CN111261886A - Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof - Google Patents
Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof Download PDFInfo
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- CN111261886A CN111261886A CN201811460090.7A CN201811460090A CN111261886A CN 111261886 A CN111261886 A CN 111261886A CN 201811460090 A CN201811460090 A CN 201811460090A CN 111261886 A CN111261886 A CN 111261886A
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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Abstract
The invention provides a trace non-noble metal modified platinum-based catalyst and a preparation method thereof. The preparation method takes high-viscosity alcohol such as ethylene glycol, polyethylene glycol, glycerol and the like as a solvent and a stabilizer, reduces platinum and non-noble metal precursors by using hydrazine hydrate, tetrabutyl borohydride, citric acid, ascorbic acid and other strong reducing agents, and combines acid etching treatment to obtain the supported superfine platinum-based alloy nanoparticles containing trace non-noble metals and a platinum shell structure. The preparation method adopted by the invention is simple and effective, and is expected to realize batch production. In addition, based on the unique structural characteristics of the obtained catalyst, including the ultra-small catalyst particle size, uniform particle size distribution, micro-stabilized non-noble metal modification and a multi-layer Pt shell structure, the catalyst has excellent catalytic activity and cycle stability for the cathode oxygen reduction reaction of the fuel cell, can effectively reduce the consumption of platinum, and has potential application prospects in low-temperature fuel cells.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a trace non-noble metal modified platinum-based catalyst for a fuel cell.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of high power density, high energy efficiency, high starting speed, small environmental pollution and the like, is an ideal clean energy, and has wide application prospect in the fields of fixed power stations, transportation and the like. However, since the kinetics of the fuel cell cathode oxygen reduction reaction are slow, which limits the performance of the fuel cell to some extent, an efficient electrochemical catalyst is needed to accelerate this process. The catalyst widely used at present is a carbon-supported Pt nanoparticle catalyst (Pt/C). However, as is well known, Pt, a rare noble metal, has a limited amount of reserves on the earth and is expensive, so that the cost of the fuel cell is high, and the commercialization development of the fuel cell is seriously hindered. In addition, although the Pt/C catalyst shows excellent activity for ORR, it generally shows insufficient stability under high potential operating conditions and acidic environment of practical PEMFCs, and it is important to explore a catalyst having a low platinum amount and high stability to promote commercialization of fuel cells.
So far, reduction in the amount of Pt used and the cost of fuel cells has been achieved by improving the catalytic activity by alloying Pt with transition metals Fe, Co, Ni, etc. Such as Chen et al, by solvothermal reduction of Pt3The catalytic activity and stability of the Ni nanocage catalyst are significantly improved compared to commercial Pt/C (Chen, C., et al.,. Science,2014.343(6177): p.1339-43.). The method for preparing Pt by combining chemical reduction with heat treatment in the precious metal industry in Japan field3Co catalyst, up to about 1.5 times higher for fuel cells than for Pt/C catalystsPower density. Although the Pt alloy catalyst can improve the oxygen reduction catalytic performance, the preparation process is complex, the energy consumption is high, and the industrial production is not facilitated. In addition, under fuel cell conditions, dissolution of transition metals can cause a decline in catalyst activity and degradation of the membrane, resulting in a decrease in the performance of the actual PEMFC. Therefore, a simple and effective method for preparing a platinum-based alloy catalyst with high activity and high stability is urgently needed to be explored.
Disclosure of Invention
Aiming at the technical problems, the invention adopts a modified alcohol reduction method and combines acid etching pretreatment to prepare the trace non-noble metal modified Pt-based alloy catalyst, and the Pt-based alloy catalyst can be used for fuel cells and can realize the remarkable improvement of catalytic activity and stability. The technical scheme adopted by the invention comprises the following steps
(1) Deionized water is used for preparing a Pt precursor and non-noble metal precursor mixed solution, wherein the atomic ratio of Pt to non-noble metal is 1:30-30:1, and preferably 1:10-10: 1. Stirring to mix them uniformly.
(2) Adding carrier into high viscosity alcohol, and performing intense ultrasonic treatment for 30-60min to uniformly disperse;
(3) stirring the dispersion at room temperature for 30-60min, and introducing N during stirring2Or Ar, forming an inert atmosphere of the reaction system;
(4) and (2) adding a reducing agent into the dispersion, and then adding the Pt and non-noble metal precursor mixed solution formed in the step (1) to ensure that the total molar concentration of Pt and non-noble metal elements in the system is 0.1-20mmol/L (preferably 0.5-10mmol/L), and the molar concentration of the reducing agent is 1-100 times (preferably 5-30 times) that of the Pt and non-noble metal elements. Reacting at 0-160 deg.C (preferably 25-90 deg.C) for 0.5-24h (preferably 3-16 h).
5) Centrifugally washing, namely washing by using a mixture of ethanol and deionized water and adding a proper amount of dilute nitric acid to remove unstable non-noble metal and form a Pt-rich surface layer; after washing, vacuum drying for 6-24h at 40-100 ℃ to obtain the Pt-based alloy catalyst product;
the non-noble metal is Fe, Co, Ni, Cu, Mn, Mo, Cr.
The Pt precursorIs a nitrate, amine complex, hydrohalic acid, or hydrohalic acid salt of Pt; the non-noble precursor is nitrate, sulfate, halide, amine complex, halogen acid or halogen acid salt of corresponding metal; the high-viscosity alcohol is glycol, polyethylene glycol, glycerol and the like, and the high-viscosity alcohol is also used as a solvent and a protective agent; the carrier is carbon carriers such as conductive carbon black, carbon nano tubes, graphene and carbon nano cages, conductive polymers such as polyaniline, polypyrrole and polydopamine, TiO2、SnO2、WO3Oxides, metal carbides, metal nitrides and composites of two or more of the foregoing.
Based on the technical scheme, preferably, the reducing agent is hydrazine hydrate, tetrabutyl borohydride, citric acid, sodium citrate and ascorbic acid.
Based on the technical scheme, the stirring reaction temperature in the step 4) is preferably 25-90 ℃.
Based on the technical scheme, the stirring reaction time in the step 4) is preferably 3-16 h.
Based on the technical scheme, preferably, in the step 5), the total molar concentration of Pt and non-noble metal elements is 0.5-10 mmol/L.
The invention also provides a catalyst prepared by the method, wherein the catalyst is in a load type core-shell structure, and a supported object is in a core-shell structure; the core of the core-shell structure is an alloy of Pt and non-noble metal; the shell of the core-shell structure is Pt; the shape of the core-shell structure is spherical nano particles with the particle size of 1-3 nm.
Based on the technical scheme, preferably, in the catalyst, the atomic ratio of Pt to non-noble metal is greater than 10.
Based on the technical scheme, the catalyst preferably has a Pt-rich surface layer with the number of layers being 2-5.
The invention also provides the application of the catalyst in a low-temperature fuel cell.
Advantageous effects
(1) The preparation method has simple process, low energy consumption and environmental protection, and is beneficial to realizing large-scale production;
(2) the catalyst has the advantages that a surfactant is not used, the catalyst is small in particle size, uniform in particle size and uniform in distribution on a carrier, and the effective active area is remarkably higher than that of commercial Pt/C;
(3) the catalyst only contains trace transition metal, so that the performance attenuation caused by the dissolution of the transition metal in the operation process of the battery is greatly reduced;
(4) the catalyst has a Pt shell structure, so that the dissolution of transition metal can be effectively avoided, and the stability of the catalyst is further improved;
(5) the catalyst has significantly better activity and stability than commercial Pt/C in both electrochemical and practical fuel cell tests.
Drawings
FIG. 1 shows Pt prepared in example 1 of the present invention36TEM image of Co/C catalyst.
FIG. 2 shows Pt prepared in example 1 of the present invention36EDS linear scan of Co/C catalyst.
FIG. 3 shows Pt prepared in example 1 of the present invention36Graph comparing the performance of the Co/C catalyst with that of the 20% Pt/C (JM) catalyst before and after 1500 cycles of half-cell acceleration decay.
FIG. 4 shows Pt prepared in example 1 of the present invention36Graph comparing the performance (I-V curve) of Co/C catalyst (4a) to that of 20% Pt/C (jm) catalyst (4b) before and after 3000 full cell accelerated decay.
FIG. 5 shows Pt prepared in example 2 of the present invention22TEM image of Ni alloy nano catalyst.
FIG. 6 shows Pt prepared in example 2 of the present invention22Cyclic Voltammetry (CV) profiles of Ni/C alloy catalyst versus Johnson Matthey 20% Pt/C (JM) catalyst.
FIG. 7 shows Pt prepared in example 2 of the present invention22Oxygen reduction polarization (ORR) plots of Ni/C alloy catalyst versus Johnson Matthey 20% Pt/C (JM) catalyst.
FIG. 8 shows Pt prepared in example 3 of the present invention30TEM image of Cu/C alloy catalyst.
FIG. 9 shows Pt prepared in example 4 of the present invention88TEM image of Fe/C alloy catalyst.
Detailed Description
Example 1
(1) H is to be2PtCl6·6H2O and CoCl2·6H2O was dissolved in 2ml of deionized water at a Pt to Co atomic ratio of 1: 2. Stirring to mix them uniformly.
(2) Adding carbon black XC-72 into ethylene glycol, and performing ultrasonic dispersion uniformly.
(3) Stirring the dispersion at room temperature for 30min, introducing N during stirring2Forming an inert atmosphere of the reaction system;
(4) adding a reducing agent hydrazine hydrate into the dispersion, and then adding a Pt and Co precursor mixed solution to ensure that the total concentration of Pt and Co elements in the system is 3mmol/L, and the molar concentration of the reducing agent is 10 times of the total molar concentration of the Pt and Ni elements. Stirred at room temperature for 6 h.
(5) Adding 2mol/L dilute nitric acid into a mixed solution of ethanol and deionized water to ensure that the pH of the mixed solution is approximately equal to 2, and washing the catalyst by using the mixed solution.
(6) Drying the catalyst at 80 ℃ for 10h in vacuum to obtain Pt36Co/C catalyst, the actual Pt to Co atomic ratio is 36: 1.
FIG. 1 is a TEM image of the Pt-Co alloy nanoparticles of this example, showing that Pt-Co has a smaller particle size and a uniform distribution on the carbon support.
FIG. 2 is an EDS linear scan of Pt-Co alloy nanoparticles prepared in this example, which reveals the presence of trace Co elements and Pt shell structures in the Pt-Co alloy
FIG. 3 shows Pt prepared according to an example of the present invention36Graph comparing the performance of the Co/C catalyst with that of the 20% Pt/C (JM) catalyst before and after 1500 cycles of half-cell acceleration decay. Scanning speed 50mV s-1And tested at 25 ℃. As can be seen from the figure, Pt36The half-cell performance and stability of the Co/C catalyst was higher than commercial Pt/C.
FIG. 4 shows Pt prepared in this example36Graph comparing the performance (I-V curve) of the Co/C catalyst with that of the 20% Pt/C (jm) catalyst before and after 3000 cycles of full cell accelerated decay. Scanning speed 100mV s-1Test at 65 ℃. As can be seen from the figure, Pt36Full cell performance of Co/C catalystAnd stability higher than commercial Pt/C.
Example 2
(1) H is to be2PtCl6·6H2O and NiCl2·6H2O was dissolved in 2ml of deionized water at a Pt to Ni atomic ratio of 3: 1. Stirring to mix them uniformly.
(2) Adding carbon black XC-72 into ethylene glycol, and uniformly dispersing by ultrasonic;
(3) stirring the dispersion at room temperature for 40min, introducing N during stirring2Forming an inert atmosphere of the reaction system;
(4) adding reducing agent sodium borohydride into the dispersion, and then adding Pt and Ni precursor mixed solution, so that the total molar concentration of Pt and Ni elements in the system is 3.6mmol/L, and the molar concentration of the reducing agent is 18.5 times of the total molar concentration of the Pt and Ni elements. Stirred at room temperature for 3 h.
(5) Adding 2mol/L dilute nitric acid into a mixed solution of ethanol and deionized water to ensure that the pH of the mixed solution is approximately equal to 3, and washing the catalyst by using the mixed solution.
(6) The catalyst was dried in vacuo at 60 ℃ for 12h to give the product.
FIG. 5 shows Pt prepared in this example22TEM image of Ni alloy nanoparticles. The average particle diameter of the particles was 1.5 nm.
FIG. 6 shows Pt prepared in this example22Cyclic Voltammetry (CV) profiles of Ni/C alloy catalyst versus Johnson Matthey 20% Pt/C (JM) catalyst. The solution is N2Saturated 0.1M HClO4Scanning speed of 50mVs-1And testing at room temperature. Compared with Pt/C (JM), the reduction peak potential of the oxide on the surface of the Pt alloy is shifted positively, which shows that the oxide on the surface of the Pt alloy is easier to remove, so that the reaction rate of ORR is accelerated.
FIG. 7 shows Pt prepared in this example22Oxygen reduction polarization (ORR) plots of Ni/C alloy catalyst versus Johnson Matthey 20% Pt/C (JM) catalyst. The solution is O2Saturated 0.1M HClO4Scanning speed of 10mVs-1Forward sweep, RDE speed 1600rpm, room temperature test. As can be seen from the oxygen reduction curve, the half-wave potential of the Pt-Ni/C alloy is higher than that of Pt/C (JM).
Example 3
(1) H is to be2PtCl6·6H2O and Cu (NO)3)2Dissolved in 2ml of deionized water with an atomic ratio of Pt to Cu of 1: 3. Stirring to mix them uniformly.
(2) Adding carbon black XC-72 into ethylene glycol, and performing ultrasonic dispersion uniformly.
(3) Stirring the dispersion liquid for 30min at room temperature, and introducing Ar during stirring to form an inert atmosphere of a reaction system.
(4) And adding a reducing agent ascorbic acid into the dispersion, and then adding a Pt and Cu precursor mixed solution, so that the total concentration of Pt and Cu elements in the system is 5mmol/L, and the molar concentration of the reducing agent is 15 times of the total molar concentration of the Pt and Cu elements. The mixture was stirred at 80 ℃ for 3 h.
(5) Adding 2mol/L dilute nitric acid into a mixed solution of ethanol and deionized water to ensure that the pH of the mixed solution is approximately equal to 2, and washing the catalyst by using the mixed solution.
(6) The catalyst was dried under vacuum at 40 ℃ for 24h to give the product.
FIG. 8 shows Pt prepared in this example30TEM photograph of Cu alloy nanoparticles. The average particle diameter of the particles was 1.6nm
Example 4
(1) H is to be2PtCl6·6H2O and FeCl3·6H2O was dissolved in 2ml of deionized water at a Pt to Fe atomic ratio of 1: 10. Stirring to mix them uniformly.
(2) Adding carbon nano tube into polyethylene glycol, and uniformly dispersing by ultrasonic.
(3) Stirring the dispersion liquid at room temperature for 60min, and introducing Ar during stirring to form an inert atmosphere of a reaction system.
(4) And adding a reducing agent ascorbic acid into the dispersion, and then adding a Pt and Fe precursor mixed solution, so that the total concentration of Pt and Fe elements in the system is 10mmol/L, and the molar concentration of the reducing agent is 20 times of the total molar concentration of the Pt and Fe elements. Stirring was carried out at 140 ℃ for 12 h.
(5) Adding 2mol/L dilute nitric acid into a mixed solution of ethanol and deionized water to ensure that the pH of the mixed solution is approximately equal to 2, and washing the catalyst by using the mixed solution.
(6) The catalyst was dried under vacuum at 100 ℃ for 8h to give the product.
FIG. 9 shows Pt prepared in this example88TEM photograph of Fe alloy nanoparticles. The average particle size of the particles was 1.7 nm.
Example 5
(1) KPtCl4、Ni(NO3)2And Mo (NO)3)2Dissolving the alloy in 2ml of deionized water, wherein the atomic ratio of Pt to Ni and Mo is 5: 1: 1. stirring to mix them uniformly.
(2) Adding carbon nano tubes into glycerol, and uniformly dispersing by ultrasonic.
(3) Stirring the dispersion at room temperature for 60min, introducing N during stirring2And forming an inert atmosphere of the reaction system.
(4) Adding a reducing agent citric acid into the dispersion, and then adding a Pt and Mo precursor mixed solution to ensure that the total concentration of Pt, Ni and Mo elements in the system is 1mmol/L, and the molar concentration of the reducing agent is 10 times of the total molar concentration of the Pt, Ni and Mo elements. Stirring was carried out at 120 ℃ for 8 h.
(5) Adding 2mol/L dilute nitric acid into a mixed solution of ethanol and deionized water to ensure that the pH of the mixed solution is approximately equal to 3, and washing the catalyst by using the mixed solution.
(6) The catalyst was dried under vacuum at 70 ℃ for 24h to give the product.
Claims (10)
1. A preparation method of a non-noble metal modified platinum-based catalyst is characterized by comprising the following steps,
1) preparing a mixed solution of a Pt precursor and a non-noble metal precursor by using deionized water, and uniformly stirring; in the mixed solution, the atomic ratio of Pt to non-noble metal is 1:30-30: 1;
2) adding a carrier into high-viscosity alcohol, and performing ultrasonic dispersion to obtain a dispersion liquid;
3) the dispersion was stirred at room temperature and N was added2Or Ar is over 30min to form inert dispersion liquid;
4) adding a reducing agent into the inert dispersion liquid, then adding the mixed solution obtained in the step (1) to form a reaction system, and then reacting at 0-160 ℃ for 0.5-24 h; the total molar concentration of Pt and non-noble metal elements in the reaction system is 0.1-20mmol/L, and the molar concentration of the reducing agent is 1-100 times of the total molar concentration of the Pt and non-noble metal elements;
5) centrifugally washing, namely washing by using a mixture of ethanol and deionized water and adding a proper amount of dilute nitric acid, and then drying in vacuum at 40-100 ℃ for 6-24h to obtain the catalyst; the non-noble metal is Fe, Co, Ni, Cu, Mn, Mo, Cr.
2. The production method according to claim 1, wherein the Pt precursor is a nitrate, an amine complex, a hydrohalic acid, or a hydrohalic acid salt of Pt; the non-noble metal precursor is nitrate, sulfate, halide, amine complex, halogen acid or halogen acid salt of corresponding metal; the high viscosity alcohol is ethylene glycol, polyethylene glycol and glycerol; the carrier is conductive carbon black, carbon nano tubes, graphene, carbon nano, polyaniline, polypyrrole, polydopamine, TiO2、SnO2、WO3At least one of metal carbide and metal nitride.
3. The method of claim 1, wherein the reducing agent is hydrazine hydrate, tetrabutyl borohydride, citric acid, sodium citrate, ascorbic acid.
4. The process according to claim 1, wherein the reaction temperature in the step 4) is 25 to 90 ℃ with stirring.
5. The process according to claim 1 or 4, wherein the reaction time in step 4) is 3 to 16 hours with stirring.
6. The process according to claim 1, wherein in step 5), the total molar concentration of Pt and non-noble metal elements is 0.5-10 mmol/L.
7. A catalyst prepared by the process of claim 1, wherein: the catalyst is in a supported core-shell structure, and the supported object is in a core-shell structure; the core of the core-shell structure is an alloy of Pt and non-noble metal; the shell of the core-shell structure is Pt; the shape of the core-shell structure is spherical nano particles with the particle size of 1-3 nm.
8. The catalyst of claim 7, wherein: in the catalyst, the atomic ratio of Pt to non-noble metal is more than 10.
9. The catalyst of claim 7, wherein: the catalyst has a shell of 2-5 layers.
10. Use of the catalyst of claim 7 in a low temperature fuel cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112201798A (en) * | 2020-09-01 | 2021-01-08 | 深圳航天科技创新研究院 | Metal catalyst, mass preparation method thereof and fuel cell |
| CN112838227A (en) * | 2021-01-25 | 2021-05-25 | 中国科学院大连化学物理研究所 | Anti-reverse anode Pt/WO of proton exchange membrane fuel cell3-Mn catalyst and preparation method thereof |
| WO2021104106A1 (en) * | 2019-11-28 | 2021-06-03 | 深圳先进技术研究院 | Graphene-supported platinum-based alloy nanoparticle catalyst and preparation method therefor |
| CN113097502A (en) * | 2021-03-22 | 2021-07-09 | 青岛创启新能催化科技有限公司 | Preparation method of carbon-supported platinum catalyst with nitrogen-doped carbon as carrier |
| CN113198489A (en) * | 2021-04-02 | 2021-08-03 | 常熟氢能源研究院有限公司 | Preparation method of platinum-series high-entropy alloy catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| CN105680054A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
| CN108075143A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of loaded PtCu nano hollow structures catalyst |
-
2018
- 2018-11-30 CN CN201811460090.7A patent/CN111261886A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| CN105680054A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
| CN108075143A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of loaded PtCu nano hollow structures catalyst |
Non-Patent Citations (1)
| Title |
|---|
| XUEJUN TANG，ET AL.: "Anchoring ultrafine Pt nanoparticles on the 3D hierarchical self-assembly of graphene/functionalized carbon black as a highly efficient oxygen reduction catalyst for PEMFCs", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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| CN113437311B (en) * | 2021-05-24 | 2022-07-19 | 上海大学 | Preparation method of Pt-M spherical catalyst for fuel cell |
| CN113437311A (en) * | 2021-05-24 | 2021-09-24 | 上海大学 | Preparation method of Pt-M spherical catalyst for fuel cell |
| CN113555573A (en) * | 2021-07-26 | 2021-10-26 | 内蒙古科技大学 | Catalyst and preparation method and application thereof |
| CN113903927A (en) * | 2021-09-16 | 2022-01-07 | 昆明贵研新材料科技有限公司 | Method for preparing N-rGO supported PtCu alloy nano catalyst |
| CN115846675A (en) * | 2022-11-08 | 2023-03-28 | 广东省科学院资源利用与稀土开发研究所 | Binary metal alloy catalyst and preparation method and application thereof |
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