, U.S.) CHI730D types electrochemical analyser (CHI Instruments Inc.,
U.S.)。
Hydrogen reduction is tested：
Electrolyte：O at room temperature2The 0.1M HClO of saturation4Aqueous solution, rotating circular disk rotating speed 1600rpm, forward scan
10mV/s, voltage scan range are 0.2~1V (compared with reversible hydrogen electrode), and test equipment is collocation rotating disk electrode (r.d.e) system
The CHI730D types electrochemical analyser (CHI Instruments Inc., U.S.) of (Pine Instruments, U.S.).
Embodiment 1：
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.45mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 3.61mL, 100mmol/L4Aqueous solution is reacted 1 minute, then heated up
To 40 DEG C of reaction 1h, loaded hollow Cu is obtained after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Fig. 1 is loaded hollow Cu2Pt1The TEM photos of/C nano particle.
Fig. 4 is the Cu prepared2Pt1/ C catalyst and the cycling for being commercialized 20%Pt/C (Johnson Matthey) catalyst
Volt-ampere and hydrogen reduction test curve, by being calculated, Cu2Pt1Electrochemically active specific surface area, the area ratio of/C catalyst are lived
Property, quality specific activity are respectively 21.4m2/g、1116.2μA/cm2, 238.3mA/mg Pt, be commercialized Pt/C catalyst electrification
Specific surface area active, area specific activity, quality specific activity are respectively 59.8m2/g、188.8μA/cm2, 149.5mA/mg Pt,
As can be seen that although Cu2Pt1The specific surface area of the more commercialized Pt/C catalyst of/C is reduced, but its area specific activity,
Quality specific activity is commercialized 5.9,1.6 times respectively.
Embodiment 2：Inert gas species
Under water bath with thermostatic control and argon gas protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.45mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 10 DEG C, adds in the NaBH of 3.61mL, 100mmol/L4Aqueous solution is reacted 10 minutes, then risen
Temperature obtains loaded hollow Cu to 40 DEG C of reaction 1h after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Embodiment 3：Metal front bulk concentration
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.09mL, 500mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 3.61mL, 100mmol/L4Aqueous solution is reacted 10 minutes, then risen
Temperature obtains loaded hollow Cu to 40 DEG C of reaction 2h after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Embodiment 4：Metal precursor species
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the H of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the Cu of 0.45mL, 100mmol/L
(NO3)2Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 3.61mL, 100mmol/L4Aqueous solution reacts 1 minute,
60 DEG C of reaction 1h are warming up to again, and loaded hollow Cu is obtained after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Embodiment 5：Metal precursor species
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl6Aqueous solution, the CuSO of 0.45mL, 100mmol/L4
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 3.61mL, 100mmol/L4Aqueous solution is reacted 1 minute, then heated up
To 70 DEG C of reaction 1h, loaded hollow Cu is obtained after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Embodiment 6：Platinoid component ratio
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.75mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 5.41mL, 100mmol/L4Aqueous solution is reacted 1 minute, then heated up
To 40 DEG C of reaction 1h, loaded hollow Cu is obtained after washed, dry4Pt1Nano-particle (Cu4Pt1/C)。
Fig. 2 is loaded hollow Cu4Pt1The TEM photos of/C nano particle.
Embodiment 7：Platinoid component ratio
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.3mL, 100mmol/L2Water
Solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 2.71mL, 100mmol/L4Aqueous solution is reacted 1 minute, then is warming up to
40 DEG C of reaction 1h, loaded hollow Cu is obtained after washed, dry1Pt1Nano-particle (Cu1Pt1/C)。
Fig. 3 is loaded hollow Cu1Pt1The TEM photos of/C nano particle.
Embodiment 8：Reducing agent species
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.45mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in 38.85 μ L hydrazine hydrates (density d=1.027,98%, Alfa companies), reaction
10 minutes, then 40 DEG C of reaction 1h are warming up to, obtain loaded hollow Cu after washed, dry2Pt1Nano-particle (Cu2Pt1/
C)。
Embodiment 9：Reductant concentration
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.45mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 120.18mL, 0.5mmol/L4Aqueous solution is reacted 1 minute, then risen
Temperature obtains loaded hollow Cu to 40 DEG C of reaction 1h after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Embodiment 10：Reductant concentration
Under water bath with thermostatic control and nitrogen protective condition, the XC72R activated carbons of 11.7mg are dissolved in 20mL ethylene glycol and 10mL
In the mixed solution of water, the K of 0.79mL, 19.1mmol/L are added2PtCl4Aqueous solution, the CuCl of 0.45mL, 100mmol/L2
Aqueous solution stirs 0.5h under the conditions of 5 DEG C, adds in the NaBH of 0.12mL, 5000mmol/L4Aqueous solution is reacted 1 minute, then risen
Temperature obtains loaded hollow Cu to 40 DEG C of reaction 1h after washed, dry2Pt1Nano-particle (Cu2Pt1/C)。
Claims (6)
1. a kind of preparation method of loaded PtCu nano hollow structures catalyst, it is characterised in that：Carrier ethylene glycol and
In the mixed solution of water, the aqueous solution of the metallic compound of Pt and Cu is separately added into, is stirred 30 minutes or more at 0-10 DEG C, with
Afterwards under conditions of stirring, inert atmosphere gases are passed through, then add in water-soluble reducing agent or its aqueous solution, 1-10 points of reaction
Clock；20-70 DEG C is warming up to again the reaction was continued 1-3h, loaded PtCu nano hollow structures catalysis is obtained after washed, dry
Agent.
2. the preparation method of loaded PtCu nano hollow structures catalyst described in accordance with the claim 1, it is characterised in that：Institute
In the ethylene glycol and the mixed solution of water stated, the volume ratio of ethylene glycol and water is 2:1.
3. the preparation method of loaded PtCu nano hollow structures catalyst described in accordance with the claim 1, it is characterised in that：Institute
The carrier stated is activated carbon, carbon nanotubes, graphene, tungsten carbide or indium tin oxide.
4. the preparation method of loaded PtCu nano hollow structures catalyst described in accordance with the claim 1, it is characterised in that：Pt
Compound is chloroplatinic acid, chloroplatinous acid, potassium chloroplatinate, platinic sodium chloride, ammonium chloroplatinate, chloroplatinic acid lithium, potassium chloroplatinite, chlorine Asia platinum
One or two or more kinds of mixtures in sour sodium, ammonium chloroplatinite, chloroplatinous acid lithium；Cu compounds for copper chloride, copper nitrate,
Mixture more than one or both of copper sulphate, the concentration of Cu compound water solutions are 1-500mmol/L, in mixed solution
The atomic ratio of Pt and Cu is 1：1~4.
5. the preparation method of loaded PtCu nano hollow structures catalyst described in accordance with the claim 1, it is characterised in that：Institute
The reducing agent aqueous solution stated is sodium borohydride aqueous solution, and molar concentration 0.5-5000mmol/L, sodium borohydride is with Pt's and Cu
The molar ratio of the sum of compound is 10-1:1；The water-soluble reducing agent is the chemical combination of hydrazine hydrate, hydrazine hydrate and Pt and Cu
The molar ratio of the sum of object is 11-20:1；Inert atmosphere gases are Ar or N2。
6. the loaded PtCu nano hollow structures catalyst being prepared according to claim 1 the method is applied to fuel electricity
Pond field.
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Cited By (8)
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| CN108987757A (en) * | 2018-08-17 | 2018-12-11 | 佛山皖和新能源科技有限公司 | A kind of preparation method of anode of microbial fuel cell material |
| CN109103473A (en) * | 2018-08-01 | 2018-12-28 | 大连理工大学 | Nitrogen-doped carbon for alkaline hydroxide reaction supports the preparation method and application of the metal nanoparticle elctro-catalyst of uniform particle diameter |
| CN109404751A (en) * | 2018-10-17 | 2019-03-01 | 宁波市鄞州利帆灯饰有限公司 | A kind of novel energy-conserving LED light |
| CN109546159A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of very thin fuel cell catalyst layer and preparation method thereof |
| CN110277565A (en) * | 2019-05-28 | 2019-09-24 | 南方科技大学 | Fuel cell platinum indium catalyst and its preparation method and application |
| CN111224117A (en) * | 2018-11-23 | 2020-06-02 | 中国科学院大连化学物理研究所 | Pt alloy catalyst with nanowire structure and preparation method and application thereof |
| CN111261886A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof |
| CN115101764A (en) * | 2022-05-10 | 2022-09-23 | 大连理工大学 | Green low-temperature preparation method and electrocatalysis application of supported high-entropy alloy material |
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| CN108987757A (en) * | 2018-08-17 | 2018-12-11 | 佛山皖和新能源科技有限公司 | A kind of preparation method of anode of microbial fuel cell material |
| CN108987757B (en) * | 2018-08-17 | 2020-12-15 | 刘伟萍 | Preparation method of anode material of microbial fuel cell |
| CN109404751A (en) * | 2018-10-17 | 2019-03-01 | 宁波市鄞州利帆灯饰有限公司 | A kind of novel energy-conserving LED light |
| CN109546159A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of very thin fuel cell catalyst layer and preparation method thereof |
| CN111224117A (en) * | 2018-11-23 | 2020-06-02 | 中国科学院大连化学物理研究所 | Pt alloy catalyst with nanowire structure and preparation method and application thereof |
| CN111261886A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof |
| CN110277565A (en) * | 2019-05-28 | 2019-09-24 | 南方科技大学 | Fuel cell platinum indium catalyst and its preparation method and application |
| CN110277565B (en) * | 2019-05-28 | 2020-12-18 | 南方科技大学 | Platinum-indium catalyst for fuel cell and preparation method and application thereof |
| CN115101764A (en) * | 2022-05-10 | 2022-09-23 | 大连理工大学 | Green low-temperature preparation method and electrocatalysis application of supported high-entropy alloy material |
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